Second Edition

REMEDIATION
ENGINEERING
Design Concepts
Second Edition

REMEDIATION
ENGINEERING
Design Concepts

Suthan S. Suthersan
John Horst
Matthew Schnobrich
Nicklaus Welty
Jeff McDonough

Boca Raton London New York

CRC Press is an imprint of the

Taylor & Francis Group, an informa business
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Library of Congress Cataloging‑in‑Publication Data

Names: Suthersan, Suthan S., author.

Title: Remediation engineering : design concepts / Suthan S. Suthersan, John
Horst, Matthew Schnobrich, Nicklaus Welty, and Jeff McDonough.
Description: Second edition. | Boca Raton : Taylor & Francis, CRC Press,
2017. | Includes bibliographical references and index.
Identifiers: LCCN 2016032437 | ISBN 9781498773270 (hardcover : alk. paper)
Subjects: LCSH: Soil remediation. | Groundwater--Purification. | Hazardous
waste site remediation.
Classification: LCC TD878 .S88 2017 | DDC 628.5/5--dc23
LC record available at https://lccn.loc.gov/2016032437

Visit the Taylor & Francis Web site at

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 This book is dedicated to the memory of Steven Bruce Blake (1956–2016), a towering
influence in all our professional lives and whose support, motivation, and continuous
encouragement enabled all of us to accomplish our dreams individually and collectively.

This book is the culmination of a long, demanding, but surely worthwhile and exciting,
journey. My wife, Sumathy, and children, Shauna and Nealon, have been a source of love,
support, encouragement, and strength all these years, and for that I am so grateful.

—Suthan Suthersan
In moments like this, you realize how deeply you rely on those you love and who love you
back—that is the true foundation of happiness, strength, and courage. To my wife, Alison, who
is an unwavering source of light in my life, I am so incredibly blessed to have you at my side.
To Lorelei and Ahren, who every day fill me with an unfathomable sense of joy and pride.

—John Horst
Life is a series of banks and rivers, with boatmen to take us across. Each passage is a new journey
marked by guides, comrades, and friends—each contributing to the voyage. None have been more
important than my wife, Maria, who has been a cheerleader and an advocate. To our boys, Macpherson,
Patrick and Peter, may your own passages be as enjoyable as mine and your gratitude to others as deep.

—Matt Schnobrich
To Katie, Holden, Eve, and Miles for being the music makers in my life and making me smile
every day. And to my parents for taking me on all those rock-collecting hikes growing up.

—Nicklaus Welty
To my Laura, who is a beacon of love, support, patience, and resiliency, and to
our son, Grayson Giuseppe, who we fully anticipate will understand the technical
concepts within this book but never understand the depths of our love for him.

—Jeff McDonough
Contents
Foreword....................................................................................................................................................................................xvii
Preface........................................................................................................................................................................................xix
Acknowledgments.......................................................................................................................................................................xxi
Authors......................................................................................................................................................................................xxiii

Chapter 1 Remediation Engineering: State of the Practice...................................................................................................... 1

1.1 Introduction................................................................................................................................................... 1
1.1.1 Growth of an Industry...................................................................................................................... 1
1.1.2 Technical Discipline to Practice....................................................................................................... 3
1.1.3 Advances in Complementary Disciplines........................................................................................ 5
1.1.3.1 Advances in Remediation Hydrogeology......................................................................... 5
1.1.3.2 Advances in Environmental Microbiology....................................................................... 8
1.1.3.3 Environmental Geochemistry........................................................................................... 9
1.1.3.4 Geophysical Methods..................................................................................................... 10
1.1.4 Role of Remediation Engineer....................................................................................................... 11
1.2 Evolution and Maturation of Technologies.................................................................................................. 13
1.2.1 Timeline: 1980s to 2010s................................................................................................................ 14
1.2.1.1 Regulatory Influences on Technology Evolution............................................................ 14
1.2.1.2 Pump and Treat to In Situ............................................................................................... 15
1.3 Regulatory Framework................................................................................................................................ 16
1.3.1 Evolving Regulatory Influence....................................................................................................... 17
1.3.2 Evolution of Cleanup Standards..................................................................................................... 17
1.3.3 Risk-Based Approaches.................................................................................................................. 19
1.3.4 Technical Impracticability Considerations..................................................................................... 20
1.4 Importance of Health and Safety................................................................................................................ 20
1.4.1 Awareness and Current Trends...................................................................................................... 21
1.4.2 Potential Hazards........................................................................................................................... 22
1.4.3 Incorporation of Health and Safety into the Design Process......................................................... 22
1.5 Current Trends in Remediation................................................................................................................... 23
1.5.1 Sustainable (Green) Remediation................................................................................................... 24
1.5.2 Emerging Contaminants................................................................................................................ 26
1.5.3 Mine Reclamation.......................................................................................................................... 27
1.5.3.1 Mine Tailings.................................................................................................................. 27
1.5.3.2 Acid Mine Drainage....................................................................................................... 28
1.5.3.3 Mining Habitats.............................................................................................................. 28
1.5.4 Current Thinking on LNAPL Management................................................................................... 28
1.5.5 Protection of Water Resources....................................................................................................... 29
1.5.5.1 Environmental Concerns from Unconventional Energy Exploration............................. 30
References.............................................................................................................................................................. 31

Chapter 2 Contaminant Characteristics.................................................................................................................................. 33

2.1 Introduction................................................................................................................................................. 33
2.2 Molecular Structure of Compounds............................................................................................................ 33
2.2.1 Covalent Bonds.............................................................................................................................. 34
2.2.2 Polar Covalent Bonds..................................................................................................................... 35
2.2.3 Hydrogen Bonds............................................................................................................................. 37
2.2.4 Ionic Bonds..................................................................................................................................... 38
2.2.5 Van der Waals Interactions............................................................................................................ 39
2.2.6 Hydrophobic Bonds........................................................................................................................ 39
2.2.7 Dispersion Forces........................................................................................................................... 39

vii
viii Contents

2.3 Contaminant Types...................................................................................................................................... 40

2.3.1 Organic Contaminants................................................................................................................... 40
2.3.1.1 Halogenated Organics..................................................................................................... 41
2.3.1.2 Ketones........................................................................................................................... 42
2.3.1.3 Petroleum Hydrocarbons................................................................................................ 42
2.3.1.4 Polynuclear Aromatic Hydrocarbons............................................................................. 43
2.3.1.5 Fuel Oxygenates.............................................................................................................. 43
2.3.2 Inorganic Contaminants................................................................................................................. 43
2.3.2.1 Metals............................................................................................................................. 43
2.3.2.2 Nitrogen Compounds...................................................................................................... 44
2.3.2.3 Perchlorate...................................................................................................................... 45
2.3.3 Other Bulk Parameters................................................................................................................... 45
2.3.3.1 Total Petroleum Hydrocarbons....................................................................................... 45
2.3.3.2 Total Organic Carbon..................................................................................................... 46
2.3.3.3 Total Dissolved Solids ................................................................................................... 46
2.4 Properties of Contaminants......................................................................................................................... 46
2.4.1 Solubility........................................................................................................................................ 46
2.4.2 Vapor Pressure............................................................................................................................... 47
2.4.3 Henry’s Law Constant.................................................................................................................... 48
2.4.4 Density........................................................................................................................................... 48
2.4.5 Liquid Viscosity............................................................................................................................. 48
2.4.6 Fluid Properties.............................................................................................................................. 49
2.4.7 Sorption and Desorption Processes................................................................................................ 50
2.4.7.1 Adsorption...................................................................................................................... 50
2.4.7.2 Absorption...................................................................................................................... 51
2.4.7.3 Multicompartment Sorption Models.............................................................................. 51
2.4.7.4 Cation Exchange Capacity.............................................................................................. 53
2.5 Transport, Mobilization, and Partitioning in the Subsurface...................................................................... 54
2.5.1 Nonaqueous-Phase Liquids............................................................................................................ 54
2.5.1.1 NAPL Architecture......................................................................................................... 54
2.5.1.2 NAPL Saturation and Mobility...................................................................................... 55
2.5.1.3 NAPL Weathering.......................................................................................................... 56
2.5.2 Hydrodynamic Transport Processes.............................................................................................. 57
2.5.2.1 Solute-Based Transport.................................................................................................. 58
2.5.3 Volatilization and Transport in the Unsaturated Zone................................................................... 60
2.6 Transformation Processes............................................................................................................................ 61
2.6.1 Abiotic Transformation.................................................................................................................. 61
2.6.1.1 Oxidation and Reduction Reactions............................................................................... 62
2.6.1.2 Precipitation and Solubilization...................................................................................... 62
2.6.1.3 Hydrolysis....................................................................................................................... 62
2.6.2 Biological Transformation.............................................................................................................. 63
2.6.2.1 Microbial Oxidation....................................................................................................... 64
2.6.2.2 Microbial Reduction....................................................................................................... 64
2.6.2.3 Cometabolic Biodegradation.......................................................................................... 65
References.............................................................................................................................................................. 65

Chapter 3 Principles of Integrated Design.............................................................................................................................. 69

3.1 Introduction................................................................................................................................................. 69
3.2 Remediation Design Process....................................................................................................................... 69
3.2.1 Element 1: Define........................................................................................................................... 69
3.2.2 Element 2: Brainstorm................................................................................................................... 70
3.2.3 Element 3: Plan............................................................................................................................... 70
3.2.4 Element 4: Test............................................................................................................................... 71
3.2.5 Element 5: Refine........................................................................................................................... 71
3.2.6 Element 6: Deploy.......................................................................................................................... 71
Contents ix

3.3 Integrated Design: An Overview................................................................................................................. 72

3.4 Key Factors in Remediation Design............................................................................................................ 73
3.4.1 Health and Safety in Design........................................................................................................... 73
3.4.1.1 Hazard Identification and Critical Failure Analysis....................................................... 73
3.4.1.2 Hierarchy of Hazard Controls........................................................................................ 77
3.4.1.3 Response Planning.......................................................................................................... 78
3.4.2 Predesign Efforts............................................................................................................................ 79
3.4.2.1 Concepts and Definitions................................................................................................ 79
3.4.2.2 Thought Experiments..................................................................................................... 80
3.4.2.3 Real Experiments........................................................................................................... 82
3.4.2.4 Predesign Characterization............................................................................................. 87
3.4.3 Biogeochemical Considerations..................................................................................................... 87
3.4.3.1 Fouling of Wells and Equipment.................................................................................... 87
3.4.3.2 Porosity Reductions in the Aquifer................................................................................. 92
3.4.3.3 Secondary Water Quality Impacts.................................................................................. 95
3.4.3.4 Material Compatibility..................................................................................................101
3.4.4 Environmental Considerations..................................................................................................... 102
References............................................................................................................................................................ 103

Chapter 4 Remediation Hydrogeology.................................................................................................................................. 107

4.1 Introduction............................................................................................................................................... 107
4.2 Fundamental Concepts in Hydrogeology.................................................................................................. 107
4.2.1 Groundwater Flow........................................................................................................................ 107
4.2.1.1 Aquifers and Their Characteristics............................................................................... 107
4.2.1.2 Aquifer Building Processes, Heterogeneity, and Anisotropy........................................110
4.2.2 Contaminant Transport Processes.................................................................................................112
4.2.2.1 Advection.......................................................................................................................113
4.2.2.2 Dispersion and Diffusion...............................................................................................113
4.3 Evolution of Remediation Hydrogeology...................................................................................................113
4.3.1 Pre-1950s: The Water Supply Origins of Hydrogeology...............................................................113
4.3.2 1950s–1980s: Early Developments in Remediation Hydrogeology..............................................114
4.3.3 1980s–2000s: The First Generation of Remediation Hydrogeology.............................................114
4.3.4 2000s–Present: Remediation Hydraulics......................................................................................114
4.3.4.1 Heterogeneous Advection and Diffusion.......................................................................115
4.3.4.2 Stratigraphic Flux..........................................................................................................115
4.3.4.3 Flux-Focused Investigation and Remediation Strategies...............................................117
4.4 Site Characterization..................................................................................................................................118
4.4.1 Limitations of Traditional Site Investigation Methods.................................................................118
4.4.2 Smart Characterization: A New Way of Investigating Sites........................................................ 120
4.4.2.1 Permeability Characterization...................................................................................... 120
4.4.2.2 Concentration Mapping Tools...................................................................................... 123
4.4.2.3 Direct Flux Mapping.................................................................................................... 128
4.4.2.4 3D Visualization........................................................................................................... 129
4.5 Conceptual Site Models............................................................................................................................. 130
4.5.1 Elements of a Conceptual Site Model.......................................................................................... 130
4.5.1.1 Site History and Operations.......................................................................................... 130
4.5.1.2 Contaminants................................................................................................................ 130
4.5.1.3 Geology..........................................................................................................................131
4.5.1.4 Hydrogeology................................................................................................................131
4.5.2 Digital CSMs: The Next Frontier................................................................................................. 132
4.5.3 Using the CSM to Guide Investigation and Design and Optimize Remediation Systems........... 132
4.5.3.1 Case Study 1................................................................................................................. 132
4.5.3.2 Case Study 2................................................................................................................. 133
References............................................................................................................................................................ 135
x Contents

Chapter 5 Dynamic Groundwater Recirculation.................................................................................................................. 137

5.1 Introduction............................................................................................................................................... 137
5.2 A New Model of Contaminant Transport.................................................................................................. 137
5.3 Design Concepts and Remedial Strategies................................................................................................ 139
5.3.1 Pump and Treat............................................................................................................................ 140
5.3.2 Complex Heterogeneous Systems.................................................................................................147
5.4 Case Study 1: Former Reese Air Force Base............................................................................................ 149
5.4.1 Background.................................................................................................................................. 149
5.4.2 The First Step: Refinement of the Conceptual Site Model........................................................... 149
5.4.3 The Second Step: Optimization of the Existing Remedy............................................................ 151
5.4.4 The Third Step: Adaptive Implementation of a Revised Remedy Strategy................................. 151
5.4.4.1 Strategy......................................................................................................................... 151
5.4.4.2 DGR.............................................................................................................................. 152
5.4.4.3 In Situ Engineered Reductive Dechlorination.............................................................. 153
5.4.5 Performance Metrics.................................................................................................................... 155
5.4.5.1 Achieving the Cleanup Objectives............................................................................... 155
5.4.5.2 Demonstrating a Complete Cleanup............................................................................. 158
5.4.6 Conclusions and Lessons Learned............................................................................................... 158
5.5 DGR Design Concepts.............................................................................................................................. 159
5.6 Case Study 2: Commercial Property and Metropolitan Setting.................................................................161
5.6.1 Conceptual Site Model..................................................................................................................161
5.6.2 Design Considerations.................................................................................................................. 163
5.6.2.1 Source Zone.................................................................................................................. 163
5.6.2.2 Plume............................................................................................................................ 163
5.6.3 Implementation............................................................................................................................. 165
5.6.3.1 Plume Adaptive Approach and Performance Tracking................................................ 165
5.6.4 Site Closure and Lessons Learned............................................................................................... 166
5.7 Case Study 3: Refueling Pad..................................................................................................................... 167
5.7.1 Introduction.................................................................................................................................. 167
5.7.2 Geology and Hydrogeology......................................................................................................... 167
5.7.3 Summary of Soil and Groundwater Impacts................................................................................ 167
5.7.4 DGR Description.......................................................................................................................... 168
5.7.5 Groundwater Extraction and Reinjection......................................................................................170
5.7.6 DGR Performance and Results.....................................................................................................170
5.7.7 Summary and Conclusions............................................................................................................171
References............................................................................................................................................................ 172

Chapter 6 Injected Reagent–Based Remedies.......................................................................................................................173

6.1 Introduction to In Situ Reactive Zones.......................................................................................................173
6.1.1 Background...................................................................................................................................173
6.1.1.1 IRZ Definition...............................................................................................................173
6.1.1.2 Types of IRZ Reactions.................................................................................................174
6.1.1.3 Contaminant Considerations.........................................................................................175
6.1.2 Key Parameters for Design...........................................................................................................176
6.1.2.1 Volume–Radius Relationship........................................................................................176
6.1.2.2 Injection Delivery Methods...........................................................................................178
6.1.2.3 Injection Pressure Considerations................................................................................ 180
6.1.2.4 Reagent Types and Selection Considerations............................................................... 182
6.1.2.5 Injection Frequency...................................................................................................... 183
6.1.3 Injection Tests and Tracer Studies................................................................................................ 184
6.1.3.1 Tracer Types................................................................................................................. 185
6.1.3.2 Test Layout and Monitoring Programs......................................................................... 186
6.1.3.3 Mobile Porosity and Velocity Interpretation................................................................ 187
Contents xi

6.1.4 Injection Configurations............................................................................................................... 190

6.1.4.1 Pulse and Drift versus Recirculation............................................................................ 192
6.1.4.2 Large Plume Treatment: Barrier Spacing Design Considerations................................ 193
6.1.5 Performance Monitoring.............................................................................................................. 195
6.1.6 Enhanced NAPL Dissolution....................................................................................................... 196
6.2 In Situ Bioremediation............................................................................................................................... 199
6.2.1 Microbiology................................................................................................................................ 201
6.2.1.1 Types of Microbial Reactions....................................................................................... 202
6.2.1.2 Microbial Energetics..................................................................................................... 203
6.2.1.3 Microbial Analysis/Molecular Techniques.................................................................. 206
6.2.1.4 Biostimulation versus Bioaugmentation....................................................................... 209
6.2.1.5 Biofilms and Biofouling................................................................................................ 209
6.2.2 Aerobic Processes.........................................................................................................................211
6.2.2.1 Contaminant Types....................................................................................................... 213
6.2.2.2 Microorganisms............................................................................................................ 213
6.2.2.3 Oxygen Delivery Mechanisms......................................................................................217
6.2.2.4 Nutrient Addition.......................................................................................................... 220
6.2.2.5 Monitoring.................................................................................................................... 221
6.2.3 Anaerobic Processes.................................................................................................................... 221
6.2.3.1 Microbial Reduction..................................................................................................... 222
6.2.3.2 Anaerobic Oxidation..................................................................................................... 249
6.2.4 Cometabolic Degradation............................................................................................................. 255
6.3 In Situ Chemical Remediation.................................................................................................................. 257
6.3.1 Chemical Reactivity..................................................................................................................... 259
6.3.1.1 Oxidation States............................................................................................................ 259
6.3.1.2 Thermodynamics versus Kinetics................................................................................ 260
6.3.1.3 Reaction Mechanisms................................................................................................... 267
6.3.1.4 Geochemical Considerations........................................................................................ 270
6.3.2 Chemical Oxidation..................................................................................................................... 272
6.3.2.1 Radical Reactions......................................................................................................... 273
6.3.2.2 Reagent Loading and Geochemistry............................................................................ 275
6.3.2.3 Reagent Selection/Types............................................................................................... 285
6.3.3 Chemical Reduction..................................................................................................................... 304
6.3.3.1 Reagent Selection/Types............................................................................................... 305
References.............................................................................................................................................................311

Chapter 7 In Situ Treatment of Metals.................................................................................................................................. 323

7.1 Terminology.............................................................................................................................................. 323
7.2 Metals: An Overview................................................................................................................................ 325
7.2.1 Metal Bonding Characteristics..................................................................................................... 325
7.2.2 Heavy Metals................................................................................................................................ 326
7.2.3 Transition Elements...................................................................................................................... 326
7.2.4 Metals Characteristics Influencing Transport and Toxicity......................................................... 327
7.2.5 Regulatory Considerations........................................................................................................... 327
7.2.6 pE–pH Diagrams.......................................................................................................................... 328
7.2.7 A Need for Consistency in Equilibrium Constants...................................................................... 329
7.3 Geochemical Strategies for In Situ Treatment of Metals.......................................................................... 329
7.3.1 Direct Precipitation...................................................................................................................... 329
7.3.1.1 Chemical Methods.........................................................................................................331
7.3.1.2 Biological Methods....................................................................................................... 344
7.3.2 Sorption/Coprecipitation.............................................................................................................. 344
7.4 Strategic Considerations............................................................................................................................ 345
7.4.1 Geochemistry............................................................................................................................... 345
7.4.1.1 Solubility of the Targeted Mineral............................................................................... 345
7.4.1.2 Precipitate Formation and Inhibition............................................................................ 346
xii Contents

7.4.1.3 Mineral Comparisons................................................................................................... 358

7.4.1.4 The “Matrix Effect”..................................................................................................... 367
7.4.1.5 Hydration...................................................................................................................... 368
7.4.2 Technology Type.......................................................................................................................... 368
7.4.2.1 Reactive Zones.............................................................................................................. 369
7.4.2.2 Permeable Reactive Barriers........................................................................................ 373
7.4.2.3 Stabilization.................................................................................................................. 375
7.4.2.4 Extraction...................................................................................................................... 384
7.4.3 Analytical..................................................................................................................................... 387
7.4.3.1 Dissolved Metal Analysis............................................................................................. 388
7.4.3.2 Solid Metal Analysis..................................................................................................... 388
7.4.3.3 Operational (Functional) Analysis............................................................................... 396
7.4.4 Characteristics of Specific Metals................................................................................................ 397
7.4.4.1 Chromium..................................................................................................................... 397
7.4.4.2 Arsenic.......................................................................................................................... 398
7.4.4.3 Radionuclides............................................................................................................... 401
7.5 Permanence on In Situ Metals Treatment................................................................................................. 404
7.5.1 Sulfides......................................................................................................................................... 405
7.5.2 Element Re-oxidation................................................................................................................... 405
7.5.2.1 Chromium..................................................................................................................... 406
7.5.2.2 Uranium........................................................................................................................ 406
References............................................................................................................................................................ 407

Chapter 8 Sparging, Venting, and Vacuum-Enhanced Recovery..........................................................................................413

8.1 Soil Vapor Extraction.................................................................................................................................413
8.1.1 Governing Phenomena..................................................................................................................413
8.1.1.1 Contaminant Partitioning..............................................................................................413
8.1.1.2 Contaminant Properties.................................................................................................415
8.1.1.3 Soil Properties...............................................................................................................419
8.1.1.4 Airflow Characteristics................................................................................................. 421
8.1.2 Applicability................................................................................................................................. 424
8.1.2.1 Contaminant Applicability........................................................................................... 424
8.1.2.2 Site Characterization.................................................................................................... 424
8.1.3 System Design.............................................................................................................................. 425
8.1.3.1 Pilot Testing.................................................................................................................. 425
8.1.3.2 Design Approaches....................................................................................................... 428
8.1.3.3 Operational Considerations.......................................................................................... 432
8.1.4 Bioventing.................................................................................................................................... 433
8.1.4.1 Laboratory Testing........................................................................................................ 434
8.1.4.2 Design of Bioventing Systems...................................................................................... 435
8.1.4.3 In Situ Respiration Test................................................................................................. 436
8.1.5 Monitoring Requirements............................................................................................................ 437
8.1.6 Vapor Treatment Technologies..................................................................................................... 437
8.1.6.1 Thermal Oxidation....................................................................................................... 437
8.1.6.2 Catalytic Oxidation....................................................................................................... 439
8.1.6.3 Adsorption.................................................................................................................... 440
8.1.6.4 Condensation................................................................................................................ 443
8.1.6.5 Cost Considerations...................................................................................................... 443
8.2 In Situ Air Sparging.................................................................................................................................. 444
8.2.1 Governing Phenomena................................................................................................................. 444
8.2.1.1 In Situ Air Stripping..................................................................................................... 445
8.2.1.2 Direct Volatilization..................................................................................................... 446
8.2.1.3 Biodegradation.............................................................................................................. 446
8.2.2 Applicability................................................................................................................................. 446
8.2.2.1 Examples of Contaminant Applicability...................................................................... 446
8.2.2.2 Geologic Considerations............................................................................................... 447
Contents xiii

8.2.3 Description of the Process............................................................................................................ 447

8.2.3.1 Air Injection into Water-Saturated Soils...................................................................... 447
8.2.3.2 Mounding of Water Table............................................................................................. 448
8.2.3.3 Distribution of Airflow Pathways................................................................................. 449
8.2.3.4 Groundwater Mixing.................................................................................................... 449
8.2.4 System Design Parameters........................................................................................................... 450
8.2.4.1 Air Distribution (Zone of Influence)............................................................................ 450
8.2.4.2 Depth of Air Injection.................................................................................................. 452
8.2.4.3 Air Injection Pressure and Flow Rate.......................................................................... 452
8.2.4.4 Injection Mode (Pulsing and Continuous).................................................................... 453
8.2.4.5 Injection Well Construction.......................................................................................... 453
8.2.4.6 Contaminant Type and Distribution............................................................................. 454
8.2.5 Pilot Testing.................................................................................................................................. 454
8.2.6 Monitoring Considerations........................................................................................................... 456
8.2.7 Process Equipment....................................................................................................................... 456
8.2.7.1 Air Compressor or Air Blower..................................................................................... 456
8.2.7.2 Other Equipment........................................................................................................... 457
8.2.8 Biosparging.................................................................................................................................. 457
References............................................................................................................................................................ 458

Chapter 9 Soil Treatment...................................................................................................................................................... 461

9.1 Introduction............................................................................................................................................... 461
9.1.1 Screening Criteria........................................................................................................................ 461
9.1.2 Sorptive Processes........................................................................................................................ 462
9.2 Soil Excavation.......................................................................................................................................... 463
9.2.1 Ex Situ Soil Treatment................................................................................................................. 464
9.2.1.1 Disposal........................................................................................................................ 464
9.2.1.2 Incineration................................................................................................................... 465
9.2.1.3 Thermal Desorption...................................................................................................... 465
9.2.1.4 Land Farming and Biopiles.......................................................................................... 466
9.2.2 Design Considerations.................................................................................................................. 467
9.2.2.1 Soil Volume.................................................................................................................. 467
9.2.2.2 Soil Stability................................................................................................................. 467
9.3 In Situ Thermal Remediation.................................................................................................................... 467
9.3.1 Energy Input and Heating Mechanisms....................................................................................... 469
9.3.1.1 Conduction.................................................................................................................... 469
9.3.1.2 Convection.................................................................................................................... 469
9.3.1.3 Joule (Electrical Resistance) Heating........................................................................... 469
9.3.1.4 Combustion/Smoldering............................................................................................... 470
9.3.1.5 Radio Frequency or Microwave Heating...................................................................... 470
9.3.2 Energy Transport and Storage Mechanisms................................................................................ 470
9.3.2.1 Thermal Conductivity and Thermal Diffusivity.......................................................... 470
9.3.2.2 Heat Capacity................................................................................................................ 471
9.3.2.3 Heat of Vaporization..................................................................................................... 471
9.3.2.4 Heat of Condensation.................................................................................................... 471
9.3.3 Treatment and Removal Mechanisms.......................................................................................... 472
9.3.3.1 Vaporization and Volatilization.................................................................................... 472
9.3.3.2 Preferential Partitioning into Vapor Phase................................................................... 472
9.3.3.3 Boiling at NAPL–Water Interface: Formation of Low-Boiling Point Azeotropes....... 472
9.3.3.4 Fluid Property Changes................................................................................................ 473
9.3.3.5 Temperature-Activated Autodecomposition Reactions................................................ 473
9.3.4 Thermal Treatment Technologies................................................................................................. 474
9.3.4.1 Electrical Resistance Heating....................................................................................... 474
9.3.4.2 Thermal Conduction Heating....................................................................................... 476
9.3.4.3 Steam-Enhanced Extraction......................................................................................... 477
xiv Contents

9.3.4.4 Smoldering Combustion............................................................................................... 479

9.3.4.5 Low-Temperature In Situ Thermal Remediation.......................................................... 479
9.3.4.6 Thermal Technologies Available in North America..................................................... 480
9.3.5 Thermal Technology Selection and Design Considerations........................................................ 481
9.3.5.1 Target Treatment Temperature..................................................................................... 482
9.3.5.2 Mass and Energy Balance............................................................................................ 483
9.3.5.3 Hydraulic and Pneumatic Control................................................................................ 483
9.3.5.4 Design Considerations.................................................................................................. 483
9.3.6 Thermal Remediation-Performance Monitoring......................................................................... 485
9.3.6.1 Thermal Well Field Monitoring.................................................................................... 485
9.3.6.2 Remote Monitoring....................................................................................................... 485
9.3.6.3 Process Monitoring....................................................................................................... 485
9.4 In Situ Soil Mixing.................................................................................................................................... 486
9.4.1 Introduction.................................................................................................................................. 486
9.4.2 Planning for Implementation........................................................................................................ 487
9.4.2.1 Reagent Selection.......................................................................................................... 488
9.4.2.2 Design Goals................................................................................................................. 489
9.4.2.3 ISS Treatability Challenges.......................................................................................... 490
9.4.3 Implementation Methods.............................................................................................................. 490
9.4.3.1 Deep Soil Mixing......................................................................................................... 491
9.4.3.2 Shallow Soil Mixing Methods...................................................................................... 491
9.4.3.3 Other Soil Mixing Methods.......................................................................................... 491
9.4.3.4 Implementation Challenges.......................................................................................... 492
9.4.4 ISS Case Studies........................................................................................................................... 493
9.4.4.1 Case Study 1: Former MGP Site (New York)............................................................... 493
9.4.4.2 Case Study 2: Former Creosote Facility (Idaho).......................................................... 494
9.4.5 In Situ Treatment (IST)................................................................................................................ 495
9.4.5.1 Chemical Oxidants....................................................................................................... 496
9.4.5.2 In Situ Soil Mixing with Zerovalent Iron and Clay...................................................... 496
9.5 Phytotechnologies...................................................................................................................................... 497
9.5.1 Chemicals in the Soil–Plant System............................................................................................ 498
9.5.1.1 Metals........................................................................................................................... 498
9.5.1.2 Organics........................................................................................................................ 499
9.5.2 Types of Phytotechnologies.......................................................................................................... 500
9.5.2.1 Phytosequestration........................................................................................................ 501
9.5.2.2 Rhizodegradation......................................................................................................... 501
9.5.2.3 Phytohydraulics............................................................................................................ 503
9.5.2.4 Phytoextraction............................................................................................................. 504
9.5.2.5 Phytodegradation.......................................................................................................... 505
9.5.2.6 Phytovolatilization........................................................................................................ 507
9.5.3 Phytoremediation Design............................................................................................................. 508
9.5.3.1 Contaminant Levels...................................................................................................... 508
9.5.3.2 Plant Selection.............................................................................................................. 509
9.5.3.3 Treatability.................................................................................................................... 509
9.5.3.4 Irrigation, Agronomic Inputs, and Maintenance.......................................................... 509
References............................................................................................................................................................ 509

Chapter 10 Reactive Walls.......................................................................................................................................................511

10.1 Reactive Barriers........................................................................................................................................511
10.2 Technology Overview.................................................................................................................................511
10.2.1 Configurations...............................................................................................................................511
10.2.1.1 Continuous Permeable Reactive Barrier....................................................................... 512
10.2.1.2 Funnel and Gate Permeable Reactive Barrier...............................................................513
Contents xv

10.2.2 Constructability Considerations....................................................................................................516

10.2.2.1 Components...................................................................................................................516
10.2.2.2 Installation Methods......................................................................................................518
10.2.2.3 Limitations of PRB Construction................................................................................. 522
10.2.3 Performance Considerations........................................................................................................ 522
10.2.3.1 Hydraulic Capture......................................................................................................... 522
10.2.3.2 Residence Time............................................................................................................. 523
10.2.3.3 Reactivity...................................................................................................................... 523
10.3 Treatment Processes.................................................................................................................................. 523
10.3.1 Reaction Mechanisms.................................................................................................................. 523
10.3.1.1 Physical Reaction Mechanism...................................................................................... 523
10.3.1.2 Chemical Reaction Mechanism.................................................................................... 526
10.3.1.3 Biological Reactive Mechanism................................................................................... 528
10.3.2 Reaction Considerations............................................................................................................... 529
10.3.2.1 Treatment Reagent Reactivity (Durability and Stability)............................................. 530
10.3.2.2 Treatment Reagent Availability (Cost)......................................................................... 530
10.3.2.3 Treatment Reagent Compatibility (Hydrogeological, Geochemical, and
Construction)............................................................................................................ 531
10.3.3 Treatment Reagent Types..............................................................................................................531
10.3.3.1 ZVI................................................................................................................................531
10.3.3.2 Mineral Treatment Reagent...........................................................................................531
10.3.3.3 Organic Treatment Reagent.......................................................................................... 532
10.4 Key Design Parameters............................................................................................................................. 533
10.4.1 Hydraulics.................................................................................................................................... 533
10.4.2 Treatment Kinetics and Minimum Residence Time.................................................................... 534
10.4.3 Contaminant Distribution and Mass Flux.................................................................................... 535
10.4.4 Longevity...................................................................................................................................... 535
10.5 Performance Monitoring........................................................................................................................... 535
10.5.1 Performance Objectives and Demonstration Considerations....................................................... 536
10.5.2 Secondary Water-Quality Concerns............................................................................................ 537
10.6 Performance Case Studies......................................................................................................................... 537
10.6.1 Case Study 1: GETS Replacement with a ZVI PRB.................................................................... 538
10.6.2 Case Study 2: Anaerobic Biological PRB for Perchlorate Treatment (Biowall).......................... 539
10.6.3 Case Study 3: Long-Term Evaluation of a ZVI PRB in Elizabeth City, NC................................ 543
References............................................................................................................................................................ 544

Chapter 11 Emerging Trends in Environmental Remediation............................................................................................... 549

11.1 Influence of Big Data on Environmental Remediation............................................................................. 549
11.1.1 Remediation-Related Data Management..................................................................................... 549
11.1.2 Types of Remediation Big Data....................................................................................................551
11.1.2.1 Sustainability (Green Remediation) Data..................................................................... 553
11.1.2.2 Smart Investigation....................................................................................................... 553
11.1.2.3 Tracer Testing Data....................................................................................................... 553
11.1.2.4 Advent of Sensors......................................................................................................... 554
11.1.3 Opportunities for Gaining Insightful Knowledge........................................................................ 554
11.1.3.1 Stratigraphic Flux......................................................................................................... 554
11.1.3.2 Developing and Validating Benchmarks...................................................................... 555
11.1.3.3 Natural Attenuation of 1,4-Dioxane............................................................................. 556
11.1.3.4 LNAPL Management.................................................................................................... 556
11.1.3.5 Realistic Values of Porosities........................................................................................ 557
11.1.3.6 Large Plume Management............................................................................................ 557
11.1.4 The Future.................................................................................................................................... 559
xvi Contents

11.2 Large Contaminated Groundwater Plumes Can Be Cleaned Up.............................................................. 560

11.2.1 Introduction.................................................................................................................................. 560
11.2.2 Back Diffusion Can Be Overcome............................................................................................... 561
11.2.3 Importance of Combined Remedies for Cleaning Up a Large Plume......................................... 562
11.2.4 Unique Success............................................................................................................................. 563
11.3 Managing Emerging Contaminants.......................................................................................................... 563
11.3.1 Background.................................................................................................................................. 564
11.3.2 Emerging Contaminants Currently in the Spotlight.................................................................... 566
11.3.2.1 Lessons Learned from the Past.................................................................................... 566
11.3.2.2 1,4-Dioxane................................................................................................................... 567
11.3.2.3 PFAS............................................................................................................................. 567
11.3.2.4 Developing Advancements in Management of 1,4-Dioxane and PFAS....................... 569
11.3.2.5 Current State of the Science......................................................................................... 575
11.4 Managing Vapor Intrusion Concerns........................................................................................................ 575
11.5 Management of Coal Combustion Residuals............................................................................................ 577
11.5.1 Coal Ash Disposal Practices........................................................................................................ 577
11.5.2 CCR Regulations.......................................................................................................................... 577
11.5.3 Pond Closure................................................................................................................................ 578
11.5.4 Recycling...................................................................................................................................... 578
11.6 Nanomaterials in the Environment........................................................................................................... 578
11.6.1 Natural Particles........................................................................................................................... 579
11.6.2 Fate of Nanomaterials in the Environment.................................................................................. 579
11.7 Managing E-Wastes................................................................................................................................... 580
11.7.1 Contamination from E-Wastes..................................................................................................... 581
References............................................................................................................................................................ 581

Appendix: Physical Properties of Common Environmental Contaminants...................................................................... 583

Index.......................................................................................................................................................................................... 593
Foreword
I am extremely honored to have been asked to write the
foreword for Remediation Engineering: Design Concepts.
The vision, passion, and technical excellence the authors
have brought to this second edition reinforce their position
at the forefront of innovation in this critical and rapidly
evolving field.
I first met Dr. Suthan Suthersan and his team in 2015, when
I joined Arcadis as chief operating officer. What had drawn
me to this industry and to this firm in particular was its com-
mitment to improving the quality of life. It is truly inspira-
tional, a point of pride and an objective I strive toward as the
end result of my labors.
Dr. Suthersan, who serves as Arcadis’ chief technical offi-
cer; John Horst, executive director of Technical Knowledge
and Innovation (TKI); Matthew Schnobrich, director of
Remediation Services; principal geologist Nicklaus Welty;
and principal environmental engineer Jeffrey McDonough—
all globally recognized thought leaders in their fields—
immediately impressed me with their dedication to practical
innovation. Never satisfied with the status quo, they are tire-
less pioneers in the development and application of cutting-
edge solutions to remediation challenges.
The first edition of Remediation Engineering, published
in 1996, broke the mold on conventional approaches to soil
and groundwater remediation. As a model of innovation, it
challenged accepted, long-term, industry-wide paradigms
and dramatically impacted regulatory trends by introducing
highly efficient and cost-effective technologies, most of which
relied on natural processes. It was quickly integrated into uni-
versity curricula, focused the environmental industry on the
practice of in situ remediation, and established Arcadis as the
leading remediation firm in the industry.
This comprehensive second edition fortifies that leadership
position. Dr. Suthersan and his team explore both the history
and the future of remediation. How can science address the
challenges of persistent and emerging contaminants? How is
the role of remediation engineers evolving to define and exem-
plify environmental stewardship? How can we work to align
historical regulatory guidelines with advanced processes for
green remediation and other worthy, cost-effective solutions?
How can we work with owners and potentially responsible
parties to sustainably and realistically return contaminated
sites to beneficial use? In short, how can we leave a last-
ing legacy that improves the quality of life for generations
to come?
The term “remediation engineering” was coined by Dr.
Suthersan and Steve Blake, a former CEO of Arcadis’ North
American operations. Together, they undertook a journey
that created the foundation for our firm and forged the path
for our industry. By combining their efforts to advance the
pure science and innovation of remediation, to advocate for
regulatory alignment with realistic environmental conditions
and human health needs, and to understand the reality of the
business and residential communities, they struck the per-
fect balance of scientific achievement, ecological care, and
bottom-line investment.
Steve Blake, a great friend to the authors of this book,
passed away this year. When we face loss like this, it brings on
a period of reflection, where we take stock of our contributions
and wonder if what we have achieved has made a difference.
The authors of this book will never have reason to be con-
cerned when that question is asked of them. They are admired
and respected experts in their chosen fields and leaders and
advocates for the interests of their fellow human beings. Their
contributions as scientists and men will endure and be looked
upon with gratitude and grace for decades to come.
I thank them for their dedication to—and passion for—
the field of remediation engineering, for their endless quest
to develop breakthrough technologies, for their commitment
to health and safety, and for sharing their expertise through
this book. I trust it will not only inspire and guide engineers,
scientists, regulators, students, and researchers but also truly
advance our shared mission of improving the quality of life—
today, tomorrow, and long into the future.
Joachim Ebert
Chief Executive Officer
Arcadis, North America
xvii
Preface
This second edition of Remediation Engineering: Design
Concepts provides a comprehensive guide to design and
implementation of the complete spectrum of remediation
technologies for all major classes of subsurface environ-
mental contamination. The types of contaminants covered
include hydrophobic and miscible organics, metals and other
high-solubility inorganics, and radionuclides. It teaches a
wide range of fundamentals that underlie the deployment of
cutting-edge but cost-effective solutions, including but not
limited to contaminant characteristics, distribution and trans-
port patterns, and chemical and biological mechanisms that
are used to achieve oxidation, reduction, and precipitation of
target contaminants. We believe this book provides remedia-
tion engineers and scientists the tools and extensive cover-
age to design, implement, and manage remediation systems
through the entire life cycle of the projects.
The first chapter covers the evolution of the remediation
industry itself over the last three decades. The development of
remediation engineering as a stand-alone technical discipline
is discussed from its infancy across multiple facets. The influ-
ence of regulatory developments, technological advances,
merging of complementary disciplines, health and safety con-
siderations, and emerging industry trends are discussed with
penetrating insight. Current and future issues and trends that
will have major impacts on further evolution of our indus-
try are covered later in this book. These trends include influ-
ence of big data, large contaminated groundwater plumes,
emerging contaminants and impacts on water supplies, and
impacts from unconventional energy exploration and vapor
intrusion. Most chapters are developed to meet current mar-
ket demands—to meet regulatory compliance in shorter time
frames at reduced costs while relying upon the most techni-
cally efficient solutions.
A broad overview of the primary and emerging contami-
nant species encountered in cleanup sites and the unique
physicochemical processes that govern their fate and trans-
port in the environment is provided in the second chapter.
These properties are related to their solubility, volatility,
retardation, susceptibility to degradation, and transport in
groundwater systems, which are all integral to understanding
a contaminant’s behavior and are essential to selecting and
deploying treatment remedies. A discussion is also included
on the transport of nonaqueous phase liquid and its transport
behavior and contribution to dissolved-phase plume develop-
ment. This information is provided as a precursor to subse-
quent chapters that delve deeper into individual contaminants
and the remedies available to address them.
The third chapter reviews the approach to remediation
design. The discussion starts with the foundational elements
of the design process and the role each element typically
plays. This is followed by a comparison of a conventional
compartmentalized design approach with integrated design,
where a multidisciplinary team works together as a collective
to understand and develop all aspects of the design. With
the basic philosophy of design approach handled, the bulk
of the chapter tackles key factors in the success of remedia-
tion design that can be major stumbling blocks if not properly
accounted for. This includes health and safety considerations
(hazard identification and critical failure analysis, hazard con-
trols, and response planning), predesign efforts (from thought
experiments to real experiments), biogeochemical consid-
erations (fouling impacts on equipment and the subsurface,
material compatibility, and secondary effects on water qual-
ity), and finally peripheral environmental factors that need to
be considered so that the proposed remediation activities will
not affect the environment or nearby receptors.
The fourth chapter provides an overview of remediation
hydrogeology, the application of hydrogeology to remedia-
tion engineering. Fundamental concepts of groundwater flow
and contaminant transport are covered before reviewing the
evolution of remediation hydrogeology from water supply ori-
gins up through the breakthroughs of remediation hydraulics.
Three exciting new areas are covered: Smart Characterization
methods, stratigraphic flux, and return on investigation (ROI).
Smart Characterization is a new way of approaching site inves-
tigation, using real-time, high-resolution methods to develop
a mass-flux-based conceptual site model. Stratigraphic flux is
a powerful new approach that shows how an aquifer deposi-
tional history creates a characteristic permeability pattern at
the site, which can be interpreted using a flux-based frame-
work to classify soils as transport, slow-advection, and storage
zones. In turn, these classifications provide insights regarding
how permeability distributions within elements of the aquifer
architecture control contaminant transport, cleanup duration,
and realistically achievable end points. ROI is the philosophy
driving Smart Characterization and stratigraphic flux—the
idea that the most powerful way to save money on remedia-
tion projects is by changing the way we investigate sites and
placing the characterization strategy in an economic decision-
making framework to deliver outcome certainty.
The fifth chapter reviews shifts in our conceptualization
of hydrogeology and contaminant transport and how this new
understanding can be applied to groundwater extraction rem-
edies. Remediation hydrogeology requires us to move away
from a simplistic depiction of permeability by recognizing
that the majority of the mass flux occurs in a small segment
of the aquifer cross section. The inclusion of slow-advection
zones along with storage and transport zones provides a more
accurate picture of the subsurface and allows us to design
highly effective groundwater extraction systems. The new
understanding of hydrogeology is used to optimize ground-
water extraction, using a system of dynamic groundwater
recirculation (DGR), which provides significant performance
improvement over traditional pump and treat. DGR has been
xix
xx
applied to cleanup plumes never before thought possible, such
as the three-mile-long plume at former Reese Air Force Base,
which was reduced to below Maximum Contaminant Levels
(MCLs) in less than ten years.
Since the first edition of this book, no other class of remedial
technologies has evolved as significantly as injection-based
cleanup strategies—which are discussed in the sixth chapter.
The combination of improved characterization techniques, a
renaissance in our understanding of groundwater contaminant
transport, and expansion of our knowledge base pertaining to
microbial ecology and chemical transformation processes has
enabled deployment and completion of in situ remedies with
considerable control and certainty. We have gained consid-
erable insights into how to leverage naturally occurring oxi-
dation and reduction processes to enhance biotic and abiotic
transformation processes in ways that reduce overall cost and
remedial time frames. The lessons learned over the course
of in situ technology innovation have been plentiful, and this
chapter highlights the key aspects of characterization, design,
and operation to achieve best success.
In situ immobilization strategies and regulatory manage-
ment of metals and radionuclides are explored in the seventh
chapter. A cursory discussion of governing geochemical con-
cepts (pH, oxidation-reduction potential, and ionic strength)
and terminology precedes identification and detailed descrip-
tions of the available physical, chemical, and biological
mechanisms for remediating metal-impacted groundwater.
Successful groundwater treatment is demonstrated through
several unique case studies that highlight the advantageous
manipulation of the three governing geochemical concepts.
Further discussion is provided on high-resolution charac-
terization, microscopy, and spectroscopy as crucial lines of
evidence confirming the immobilization mechanism. The
chapter closes with a discussion on imparting permanence of
the implemented remedy and underscores the importance of
proactive communication and knowledge sharing to manage
regulatory and stakeholder concerns.
In the eighth chapter, we look at sparging and venting—
remediation techniques that have been in practice since the
first edition of this book in 1996. This chapter covers the
application of these techniques with updates that reflect
how they have evolved. For example, the ability to remove
Preface
a contaminant from water through sparging was historically
attributed solely to Henry’s law, describing the contaminant-
specific rate of dissolved-phase/vapor-phase partitioning. In
our discussion, we introduce the dual-rate model for contami-
nant stripping where, in addition to Henry’s law, molecular
weight plays a role by controlling contaminant diffusion from
untreated areas to the air channels formed by sparging. With
soil venting, we introduce the pore volume exchange approach
to design an advancement beyond the empirical and radius
of influence approaches. The pore volume exchange approach
emphasizes the actual exchange of the air-filled pore volume
as a driver for cleanup, along with how air movement occurs
in venting wellfields and how their operation can be cycled to
maximize venting effectiveness.
The ninth chapter covers soil treatment technologies where
the focus is primarily on mass removal, extraction, or destruc-
tion. Ex situ and in situ treatment methods are described for
soil treatment options under different conditions. The technol-
ogies covered are thermal technologies, including incinera-
tion, in situ soil stabilization (ISSS), and phytotechnologies.
A detailed discussion on the suitability and implementation
of ISSS methods is provided with some case studies. Multiple
configurations for the application of in situ thermal remedia-
tion technology are discussed in detail. A state-of-the-science
update on phytotechnologies and their applications are also
presented in this chapter.
Permeable reactive barriers (PRBs) have gained con-
siderable popularity since the first edition of Remediation
Engineering, and the tenth chapter is devoted to discussing
the advancements and wealth of case study information avail-
able in the literature. The holistic PRB process is explored,
including available configurations, innovative installation
techniques, key design parameters, and typical regulatory
recommended performance monitoring. Since the first PRB
field-scale installation in 1991 by the University of Waterloo,
more than 200 field-scale PRBs have been installed world-
wide, and a collective accounting of successes and lessons
learned has identified groundwater hydrogeology and reac-
tivity as the two driving design parameters for PRBs. These
critical design parameters are explored in terms of three
large-scale case studies, one of which has more than 15 years
of performance monitoring data.
Acknowledgments
First and foremost, I thank the large group of like-minded col-
leagues throughout Arcadis and our base of forward-looking
clients who share our passion and enthusiasm for constantly
updating our knowledge base and being at the cutting edge of
implementing remediation solutions. I also thank Joachim Ebert,
our chief operating officer, for his inspirational support to finish
this ambitious effort of completing the combined second edition
of three successful books. I specially thank Dr. Scott Potter for
giving us permission to use his figure for the cover design.
Mere words cannot express our gratitude to Carol Yochum,
who functioned as the glue and the task master, for coordinat-
ing the efforts of all the authors in the midst of busy schedules
and the demands of their day jobs. The significant inputs pro-
vided by John LaChance, Eric Panhorst, Don Malone, Adam
Chwalibog, Dave Caballero, Margy Gentile, Caitlin Bell, and
Davinder Randhawa are immense. Rachel Stevens did an
excellent job in utilizing a figure that captured the essence of
this book in an attractive cover design. The drafting support
provided by Matt Wasilewski is greatly appreciated.
—Suthan Suthersan
The insights captured in this book draw from a long list
of collaborative inputs over the years from both mentors and
teammates. This includes Fred Payne and Scott Potter, who
were always ready to share their knowledge and champion the
value of critical thinking, and Margy Gentile, Mark Klemmer,
Dwayne Campeau, and Jeff Gillow, all of whom contributed
their time and enthusiasm to making sure we got it right.
—John Horst
While this book ultimately provides the authors’ knowl-
edge and understanding of remediation processes, technology,
and assessment techniques, the body of information presented
in this resource is the end result of countless individual engi-
neers, geologists, and scientists who have shed sweat and
brain power to contribute in some form to shaping this area of
practice. While acknowledging every individual by name is
impossible, Mushtaque Ahmad, Caitlin Bell, Jon Spitzinger,
Shawn Burnell, and Denice Nelson all contributed either
detailed information, critical review, or supporting reference
materials to expand the material presented in these chapters.
—Matt Schnobrich
I thank Joe Quinnan for his continued mentorship over
the past ten years and his thoughtful review of this book.
Many of the concepts around Smart Characterization were
developed by or with Joe’s help. The chapter on DGR could
not have happened without the help of both Scott Potter for
his guidance and Jennifer Wahlberg for her modeling sup-
port. I also thank Patrick Curry, Jesse Wright, Allison
Yanites, Allan Horneman, Mark Klemmer, Dan Lang, Aaron
Bobar, Craig Divine, Randy St. Germain, Dave Favero, and
Matt  Wasilewski for their helpful reviews and contributions
to the book.
—Nicklaus Welty
The technical content of the contributed chapters was
inspired and informed by the passion and excellence of
Dr.  Jeff Gillow, Dr. Donald Carpenter, Dr. Margy Gentile,
Dr.  Michael Hay, Jeff Burdick, Shawn Burnell, Dr. Scott
Potter, John Horst, and Dr. Mushtaque Ahmad. Carol Yochum
and Matt Wasilewski were more than instrumental in manag-
ing our technical content and organizing the framework of
this book. A gracious appreciation and thank you is extended
to the following esteemed colleagues, who supported this
book: Chase McLaughlin, Caitlin Bell, Jon Spitzinger, Mike
Misakian, Jennifer Halcomb-LeBeau, Erik Mantor, Matt
Carney, Mike Bedard, and Carmen Vidal.
—Jeff McDonough
xxi
Authors
Dr. Suthan Suthersan, PE scale and complexity. John stays heavily engaged in technical
is chief technical officer and support and technology/intellectual property development
executive vice president at and in his current role supports in Arcadis toward the devel-
Arcadis, a global environ- opment of entrepreneurial technical leaders that can connect
mental, water, buildings, their expertise with market trends and the business perfor-
and infrastructure services mance drivers of clients (financial, nature, community, etc.).
company. He has enabled John earned a   BS in engineering at Drexel University,
Arcadis to be one of the where he participated in a National Science Foundation pilot
most respected knowledge- program to produce more business-savvy graduates. He has
based environmental ser- published on remediation topics ranging from restoration geo-
vices companies in the chemistry to specific treatment technologies and has given
world through his contributions toward technology develop- courses on in situ bioremediation. In his 19 years at Arcadis,
ment and the development of best practices and knowledge he has helped establish new capabilities, captured dominant
sharing platforms. His expertise and experiences are gained market positions in a number of key competencies, and devel-
from participating in hundreds of environmental remediation oped the first innovation program for the company, which is
projects in the United States, Canada, Europe, Latin America, now implemented globally.
and Asia.
Dr. Suthersan earned a BS in civil engineering at the Matthew R. Schnobrich is
University of Sri Lanka and a PhD in environmental engineer- a technical expert and asso-
ing at the University of Toronto. He has more than 35 years ciate vice president at
of experience. His groundbreaking book, Remediation Arcadis. He currently serves
Engineering, was published in 1996, and he has also authored as the director of remedia-
two additional books, Natural and Enhanced Remediation tion and has over 15 years of
Systems and In Situ Remediation Engineering, and has been experience in the design,
awarded 20 patents (and more pending) for remediation tech- implementation, and com-
nology applications. His column, “Advances in Remediation pletion of a variety of reme-
Solutions,” is regularly featured in the Journal of Groundwater diation technologies, in
Monitoring and Remediation. addition to the characteriza-
Dr. Suthersan has taught courses in remediation engi- tion, pilot testing, and strategy behind their development. He
neering at the University of Pennsylvania; University of also provides technical support for these systems within the
Wisconsin, Madison; and Northeastern University, Boston. United States and abroad. Through his direct experience on
He founded the biannual RemTEC conference on advanced hundreds of sites, he has the opportunity to consolidate and
remediation solutions and is also currently collaborating with evaluate data and extract information to develop best practices
the National Groundwater Association on a new conference and technical standards. From this experience, he continues to
combining the themes on emerging contaminants, large con- develop innovative approaches and remedial solutions to
taminated plumes, and their impacts on water supplies. enhance existing technologies for future implementation.
He has written extensively on the topic of in  situ biore-
John Horst, PE, is the exec- mediation and received the 2011 Samuel Greeley award from
utive director of TKI for ASCE. He has lectured at numerous conferences and con-
North America at Arcadis. tributed regularly to peer-reviewed publications to dissemi-
John is an expert in the nate best practices and emerging technologies throughout the
development, application, industry.
and optimization of new and He is a registered professional engineer with a BA in biol-
innovative environmental ogy and Spanish from St. John’s University and an MS in
restoration technologies and environmental engineering from the University of Minnesota.
integration of multiple disci- Outside of his engineering career, he also competed interna-
plines to address restoration tionally in the sport of rowing and won a bronze medal at the
challenges with significant Beijing Olympics with the US Men’s Eight.

xxiii
xxiv Authors

Nicklaus Welty, PG, CPG, Jeff McDonough, PE, is a

is the director of site inves- principal engineer at
tigations for Arcadis, and Arcadis with 10  years of
has been with Arcadis for professional experience in
over ten years. Prior to his in  situ remediation applica-
current role, he founded and tions. Through his role as a
led the high-resolution site technical leader within
­characterization program at Arcadis’s TKI platform, he
Arcadis. He is the company brings informed and proven
expert in dynamic, adaptive in  situ remediation experi-
high-resolution site investi- ence to a broad range of
gations with real-time 3D hydrostratigraphic and plume multinational clients. He has published and presented on
modeling, and he led the first commercial applications of diverse subjects within remediation engineering, and his
several advanced site characterization tools and strategies knowledge base incorporates geochemistry, microbiology,
and the first real-time, adaptive Smart Characterization proj- systems engineering, and hydrogeology to establish balanced
ects on several international projects. Nicklaus has taught solutions to challenging site restoration. He earned a BS in
internal and external workshops to regulators, clients, and civil and environmental engineering, with a minor in environ-
consultants on innovative site characterization strategies and mental engineering, and an MS in environmental engineering
leads Arcadis’ company-wide training initiative for high- at Pennsylvania State University. His master’s research
resolution site characterization methods for geologic, per- focused on the influence of manipulated rate kinetics on the
meability, and contaminant mapping. He earned a BA in permanence of biologically immobilized radionuclides.
geology at the College of Wooster and an MS in environ-
mental geosciences at Michigan State University.
 1 State of the Practice
Remediation Engineering
1.1 INTRODUCTION
The environmental remediation industry has grown from
its small roots in the late 1970s to be a multibillion dollar
global industry during the last four decades. At its birth,
hazardous waste handling, transport, and disposal were the
primary activities in the industry. During the 1980s, the face
of the industry changed with the introduction of the under-
ground storage tank (UST) regulations and passage of the
Comprehensive Environmental Response, Compensation,
and Liability Act (CERCLA or Superfund) and the Hazardous
and Solid Waste Amendments to the Resource Conservation
and Recovery Act (RCRA). The volume and complexity of
the hazardous waste cleanup sites set the stage for the growth
of the remediation industry. Traditional engineering and con-
struction firms were the first to enter this market followed by
many smaller, regional firms in addition to many niche firms
with specialized skills and expertise.
Today, the remediation industry is quite different in com-
parison to its early beginnings. Regulatory trends are in a
constant state of flux with a variety of standards enforced
at national, state, and local jurisdictions. Dramatic swings
along legislative, technological and economic fronts have
occurred during the growth and expansion of this relatively
young industry. The staggering dimensions of cleaning up our
nation’s hazardous waste sites, and also across the world, pro-
duced a substantial need for the introduction and development
of efficient and cost-effective technologies.
The hazardous waste cleanup business was supposed to be
working itself out of a job since much of the contamination
at these legacy sites had their origin from the operation of
industrial facilities prior to the establishment of modern regu-
lations. Before the onset of current regulations, methods of
hazardous waste disposal included industrial lagoons, unlined
landfills and dumps, and waste piles. Thus, the historical
inventory of sites requiring cleanup was very large and varied
from region to region depending on the degree of industrial
activity. However, for those of us in the remediation business,
the work has kept coming as waves of new sites have come
into play over the past decade as new and emerging contami-
nants are identified and regulated. In addition, new categories
of contaminated sites like manufactured gas plants, fire train-
ing locations, and shale gas sites will require remediation due
to upcoming regulatory developments.
As the remediation industry started to evolve over the
years, advances in cleanup technologies have gained accep-
tance from both an economic and technical efficiency per-
spective. Science and technology have never been static in
our  business. Motivated by “there must be a better way,”
scientists and engineers always look for innovative methods
and solutions that evolve into accepted practice and preferred
techniques. However, it should also be noted that the ability
to separate emerging technologies built on a sound scientific
platform from the ones practiced on a speculative basis has
always been a challenge in our still maturing industry.
Since the time the term “remediation engineering”
was coined by Suthersan and Blake in 1990,1 an enormous
amount of data and information have been collected within
the umbrella of this overarching and multidisciplinary techni-
cal discipline. This rising tide of data and information should
be viewed as an abundant, vital, and necessary resource to
continuously expand the depth and breadth of the scientific
knowledge within remediation engineering. The sequential
evolution and conversion of data to information to knowledge
to insights represent an emergent continuum, and the progress
along this continuum was essential for this relatively young
technical discipline to become the foundational pillar of a
growing, global industry (Figure 1.1).
1.1.1  Growth of an Industry
In spite of nearly four decades of efforts in our country and
across the globe, remediation of contaminated sites to its
pristine, precontamination conditions remains a significant
technical and institutional challenge. Since the 1970s, bil-
lions of dollars have been spent to mitigate the human health
and ecological risks posed by contaminants released to the
subsurface environment. These investments and efforts
have shown reasonable progress within the major regulatory
programs. For example, 20% of the 1723 sites listed on the
National Priorities List have been permanently removed by
the U.S. Environmental Protection Agency (USEPA) because
all the remediation actions required to remove the risks posed
to human health and the environment were completed.3,4 Of
the 3747 hazardous waste sites regulated under the RCRA
corrective action program, 70% also have achieved control of
human exposure to contamination, and 686 have been desig-
nated as corrective action completed.5 The UST program has
reported the most significant success with the closure of over
1.7 million USTs since the initiation of the program in the
early 1980s.6
Growth rates of many environmental industry segments
have been strong in recent years. Traditional environmental
markets are driven by the demand for essential services (such as
water supply and wastewater collection and treatment) and have
increasingly become mature markets. However, the emerging
1
2 Remediation Engineering

matters for firms that need to meet the demands of multina-

Insight is simplified
complexity tional clients who are focused on maintaining their image
Insight (wisdom) on environmental consciousness and sustainability across
Complex
true potential and future
the globe.
Number of components or

capabilities of remediation
context independence

Knowledge from
technologies In spite of the progress mentioned earlier, thousands of
accumulated experience, contaminated sites across federal, state, and local programs
observations and conclusions
from multiple sites are thought to still have contamination at levels preventing
and sources
them from reaching closure. The source of funding for the
Information from implementation of remediation projects is an important con-
common trends from
similar sites and sideration on the rate and volume at which these projects are
technical applications
Commonsense undertaken and completed. Responsible parties required to
Data from
individual implement remediation activities face a certain level of uncer-
sites
tainty initially in determining the maximum level of costs and
Level of understanding or connectivity in ensuring that the total expenditure produces a certificate of
regulatory compliance at the end. It is widely agreed that long-
FIGURE 1.1  Knowledge management continuum within remedia- term management will be needed at some sites for the foresee-
tion engineering. (From Suthersan, S. and Horst, J., Ground Water able future, particularly for the more complex sites in terms
Monitor. Remed., 27(3), 133, 2007.) of the type of contamination and/or the geologic conditions.
Considering the extent of the number of hazardous waste
regulation-driven markets like remediation are still expand- sites that require remediation, one question that has arisen
ing due to globalization, identification of emerging contami- consistently is the definition of site closure in relation to these
nants, and the investments on technologies, equipment, and sites. Does a closed site mean no residual contamination
delivery systems (Figure 1.2). Regulation-driven markets also above regulatory limits or is the definition flexible enough
fall into their own cycles depending on the time frames set for depending on the exposure pathways to the residual contami-
complying with the new standards or regulations or economic nation at the site? This confusion may not be limited to the
factors such as real estate booms and busts. general public but also to all the stakeholders, which may
The current remediation market is becoming global with include the regulators too. It should be noted that the defini-
international competition on all continents where the legis- tion of site closure varies within the different regulatory pro-
lation and regulatory requirements have been in place for a grams. Based on this discussion, it becomes philosophically
while. Competition is driven by experience and the presence important to distinguish remediation from another category
of large global companies from mature markets that have of corrective action, namely restoration. Attempts at restora-
expanded their activities outside their traditional borders and tion more typically lead to new end points and environments
operate at the global level. Broader geographic coverage also that share substantial, ecological, and aesthetic properties

10
Remediation market size (billions of dollars)

0
1980
1981
1982
1983
1984
1985
1986
1987
1988
1989
1990
1991
1992
1993
1994
1995
1996
1997
1998
1999
2000
2001
2002
2003
2004
2005
2006
2007
2008
2009
2010
2011
2012
2013
2014
2015
2016
2017
2018

Time

FIGURE 1.2  The trend showing the growth of the remediation industry during the last 35 years. The growth data prior to 1988 are anec-
dotal and from personal communications. Growth data from 2016 to 2018 are projections. (From EBJ, Environ. Business J., 2014; EBJ,
Environ. Business J., 2015.)
Remediation Engineering
with the original precontamination site. Remediation aims
to return a space to the exact condition in which it existed
before the contamination took place, whereas restoration
aims to return the space to a usable condition similar to which
existed before with new materials. If the logic of restoration
is one of reproduction or recreation, the logic of remedia-
tion is one of counteraction or undoing the harm.
The remediation industry’s future relies upon trends in
ecological management of the natural and built environ-
ments, and sustainability and resilience is its evident future.
Another significant issue facing the remediation industry is
the need for long-term stewardship at sites with institutional
and engineering controls. By their definition, these controls
are intended to last for an extended period of time and, in
most cases, in perpetuity, or until new technologies are devel-
oped and implemented to further decrease the risk posed by
the residual contamination. Although recorded on deeds,
there is generally little a property owner can do to ensure
that these controls remain in effect after the property is sold.
The industry is grappling with this issue and is in the process
of developing policies and procedures to address this issue.
The term “stewardship” has become an industry buzzword
that is defined in numerous ways or not defined at all within
the context of cleanup projects. To date, no formal policies
or consistent procedures have come from within the regula-
tory programs specifically defining long-term stewardship
related to remediation, specifically institutional and engineer-
ing controls. What is needed is a comprehensive definition of
the term stewardship that includes a specific long-term plan
for implementing realistic and fully enforceable institutional
controls at remediation sites.
Establishing universally accepted standards for the deliv-
ery of remediation services and promoting the integration of
environmental performance in construction standards are
also important for further maturation of the industry. In the
framework of the industry’s efforts to promote sustainable
field activities and consumption, the development of sustain-
ability standards and quality labels for environmental goods
and services will contribute to promote their quality and to
develop further market expansion. As technical standards are
not systematically harmonized at the national or global level,
some emerging advanced technologies face barriers when
trying to penetrate new markets. Establishing technical stan-
dards will also play a decisive role in ensuring the customer of
a guaranteed level of quality. Integrating environmental per-
formance requirements in production standards for the build-
ing and transportation industry can strongly develop markets
for eco-construction in general and for technologies related to
recycled materials, energy efficiency, water and waste man-
agement, noise reduction, and renewable energy consumption.
Technology development is key in this industry as the sup-
pliers are differentiated by technical solutions that make it
possible to achieve the cleanup goals at reasonable cost. High
level innovation capacity and the ability to provide creative
solutions for complex problems is a critical factor to be suc-
cessful in this competitive market as they   enable the par-
ticipants to continuously adapt to new market demands. The
3
development of new remediation technologies has historically
suffered from the fact that investing in such research activi-
ties presents a strong financial risk due to uncertainties in the
potential markets for these technologies. Financial support for
research and development efforts is critical to ensure continu-
ous innovation and to maintain the sector’s competitiveness.
The influence of collaboration between the federal gov-
ernment and the remediation industry on research and devel-
opment activities is already very high through the financial
support provided to research programs and projects and
through the ability to highlight potential new market oppor-
tunities. Evaluating the commercial application of emerg-
ing environmental technologies, most of which fail to reach
the market either because the technology is not sufficiently
mature or because it does not meet the market’s current needs,
is crucial for the technology evolution. Focusing on support
for technologies that present the highest potential for market
application could be an efficient way to promote the most rel-
evant research programs.
1.1.2 Technical Discipline to Practice
Remediation engineering is a unique technical discipline with
a history of integration of components from many scientific
subjects and different fields of engineering. The reality of
dealing with significantly complex systems, such as the sub-
surface environments contaminated by a multitude of chemi-
cal compounds, led us to appreciate the need for the evolution
of this emerging engineering discipline. Prior to the 1970s,
civil (or sanitary) engineers were primarily responsible for
environmental protection through design of municipal and
industrial wastewater treatment plants. By the 1980s, sani-
tary engineers with civil engineering training were renamed
“environmental engineers” to better integrate the broader
engineering mission. Technological advances during the last
three decades have gradually altered the landscape on how
we deal with recent and legacy environmental contamination.
Remediation engineering has become part of the very fabric
of the progress of the environmental industry during the last
few years, and the practitioners working within this young
industry have been amassing a large body of knowledge. It
is vital that this knowledge and experience be expanded and
shared and that vision is the impetus to write this second
edition.
The short history of remediation engineering is highly
insightful because it reveals the technological, regulatory, and
cultural aspects of its rapid evolution that will help current and
future students better understand the subject and take pride in
their chosen career. Decades-long interplay between research
in academia, industry, and concurrent advances in multiple
subdisciplines gave rise to a rich knowledge base from which
emerged the high profile practice of remediation engineering.
As mentioned before, advances in remediation engineering
have spurred the growth of a multibillion dollar industry.
The inherent need to understand the assimilative capacity
of the subsurface environment in dealing with the fate of con-
taminants has underscored the interdependence of knowledge
4 Remediation Engineering
from multiple technical disciplines. In many ways, the ground
beneath our feet is as alien as a distant planet. The scientific
techniques and approaches required to understand aboveg-
round ecological systems don’t translate well to the subsurface
environment. Scientists have traditionally portrayed the sub-
surface environment as a black box due to the spatial, chemi-
cal, and biological diversity within a few cubic centimeters.
During the emergence of remediation engineering as a
stand-alone technical discipline, a productive collaboration
between the science and engineering communities grew.
Recently, there has been much discussion about the future
development of remediation engineering as a stand-alone
practice. Three parallel paths of evolution have taken place
within remediation engineering during its march toward
becoming a full-blown practice (Figure 1.3). The first is based
on the framework of understanding the fate and transport of
contaminants such as hydrobiogeochemistry. The second path
focuses on the integration of diverse engineering principles
required for the design and implementation of various reme-
diation technologies. The third is the green remediation or
sustainability model requiring the integration of sustainabil-
ity concepts into all phases of remediation projects.
Remediation of contaminated sites initially was thought
to be an expensive and technically complex process. During
the early years, this industry has tended to rely primarily on
heavy engineering solutions, which were expensive but were
quick-fix answers. As the practice evolved over the years,
economical and technical effectiveness became the primary
deciding factors. As the coalescing and emerging practice of
remediation engineering developed a wide variety of cost-
effective technical solutions, technologies were developed to
address the simple as well as complex sites. It should also be
noted that during the same period, rapid evolution of environ-
mental investigation and analytical techniques with regard to
sampling, detection, and analysis also took place.
As remediation engineers, we are recognizing that differ-
ent subsurface media are all linked in one way or another,
and the significance of an integrated practice like remediation
engineering brings together the linkages between the various
Remediation engineering
Hydro-bio-geo-chemistry
engineering disciplines
Integration of multiple
Sustainable and green
remediation models
knowledge base
FIGURE 1.3  The three foundational columns that support the
advancement of remediation engineering as a practice.
physical, biological, chemical, and engineering disciplines.
Assessing transformation processes of organic and inorganic
compounds in complex environments requires a lot of tools,
and it is necessary for the knowledge transfer to occur from the
basic sciences to be applied in the implementation of field scale
systems. There seem to be numerous unexplored possibilities
to further the understanding and answer some questions on
transformation processes by utilizing the latest techniques
available in the chemistry and microbiology toolboxes.
The need to develop and field-test combined remedies for
cost-effective remediation of contaminated sites became a
necessity to achieve reasonable end points at sites with large
footprints of contamination, complex geology, and recalci-
trant contaminants. Robust, aggressive technologies designed
for rapid source-zone mass removal must be linked to tech-
nologies for achieving cleanup of the downgradient dissolved
plume. Integration of remediation technologies should mini-
mize the overall cost of the project by selecting treatment trains
that work in a synergistic manner. As such, strong themes
have emerged commensurately and the multiple connected
disciplines have been woven together intricately to address
the growing scale of remediation engineering as a practice.
When full-scale remediation systems are being designed and
implemented successfully in the field, the distinction between
the various scientific and engineering disciplines started to
blur within the practice of remediation engineering.
Revolutionary improvements in site investigation tech-
niques also had a significant impact on the evolutionary
growth of remediation engineering as a practice. Direct
push drilling technologies, routinely used in the geotechni-
cal engineering arena, have allowed the use of a wide variety
of tooling and instrumentation that can be advanced into the
subsurface lithology. Compared to other types of environ-
mental drilling techniques, direct push techniques have many
benefits with respect to environmental sampling, and they are
as follows: small volume or no drill cuttings, easy to handle
and maintain thus resulting to higher daily productivity,
easier to decontaminate properly, much smaller volumes of
decontamination wastes, easier to mobilize and demobilize,
and much better access when access is limited or the site is
in a remote location. Direct push sampling today is routinely
used for soil sampling, groundwater sampling, and soil gas
sampling because of the reasons given here.
There have been significant advances over the last few
years in the development of field sampling as well as ana-
lytical chemistry techniques. Research was focused on
improving sample representativeness in highly heterogeneous
systems, reducing sampling effort, and developing fundamen-
tal and practical aspects of passive sampling methods. The
design of new samplers or modification of existing ones has
permitted the development of improved strategies in in  situ
sampling and the expansion of passive sampling to a broader
range of contaminants. Significant advances have been made
in sample handling methods as well as in contaminant sepa-
ration and extraction techniques as well. The use of sensors,
biosensors, and nanomaterial is an active area of research in
this arena. Environmetrics, which is the field involved with
Remediation Engineering 5

TABLE 1.1
Some Key Milestones in the Evolution of Remediation Engineering as a Full-Fledged
Technical Discipline and Practice
1970 20 million people celebrate the first earth day.
1970 President Nixon establishes the USEPA with a mission to protect the environment and public health.
1976 Congress passes Resource Conservation and Recovery Act, regulating hazardous waste from its
production to disposal.
1976 President Ford signs the Toxic Substances Control Act to reduce environmental and human health risks.
1978 Love Canal, NY, residents discover contamination from buried leaking chemical drain.
1980 Congress passes Comprehensive Environmental Response, Compensation, and Liability Act and creates
National Priorities List, and revises the national contingency plan.
1984 UST Regulations shift the focus of tank regulations based purely on safety (e.g., fire codes) to
regulations meant to protect the environment and public health.
1984 Health and Safety at Work Act promulgation stipulates corrective action requirements at facilities with
ongoing operations and introduces land ban of specific contaminants.
1980s Dig-and-haul and pump-and-treat technologies dominate due to “remove the source” and “contain the
plume” mind-set as a result of initial public reaction to subsurface contamination.
1980s Petroleum contamination is the primary factor influencing the evolution of in situ remediation
technologies—thus, soil vapor extraction (SVE), air sparging, and aerobic bioremediation become the
emerging technologies.
1990s Further development and enhancement of in situ technologies relying on physical mass removal such as
venting and air sparging and aerobic bioremediation.
1990s Chlorinated solvents become the primary focus of concern.
1990s Development of anaerobic bioremediation relying on engineered reductive dechlorination to address
chlorinated solvents.
1990s Sediments contamination starts to get attention.
1990s Dissolved metals also become an area of concern.
1990s Development of in situ metals precipitation.
1990s Development of thermal technologies.
2003 Development of remediation hydraulics revisiting the age old understanding and assumptions in
remediation hydrogeology.
2000s Green and sustainable remediation became an accepted practice.
2000s Focus is placed on multiple emerging contaminants.
2000s Combined remedies are included in large-scale system designs.
2010s Regulatory standards for some emerging contaminants are in place.
2010s Remediation of large plumes becomes a discipline on its own.
2010s Convergence of the remediation industry and water supply industry is beginning to take shape.

development and application of quantitative methods for envi-
ronmental analysis, has become an essential supporting disci-
pline within the remediation practice.
1.1.3 Advances in Complementary Disciplines
Most fields of science and engineering evolve rather than
being invented as a result of someone’s burst of inspiration.
Remediation engineering is an applied field of study that evolved
from early foundations of several related technical and scien-
tific disciplines. Significant elements of hydrogeology, geology,
chemistry, geochemistry, microbiology, biology, and physics in
addition to the many engineering disciplines such as environ-
mental, civil, chemical, mechanical, and electrical form the core
foundation of the current incarnation of remediation engineer-
ing. Although we have witnessed a period of tremendous growth
for remediation as a global industry, remediation engineering as
a field of study is still in a transitional phase waiting to become a
fully fledged academic program. Several key events can be cited
in the transformation of remediation engineering into a broader
practice area with its own intellectual merit (Table 1.1).
Defining an emerging engineering or scientific field is dif-
ficult because of the overlapping nature of related scientific
disciplines as illustrated in Figure 1.4. The theoretical rigor of
the fundamental processes that are involved in contaminant
mass removal mechanisms provides the basic framework for
integrating relevant disciplines across a diverse set of natural
and engineered environments. The focus is not so much on the
subsurface environment itself but on what is in it as contami-
nants that has to be removed and the preferred techniques to
remove them. Recent advances in some of the core relevant
disciplines are discussed in the following sections.
1.1.3.1  Advances in Remediation Hydrogeology
The early developments in hydrogeology mainly dealt with
the development of groundwater and mineral resources.
6 Remediation Engineering

Modeling Geophysics
Hydrology Site inv

Groundwater Mineralogy
hydrogeology
Process
Fluid engineering
mechanics Hydrogeology Geology
Safety
Structural
design
engineering
Chemical
Civil engineering
engineering
Geotechnical Metallurgy
engineering
Remediation
engineering
Wastewater
treatment Ecology
Environmental Biology
Air engineering
quality
Toxicology

Water Geochemistry Chemistry

treatment Microbiology

Soil Analytical
chemistry chemistry
Water Biochemistry
chemistry

FIGURE 1.4  Illustration of the multiple technical disciplines that contribute to the foundational knowledge base of remediation engineering.

When the focus on potential drinking water sources designed, the subsurface is strikingly heterogeneous, and
shifted from surface water to groundwater extraction dur- large-scale averaging and steady-state observation obscure
ing the middle of the last century, the science of ground- details of aquifer structure that are essential for the design
water hydrogeology emerged as a scientific discipline. In and operation of successful groundwater remediation sys-
the water resources industry, groundwater extraction is tems (Figure 1.5).
designed and implemented at relatively large scales, and
(e.g., permeability, porosity, geochemistry)

the developments in groundwater hydrogeology was based

on a foundation of macroscale hydrogeologic and hydrody-
Observable aquifer characteristic

Representative elementary volume (REV)

namic principles.
The hydrogeologists who designed the early groundwater
remediation systems primarily were migrants from the water Avg value
resources and oil exploration industries to the remediation
industry. This was the reason for the initial dependency on a
conservatively designed groundwater pump-and-treat (P&T) Classical Darcian hydrogeology
systems for mass removal and containment of contaminated
groundwater plumes. The designs of these systems were Remediation
based upon pumping tests and capture zone analyses, and hydraulics
the proof of a system’s effectiveness being the successful
Scale of observation
redirection of groundwater flow toward the extraction points.
Large-scale averaging of key system variables has been an FIGURE 1.5  Differences in the domains of observation and utili-
essential and effective strategy in designing water supply zation of hydrogeologic parameters between traditional groundwa-
development and water resources development systems. ter hydrogeology and remediation hydrogeology. (From Payne, F.C.
However, within the scale in which remediation systems are et al., Remediation Hydraulics, CRC Press, Boca Raton, FL, 2008.)
Remediation Engineering
The concept of remediation hydrogeology began to evolve
recently and encompasses the broader goals of understanding
the subsurface environment and the necessary technical tools
to design effective groundwater remediation systems. Thought
leaders of this emerging discipline realized that a more fun-
damental approach was needed based on the premise that all
porous media are heterogeneous at the smallest scales and
natural aquifers are heterogeneous over all scales. They began
emphasizing fundamental scientific rigor and quantitative
approaches in the areas of fate and transport of contaminants,
fluid flow in porous media, and properties and interpretation
of aquifer stratigraphy. Among the key events transforming
remediation hydrogeology into its current thinking and utility
are the introduction of the dual-domain concept and question-
ing the age old concept of bulk hydrodynamic dispersivity in
analyzing and predicting contaminant transport.9
Only within the past few years, there has been considerable
focus on the adequate delivery and distribution of injected sub-
strates for the design and implementation of in situ remediation
systems. Tracer studies have emerged as the most powerful tool
to unmask the heterogeneous structure of groundwater flow and
to understand how injectants and contaminants behave in an
aquifer. In the past few years, a rich base of tracer study data has
been collected, and the results from these tests have made us to
rethink how we design injection-based systems specifically and
extraction systems as well. A significant insight derived from
the accumulated knowledge from tracer testing was regarding
the presumptive assumptions of porosity of different types of
soils and how we estimate groundwater velocities. These tracer
tests have helped us to open the black box of fine-scale aquifer
architecture and understand contaminant and reagent migra-
tion in the subsurface. As a result of this fundamental shift, a
significantly different thinking has been developed in how we
design injection-based in situ systems. The standard design and
operating procedure, until recently, involved the use of high-
concentration low-volume injection of reagents, under pressure
Overall cost of remediation
Traditional
Investigative methods
FIGURE 1.6  Overall cost savings utilizing smart investigation methods and developing better conceptual site models for cleaning up
contaminated groundwater plumes using the mass flux-based approach. (From Suthersan, S. et al., J. Ground Water Monitor. Remed., 35(3),
25, 2015.)
7
when warranted. Current injection-based systems have shifted
to high-volume, lower to moderate concentrations based on the
current understanding in remediation hydrogeology.
A more frequent implementation of next-generation meth-
ods such as high-resolution site characterization techniques
has enabled the development of far more accurate conceptual
site models (CSMs). Realistic conceptualization of an aquifer
structure recognizes that the majority of groundwater flow
and contaminant mass flux occurs through the most perme-
able materials and that these can represent a relatively small
percentage of the overall aquifer volume at most sites. As a
result, remediation engineers of today have an increased level
of understanding of contaminant transport mechanisms from
a very large body of empirical observations of plume dynam-
ics and remediation system performance. There has been a
shift in thinking from a remediate everywhere mind-set to a
focus on mass flux—contaminant mass that moves.
To maximize the return and benefits of CSM development,
it’s necessary to move beyond conventional investigation
methods developed decades ago and to use smart investiga-
tion tools with a dynamic, adaptive approach. Smart inves-
tigation tools are more than a catch phrase—they enable
better, more cost-effective decision-making by increasing the
information content and quality from the investigation efforts.
Compared to the conventional linear, iterative investigation
cycle using monitoring wells, this approach provides real-
time, high-density data to accurately map the geology and
contaminant distribution at high resolution. What’s unique
about this approach is that the investigation can be done not
only better and faster but also cheaper. The cost savings are
realized (Figure 1.6) during every stage of the project life
cycle by
• Replacing the inefficient repeated investigation cycle
of work plan, data collection, and report writing with
a streamlined, real-time communication process that
∆Project
ROI =
$ (IC)
ΔProject
Remediation
cost
Site investigation
cost
Investigation
costs = $ (IC)
Smart methods
8 Remediation Engineering
informs stakeholders and builds consensus before
the final report is written
• Minimizing the use of monitoring wells, which
are meant for monitoring and not characterization,
resulting in reduced short-term and long-term moni-
toring costs over the life cycle of the project
Mapping the site in terms of contaminant flux, rather than
simple concentration, is a cornerstone of the approach.
Knowing that contaminant mass moves in high permeability
zones and is stored in lower permeability zones is essential
to remediation success. Distinguishing the mass in the trans-
port zones from storage zones with this investigative approach
enables you to focus your remedy on the mass that matters
because of the following:
• Of the contaminant transport, 90% is typically con-
centrated within 10%–20% of the cross section of
the aquifer.
• The interaction between transport and storage zones
determines realistic remedial end points and remedy
time frames.
Although many things have been improved with time within
the larger context of remediation hydrogeology, one of the
most difficult practical challenges remains—namely, how
we deal with large dissolved plumes. Presumptive think-
ing emphasizes containment and management of these large
plumes rather than focusing on mass removal and site clo-
sures. However, evolving insights related to plume structure
and solute transport processes at the remediation system scale
is providing the opportunity to move from merely plume man-
agement strategies to successful remediation and relatively
shorter time frames for closure of many large plumes. The
combination of a mass flux perspective with dual porosity
concepts and the advection–diffusion transport concepts has
helped us to understand how a contaminant plume matures in
its path from the source to the leading edge. Understanding
the continuum of plume maturity is the cornerstone to design
the remediation system that will help us to look at different
strategies and combined remedies being adopted in different
portions of a large plume.
Significant developments in contaminant mass flux and
mass discharge measurement techniques in recent years have
increased the spotlight on the debate as to whether post-
remediation or closure standards should be based on con-
centrations or mass flux. This approach provides a pragmatic
and scientifically based means to prioritize and allocate finite
resources to remediate a site for maximum return of benefits.
Recommendations have been made during regulatory policy
discussions that a mass flux framework should be used to sys-
tematically develop performance and compliance monitoring
programs. This framework will focus efforts on the high flux
zone—zones that would potentially be used as a groundwater
resource and provide a direct measure of remedy performance
and potential risks associated with contaminant migration.
This approach, aptly captured as Flux-Informed Remediation
Decision Making, sharpens the focus on the contaminant mass
that moves to maximize the remediation benefits at any site.
1.1.3.2  Advances in Environmental Microbiology
Since its inception, environmental microbiology has been
the science of the presence, abundance, interactions, and
physiological activities of microorganisms in terrestrial and
aquatic environments. The earth’s habitats present complex
gradients of environmental conditions that include variations
in temperature, light, pH, pressure, salinity, and the presence
of both organic and inorganic compounds. Microorganisms
are the primary agents of biogeochemical changes in the
subsurface environment. Their small size, ubiquitous distri-
bution, high specific surface area, potentially high rate of
metabolic activity and growth rates, physiological respon-
siveness, genetic malleability, and enzymatic and nutritional
diversity provides them with an unrivaled opportunity to
play a significant role in many in situ and ex situ remedia-
tion processes.
Over the past few years, microbial ecologists have demon-
strated the importance of understanding microbial processes
controlled by environmental variables and limited resources.
These processes are highly specific in terms of what, when,
where, and why they are active and how they impact ecosystem
dynamics. Advances in analytical, imaging, micro-sensing,
and computational techniques in concert with molecular bio-
logical tools have revealed levels and mechanisms of micro-
bial organization and interaction that are both remarkably
complex and intriguing. Before the widespread application of
genetic tools, our estimates of microbial diversity were based
on observations obtained from enriched cultures despite the
realization that only a few percent of strains were culturable.
As a result, we have learned that, if nothing else, microbial
diversity is astounding and greatly exceeds anything we could
have imagined only 10 years ago.
These advancements in environmental microbiology are
helping us to make the functional connection between the
seemingly infinite diversity and the multitude of environ-
mentally relevant processes that diverse taxonomy groups
carry out. The knowledge base developed has helped in link-
ing the multitude of players to these processes under varying
environmental conditions and constraints that characterize
habitats, ecosystems, and even regions. Characterizing and
developing a good understanding of relevant spatial and
temporal scales over which microbially mediated remedia-
tion processes operate is of additional importance from an
interdisciplinary perspective. This is the realm of sliding
scales where environmental microbiologists must interact
with hydrogeologists, geochemists, biochemists, limnolo-
gists, and modelers to determine the boundary conditions
over which monitoring measurements and analysis have to
be made.11
In some instances, ecosystem function can be inferred by
relating groups to the physical, chemical, and biological char-
acteristics of the particular environment of interest to imple-
ment remediation. This strategy can work well in simple,
structured environments where local microbial communities
Remediation Engineering
are dominated by only a few morphologically distinct organ-
isms. In more complex communities where the microbial
populations are heterogeneous, it remains difficult to unravel
specific ecological roles played by particular organisms
within a group. As mentioned earlier, advances in molecular
techniques have shifted the emphasis from culturing to the
analysis of signature molecules, in particular, specific gene
sequences. The resurgence of the application of molecular
tools for expression analysis from environmental samples is
generally seen as a consequence of reduced technology costs,
together with more effective methods for recovery for genetic
material and increasing amounts of data on the quantitative
systems that are available.
Finally, the structure of knowledge in environmental
microbiology emerges as an effort at balancing real-world
significance of field sites and their puzzling complexity
between molecular insights from reductionism and the pos-
sible inapplicability of information gathered (Figure 1.7).
The reductionism mentioned here refers to the reductionis-
tic progression from field sample to laboratory incubation, to
enrichment culture, to the isolation of pure cultures, and to
elucidation of genetic information. As each layer of reduc-
tionism unfolds, the likelihood of the resultant informa-
tion being ecologically relevant in the field also diminishes.
Environmental microbiology traverses from highly relevant,
but uncontrolled and sometimes uninterpretable field site
measurements to sophisticated yet much more simplified lab-
oratory systems. Laboratory systems are increasingly likely
to induce artifacts and hence maybe of uncertain relevance to
the microbial processes relevant to the remediation system in
the field. The in situ biogeochemical processes of interest are
likely affected by intact, naturally occurring communities to
intricate biogeochemical food webs.
High
microbial processes in field sites
Relevance to knowledge of
Low
Microbiology
techniques
FIGURE 1.7  Relationship between means of producing environmental microbial information relevant to designing a remediation system
and to the microbial methodologies used. (From Madsen, E.L., Environ. Sci. Technol., 32(4), 429, 1998.)
9
1.1.3.3  Environmental Geochemistry
Geochemists have been interested in the chemistry of ground-
water systems for over a century. Environmental geochemis-
try is the discipline that explores the processes controlling the
chemical composition of the subsurface environment. It deals
with the physical, chemical, and biological conditions of the
subsurface such as mineral composition, state of matter, tem-
perature, pH, redox potential, and microbial activity. These
factors and others influence the mobilization, dispersion,
deposition, distribution, and concentration of dissolved com-
pounds, specifically metals, often due to natural and anthro-
pogenic influences. Beyond defining and identifying chemical
impacts to an ecosystem, environmental geochemistry has a
big role to play in assessing the potential and feasibility of
physical, chemical, or microbial remediation technologies
that can be implemented at any given contaminated site
(Figure 1.8).
Geochemistry has played an important role in the devel-
opment of remediation engineering, in part because of the
important role of biogeochemical processes in the design and
implementation of remediation systems. Remediation system
designers need geochemical data integrated with microbial,
geological, and hydrogeological site information to evalu-
ate the effectiveness of different remediation alternatives.
Geochemists respond to that need by designing and oversee-
ing geochemical investigations during the baseline and imple-
mentation phases and also help in the design of bench-scale
and field-scale pilot studies. In developing CSMs, geochemists
work with specialty laboratories and utilize advanced analyti-
cal techniques to characterize and identify contaminants of
concern. Understanding the physical and biogeochemical pro-
cesses that determine the transport and fate of contaminants
is a major challenge and represents an important requirement
Means of producing information
Field Laboratory Pure cultures
Cells Genes
site incubations extracts
10 Remediation Engineering

Laboratory analyses

Sample digestion methods

Wet chemistry
Specialized methods for non-
routine analytes
Speciation
Advanced microscopy

Data/information/
knowledge management
Field measurements

Water and soil chemistry: COCs distribution

Geochemical mechanisms
pH Major cations and
Controlling COCs
Turbidity anions
Minor trace Geochemical CSM
Total and dissolved elements Data presentation
solids Geochemical modeling
ORP
Organics Strategy inputs
Conductivity
Anoxic or oxic Alternative end points
collection Temperature Remedy optimization

FIGURE 1.8  Importance of geochemistry in the everyday practice of remediation engineering.

to quantify the effectiveness of engineered remediation sys-
tems. Geochemical investigations and data collection usu-
ally include, but are not limited to, characterization of solid
matrix of the subsurface at the site, sequential and regulatory
leaching procedures, mineral and element identification pro-
cedures, chemical fingerprinting, compound-specific isotopic
analyses, and determination of sorption coefficients.
The issue of by-product formation due to solid-phase inter-
actions as a collateral effect of in  situ remedies has gained
more attention in the scientific, regulatory, and consulting
communities. Properly designed geochemical investigations
and analysis can help in the design process to determine what
secondary effects can be expected, what is the potential for
these impacts to spread beyond the targeted treatment area,
what are the time frames that can be expected for complete
recovery of the treatment zone and what is the permanence and
longevity of the treatment itself. The concept of geochemical
gradients becomes relevant in this context, and the geochemi-
cal model will help us to understand these gradients.13 Thus,
conceptual geochemical site models are important for the suc-
cessful deployment of in situ remediation systems to balance
the design, implementation and site closure objectives.
Major analytical methods and speciation techniques for
determining the solid-phase species and their physical distri-
bution to understand the mobility, bioavailability, and fate of
the contaminant metals in soils, sediments, and natural waters
by heavy metal forms have been used extensively in envi-
ronmental geochemistry. These methods include advanced
chemical extraction methods, scanning electron microscopy,
low-energy electron diffraction, x-ray methods, and advanced
mass spectrometric methods.14 With the development of
advanced chromatographic and spectrometric techniques,
compound-specific isotopic analysis provides a more efficient
means of identifying subsurface biogeochemical processes by
examining changes in the isotopic composition of the con-
taminants directly.
Compound-specific isotopic analysis is a method that has
the potential to differentiate between contaminant degradation
and other nondegradative processes of mass loss. Laboratory
studies have shown large shifts in the stable carbon isotope
values of tetrachloroethylene (PCE), trichloroethylene (TCE),
cis-­dichloroethylene (Cis-DCE), and vinyl chloride (VC) dur-
ing reductive dechlorination of these compounds. In contrast,
nondegradative processes such as sorption, dissolution, and
volatilization involve only relatively small isotopic shifts at
equilibrium.15 Isotopic studies coupled with chemical data are
powerful tools to trace single and multipollutant contamination
events and to evaluate in detail the chemical and fractionation
processes that occurred. Full validation of the applicability and
effectiveness of the isotopic approach in characterizing the deg-
radation or transformation processes will require additional field
and laboratory studies. Knowledge of the microbial ecology and
metabolic functions of microorganisms involved in the process
is essential to arrive at reliable conclusions.
1.1.3.4  Geophysical Methods
Geophysics is the process of measuring and analyzing con-
trasts in the physical properties of materials in the subsurface
in order to characterize geologic properties of interest and the
distribution of materials of interest within the geologic frame-
work. Rarely are the physical properties of interest measured
directly. Instead, contrasts in physical properties that can be
Remediation Engineering
used to deduce material properties of interest are measured.
For example, variations in the electrical resistivity of buried
soils are related to the occurrence and relative abundance of
clay minerals, the soil porosity, and the properties of materi-
als filling the pore spaces (gases or fluids). By measuring the
electrical resistivity of geologic materials, desired geologic
properties can be deduced including lithology, porosity and
permeability, and pore-fluid characteristics.
Geophysical methods are commonly applied to character-
ize geologic and hydrogeologic phenomena during site inves-
tigation and remediation applications. The following are some
examples:
• Lithology, porosity, and permeability
• Soil texture (grain size, sorting)
• Vertical and lateral distribution of geologic proper-
ties and structures (e.g., geologic facies and faults)
• Presence and degree of saturation in pores
• Physical and chemical properties of pore fluids
• Occurrence of anthropogenic features or structures
Typical methods include the use of airborne, surface, and
subsurface acquisition tools. Resolution generally varies
from hundredths of a meter to several meters (10 −2m to 105m)
depending on the method and desired objective. Borehole
geophysical methods provide vertically continuous, high-
resolution data at a single location that can be correlated to
other locations for lateral characterization. Surface geophysi-
cal methods provide both vertical and lateral characterization
of the subsurface, but at lower resolution, and the resolution
generally varies (decreases) with the depth of investigation.
Most geophysical tools were initially developed for
geotechnical engineering, mining, and petroleum explora-
tion purposes, but many of those tools have been adapted
to environmental applications in recent times. Advances
in surface geophysics acquisition and processing methods
have yielded higher-resolution methods for the identification
and characterization of geologic parameters, the occurrence
and extent of contaminants in porous media, and the iden-
tification of anthropogenic materials such as buried drums
or military munitions and landfill delineation. Near-surface
methods such as ground-penetrating radar and radio fre-
quency are commonly used for utility location and shallow
investigations.
Traditional borehole geophysical tools have long been
applied to deeper environmental investigations, but new
applications have been designed for shallow investigations.
Acoustical and optical televiewers provide visual data regard-
ing subsurface conditions, and flow meter tools that can be
applied to extraction and production wells to identify and
quantify yielding intervals. Moreover, advances in push-tool
technologies such as conductivity dipoles, cone penetration
testing, membrane interface probes, laser-induced fluores-
cence, hydrologic profiling tools, and other technologies are
providing high-resolution data specific to environmental
investigation and remediation needs. These tools are revo-
lutionizing environmental investigations by aiding in the
11
development of accurate CSMs that will ultimately facili-
tate and deliver more efficient and cost-effective remedial
strategies.
Electrical resistivity surveys also have a large pedigree in
the mineral resources industry. As with seismic techniques,
advances in computing power have provided investigators
with a new tool for monitoring moisture travel in the vadose
zone in real time. The latest deployment of high-resolution
resistivity, a modified resistivity network with advanced ana-
lytical techniques, is revolutionizing soil-moisture monitor-
ing in highly contaminated zones by moving beyond dry well
logging. The data obtained from high-resolution resistivity
surveys indicate both the time of release and the direction
of a spreading plume. High-resolution resistivity can also be
applied to existing contaminant plume by mapping the charge
distribution of a current-fed plume. The resulting map shows
areal distribution of the charged body in plain view. Similar
cutting-edge applications of electrical resistivity include exci-
tation of mass and residual potential mapping, both of which
have been successfully applied to contamination studies.
Recent advances in geophone construction, high-speed
microcomputers, and processing algorithms have also moved
seismic techniques into the fields of subsurface moisture map-
ping, aquifer boundary studies, and 3D vadose zone charac-
terization. Field-grade geophysical instruments are equipped
with digital signal processing and recording capabilities once
restricted to large corporate computing centers. The use of
geophysics in environmental applications is neither new nor
unique, but the advancement of geophysical tools designed
specifically for environmental applications continues to pro-
vide cutting-edge technologies that will improve investiga-
tion methods and result in more efficient and cost-effective
solutions to environmental problems. The incremental cost
associated with geophysical applications will in most cases be
significantly offset by savings in life-cycle costs for achieving
remedial objectives and project closure.
Geophysical investigation should be considered early in
the development of site characterization. Monetary and time
efficiency will be greatest when the geophysical surveys are
part of a phased program, especially at large and geologically
complex sites. Early geophysical exploration allows subse-
quent geologic engineering or hydrogeologic verifications in
an efficient and logical manner. Problems encountered late
in the field assessment may have little funding for their reso-
lution or verification. Further, there will be little advantage
from geophysics performed during the later stages of investi-
gation activities, as compared to early geophysical application
where subsequent investigations may be revised or replanned
in scope in terms of specific locations and detail.
1.1.4 Role of Remediation Engineer
The practice of remediation engineering has undergone sig-
nificant evolution during the last three decades. Nonetheless,
it has retained four major characteristics from its earlier days.
First of all, it still focuses primarily on issues related to human
health and ecological impacts on the environment caused by
12
hazardous waste contamination. Remediation engineering
thus is highly relevant for the quality of life of populations
living within and surrounded by natural and built environ-
ments. Second, it encourages a multidisciplinary perspective
based on integrated scientific principles and also extending
across many connected engineering disciplines. Remediation
engineers are comfortable in leading multidisciplinary teams
trying to understand contaminant behavior in the subsurface
and the subsequent removal of it. Third, remediation engi-
neers still view their domain to include all environmental
media: soil, water, air, surface water and groundwater, natu-
ral and engineered systems, and the gaseous and solid phases
with which water is in contact. Fourth, remediation engineers
always have borrowed concepts and technologies freely from
other fields of inquiry and applying them to enhance the qual-
ity of the environment by removing the risks to human health
and the ecosystem.
Given the interdisciplinary nature of remediation engi-
neering, the practice will continue to benefit from advances
in information management, analytical chemistry, molecular
biology, and transfer of more advanced technologies from
other fields of engineering. Remediation engineers, who
work across multiple scales, ranging from molecular level
contaminants to global portfolios of contaminated sites, are
poised to make additional contributions to improve the qual-
ity of the environment we live in. However, the role of the
remediation engineer today is much different than when the
role was defined during the early stages of the remediation
industry.
The issue of setting upon remediation objectives touches
upon the core aspects of remediation engineering today,
but none more so than realistically evaluating the feasibil-
ity of site closure. Whether a site can be regulatorily closed
depends largely whether the remediation objectives, defined
on the regulatorily accepted closure plan or the Records of
Decision (ROD), can be achieved from a practical perspective.
Evaluations of such practicality can be very difficult to make
when the objectives stated in the regulatory documents are in
such ill-defined terminology as removal of mass to the maxi-
mum extent practicable. We can find many other examples
of similar ambiguous and ill-defined remediation end points.
Thus, the role for the remediation engineer becomes one of a
leadership role in elucidating the practicality of the direction
of any remediation project from a technical and cost-effective
perspective.
Another positive development in the industry is related to
the healthy debates taking place within many regulatory juris-
dictions. These debates are focused on whether or not to alter
long-standing cleanup standards when they are unobtainable
in a reasonable time frame and also within reasonable cost
estimates in comparison to the overall benefit to the environ-
ment. These are the instances where remediation engineers
will be expected to ask the question, “Are we going to reme-
diate the site meeting absolute standards or restore the site to
beneficial use by removing or stabilizing the source mass and
eliminating all exposure pathways to the residual contamina-
tion at the site?”
Remediation Engineering
Remediation engineers have utilized many strategies
acceptable to regulators and other stakeholders, which
acknowledge site complexity and inherent technical and cost
barriers to achieving stringent cleanup standards, yet pro-
vide an effective path forward that reduces risk and retains
the ability to determine when unrestricted use is appropriate.
Examples include applying for and being granted a technical
impracticability (TI) waiver, utilizing the potential flexibility
on regulatory guidance, developing alternate concentration
limits (ACLs) as compliance values, groundwater zone reclas-
sification, institutionalized restrictions on future site use, and
using flux-based compliance instead of groundwater concen-
trations. These strategic alternatives can meet most regulatory
requirements and stakeholder expectations while protect-
ing human health and ecological impacts through exposure
controls.
Convergence of viewpoints toward a more mature, com-
mon vision to implement an environmentally protective and
cost-effective project is needed. Cleanup programs are chang-
ing under the influence of regulatory and economic initiatives
and the different types of liability management programs.
Investigations and cleanups increasingly need to be afford-
able, yet transparent and defensible. Technical goals and
terminology need to better reflect real-world site conditions
while being more supportive of project needs. Yet technical
considerations alone will not ensure project success, and bet-
ter integration of human factors into project management is
also required. We need to catalyze the continuous maturation
of the remediation industry by emphasizing a central theme of
managing decision uncertainty, elimination of unambiguous
technical, regulatory, and stakeholder communications, and
streamlining varying project life cycles and multidisciplinary
interactions. Remediation engineers need to lead the cleanup
industry toward an integrated, practical, second-generation
paradigm that can successfully manage the complexities of
today’s cleanup projects.
A recent development within the practice of reme-
diation engineering is the use of best-value remediation
design combined with traditional design principles. This
is achieved by prescriptive specifications with the use of
open competition to determine design elements specified by
performance requirements instead of traditional end points.
Compelling reasons to use best-value remediation design
include the potential realization of life-cycle cost savings,
an inherent flexibility that can accommodate changing reg-
ulatory, and public priorities, as well as evolving innova-
tive technologies and still maintain the ability to provide
a protective cleanup action. A major administrative and
implementation challenge is the development of a partner-
ing relationship, which fosters trust between project stake-
holders with differing interests. The best-value approach is
appropriate for most projects where the stakeholders have
a genuine desire to pursue environmental restoration in
an effective, open, and cost-effective manner. It is impor-
tant that the state of the practice will evolve in terms of
effectiveness and cost savings as a result of the best-value
approach because remediation engineers will be required
Remediation Engineering
to consider critical nontechnical elements during the pre-
design and design stages of a project. The quest for sound
financial performance in completing remediation projects
measured by reducing costs and technical innovations will
spur this concept further.
1.2 EVOLUTION AND MATURATION
OF TECHNOLOGIES
During the early years of the remediation industry, direc-
tion and efforts were mostly influenced by the regulations in
place and the need for compliance and protection of human
health and the environment. The industry, now three decades
old, continues to evolve and is influenced today by regula-
tory changes, economic factors, emerging contaminants, and
sustainability considerations. However, the most important
evolution has been, and will continue to be, in the area of
technological developments and enhancement of existing
technical solutions. The demand for continuous evolution of
cost-effective technologies led to a technological convergence
based on the merger of different scientific disciplines within
the overarching practice of remediation engineering. The
expression “emerging technologies” is used to cover such new
and cutting-edge technologies such as genetic engineering,
artificial intelligence, and nanotechnologies. Since remedia-
tion engineering is a young and emerging industry, many of
the innovative technologies that have been employed in this
industry go through the phase of being field-tested and proved
to be “performed as designed” until they become conven-
tional technologies.
In the traditional world of engineering practice, design
and construction of a dam, a multistoried building, or a high-
way has to take into consideration that these structures have
to be built to last a lifetime and meet or exceed every design
standard and specification. However, when we design reme-
diation systems, these systems are designed as temporary
systems expected to last only until the contaminant mass
is removed or the remediation performance objectives are
achieved—whichever comes first. Thus, the design process
and procedures employed in remediation engineering, with
respect to durability, is not standardized and universal as
practiced in the traditional and established engineering dis-
ciplines. The focus is more on operational efficiencies and
keeping the systems running continuously with minimum
downtime.
Evolution of remediation technologies was influenced not
only by changing regulatory and economic factors, but also by
the type and chemical characteristics of contaminants under
focus. An example is the shift in emphasis from engineered
aerobic bioremediation systems of the 1980s to remediate
petroleum hydrocarbons to engineered anaerobic bioremedia-
tion systems of the 1990s treating chlorinated solvents. Since
the 1990s, the ever-increasing understanding of the behavior
of most contaminants and the assimilative capacity of natu-
ral environments have also led us toward understanding and
maximizing the remediation poise and potential of natural
systems.
13
Although using the contaminant type provides a useful
starting point for assessing the appropriateness of remedia-
tion technologies, it is a gross simplification of what in reality
is likely to be a much more complicated scenario. Many con-
taminated sites will contain more than one contaminant cat-
egory, and this may necessitate the evaluation of a combined
remedy consisting of multiple technologies. Even within the
same contaminant grouping, for example, nonhalogenated
organics, biodegradation may be more amenable to some
compounds and not for others. There are also instances when
a technology may be feasible in theoretical terms or even
demonstrated at laboratory scale, but there may be practical
reasons why it cannot be applied at full scale, such as health
and safety concerns or scaling-up issues.
Another perspective in viewing the evolution of tech-
nologies within the remediation industry can be by looking
through the lens of primary mechanisms for mass removal.
Remediation technologies for treating organic, inorganic, and
metal contaminants from soil and groundwater have evolved
through three pathways with primary emphasis on (1) extrac-
tion or gross removal processes with or without ex situ treat-
ment, (2) in situ remediation of contaminants, and (3) reliance
on natural degradation and mass transfer processes. Some
technologies from each generation can be modified in order
to reach the next generation along the evolutionary path. The
progression reflects the increasing sophistication of society,
science, and engineering in dealing with environmental con-
tamination. The current generation is sustainable technolo-
gies, and because of the need to achieve a combination of
environmental, economic, and social objectives, the transition
to sustainable technologies is becoming imperative.
Following the initial synthesis of new remediation tech-
nologies, innovation efforts are typically directed toward
improving functionality and discovering stakeholder prefer-
ences. As the initial excitement stabilizes, the basis for com-
petitive advantage shifts from technological differentiation
to operational functionality and cost-effective implementa-
tion and cost management. The whole industry goes through
a phase of ferment when technology discontinuities are
caused, specifically, by the emergence of new type of con-
taminants. The rate of technological change and innovation
begins to accelerate and new solutions rapidly get introduced
and old ones obsoleted. In an environment of confusion for
the stakeholders, technology developers who had the ability
to integrate rapidly changing technologies into functional,
complete, easy-to-use, and supportable solutions had a sig-
nificant advantage over their competitors. When a technology
reaches the maturation phase, remediation system designers
are judged on the functionality, cost of the system, delivery
and performance of the system.
While many industries have developed uniform standards
for evaluating product or technology performance, no such
standards exist for remediation technologies. Different stake-
holders for site cleanups (such as responsible parties, regula-
tors, and community groups) may have different expectations
and perspectives on how technologies should be evaluated and
selected, let alone perform. Currently, there is no standardized
14
mechanism for reconciling these differing expectations. In
addition, multiple technologies may be available to reach the
remediation objective and end point. A particular technology
must not only be a success in that it meets the technical per-
formance criteria, but it also must be accepted by the numer-
ous stakeholders involved in site remediation.
1.2.1 Timeline: 1980s to 2010s
The evolution of remediation technologies has occurred at
a relatively rapid pace, and the most profound changes have
occurred in incremental changes in how we apply exist-
ing technologies. This was a result of the pressure from the
responsible parties and other stakeholders to improve techni-
cal efficiency and cost effectiveness. During the early years,
contaminated groundwater and vapor intrusion from soil con-
tamination were the driving concern because of the mobility
of the contaminated mass and potential liability moving off-
site. The need to contain the contamination immediately on-
site led to the universal application of pump and treat (P&T)
systems and excavation for source control and mass removal.
The need to develop cost-effective remediation solutions
led us to focus on aggressive technologies and risk-based
rational end points. While it can be argued that the initial
motive for applying these technologies has been one of sav-
ing money, the end result is much quicker cleanup times to
more acceptable cleanup levels. The metrics that influenced
the design and performance of remediation systems include
mass removal, concentration reduction, mass flux reduction,
reduction of source migration potential, plume size reduc-
tion, and changes in toxicity or mobility of residuals.
1.2.1.1  Regulatory Influences on Technology Evolution
Historically, regulators have used drinking water standards
as baseline cleanup goals for contaminated groundwater. For
soil, regulators have commonly set cleanup goals designed to
protect the groundwater beneath the soil and to prevent expo-
sure to contamination via vapor migration, soil ingestion, or
inhalation. However, these policies are changing rapidly. New
policies for groundwater and soil cleanup will affect the range
of remediation technology options and will therefore influ-
ence priorities for technology selection.
Despite the obvious demand for new and innovative reme-
diation technologies to enter the market to address the chang-
ing landscape of treatment objectives, numerous regulatory,
marketing, technical, and financial barriers have impeded the
progress in remediation technology development. As new or
redesigned technologies became available, a new problem
surfaced—the unwillingness of regulatory agencies and the
cleanup community to embrace them even as pilot tests. Many
of the new technologies were considered unproven, and the
risk of their use and potential failure was unacceptable. In
the environmental technology development community, this
phenomenon became known as part of the “valley of death,”
symbolizing the failure of some remediation technologies
to progress successfully from the research and development
stage to full-scale implementation. Many good aggressive
Remediation Engineering
technologies never reached the commercial stage because of
real or perceived risks in using them.
Regulatory concerns have also interfered with deployment
of full-scale innovative remediation technologies at many
remediation sites. Especially problematic are the slow, linear
nature of the regulatory process and inconsistencies in the
way the process is applied from site to site. These regulatory
concerns can delay the selection of remediation technologies
(which further reduces demand) and result in the use of out-
dated technologies chosen years before site cleanup begins
(although at some sites regulators do allow changes to the
original cleanup plans). Regulatory inconsistencies create
uncertainties about whether a technology proven at one loca-
tion will meet the regulatory requirements at another location,
making the stakeholders hesitant to take the risk of using an
innovative technology.
Innovative technology as applied to the cleanup of
groundwater and soil is an elusive term, for various reasons.
Regulators and other stakeholders may have different per-
spectives on which technologies are innovative. Another rea-
son why innovative is hard to define is that technologies are
continually evolving. In this industry, only a few technolo-
gies represent true breakthroughs, in the sense that they apply
concepts never before used in the field. More commonly,
innovation occurs incrementally, evolving from existing tech-
nologies. Experience and accumulated knowledge that lead
toward the best practices and technical standards are the best
metric in accepting innovative technologies.
Until the mid-1990s, changes to selected technologies in the
record of decision (ROD) of Superfund sites to allow the use of a
more effective technology were extremely rare. The inability to
change to a different remediation technology once the ROD had
been signed created a barrier to the use of innovative remedia-
tion technologies. Years can pass between signing of the ROD
and construction of the cleanup remedy and during this time,
new technologies may emerge that could improve the prospects
for site cleanup or reduce costs. However, since the late 1990s,
EPA has changed its policies concerning ROD revisions and
increasingly is allowing modifications to remedies specified in
RODs to reflect new information about cleanup technologies or
new understanding about the site. Remediation engineers must
be familiar with these policy changes because the new policies
open an avenue for increasing use of innovative, cost-saving
remedies. Recently, many changes were approved to allow mod-
ifications to the design of the original remedy, often to reflect
new monitoring from the site data. At many sites, conventional
pump and treat systems were eliminated or changed to in situ
remediation or monitored natural attenuation remedies to reflect
the improved site conditions by natural processes. Changes in
required cleanup levels (usually to less stringent levels) were
also allowed at a number of sites.
An increasing number of state environmental agencies are
adopting a process known as “risk-based corrective action”
(RBCA) to evaluate and select cleanup remedies for sites that
the states oversee. The RBCA process was developed by the
American Society for Testing and Materials and published
in the form of two industrial standard guides.16,17 The first
Remediation Engineering
standard guide, published in 1995, applies to sites contami-
nated with petroleum hydrocarbons. The second, published in
1998, applies to sites with other chemical contaminants. Most
states allow use of the RBCA process or a variant.
The petroleum RBCA standards and the super RBCA
guidelines dealing with other contaminants combine site
assessment, risk assessment, risk management, and reme-
dial action into a single framework. Rather than aiming for
a uniform goal of reducing site contaminants to natural or
background levels or achieving maximum cleanup possible
with current technology, the RBCA framework assesses cur-
rent and potential future risks at a site and sets cleanup goals
accordingly. RBCA proceeds in a tiered progression; the
analysis moves from simple to complex only as necessary and
becomes more site specific at each stage.
1.2.1.2  Pump and Treat to In Situ
In the 1980s and 1990s, P&T remediation systems were
installed at many sites to mitigate risk and remediate contam-
inants in groundwater. Although recognized as an effective
containment strategy, P&T systems may require decades to
reach stringent cleanup goals such as maximum contaminant
levels (MCLs). For this reason, in situ remediation technolo-
gies, particularly those targeting source zones, have been
developed and applied with increasing frequency in recent
years (Figure 1.9). In situ remediation technologies currently
include in  situ air sparging, soil vapor extraction, in  situ
chemical oxidation, in  situ chemical reduction, engineered
in  situ bioremediation, in  situ metals precipitation, thermal
treatment, and in situ stabilization.
These technologies advanced through basic research and
field demonstrations and have become commercially available
technologies during the last two to three decades. The perfor-
mance of these technologies under full-scale field applications
MNA with source reduction
Conventional pump and treat
In situ reactive zones (IRZ)
In situ air sparging
Concentration
Only when
contaminants
are aerobically
biodegradable
Clean-up standards
Time
FIGURE 1.9  Comparison of progress toward achieving concentration reductions via different technologies.
15
has been assessed to varying degrees and documented numer-
ous times. In situ technologies have application for both soil
and groundwater remediation and offer the potential to reme-
diate large areas and to greater depth with less site disruption
and faster cleanup times. A growing body of evidence gives
increasing level of confidence in their long-term success.
Recent advancements in related disciplines such as bio-
technology and information management will help in expand-
ing the breadth and depth of in situ bioremediation. The term
“environmental biotechnology” has a certain air of modernity
when in fact it already has a long history of use, if one consid-
ers the underlying principles and not the appellation. There is
a dynamic new definition and purpose in this discipline with
regard to bioremediation. The ability to probe the environ-
ment at the molecular level with exquisite methods, to create
a new awareness of fundamental biological processes therein,
has created an important new paradigm within remediation
engineering with respect to design and management of in situ
remediation systems. Further, biological lines of evidence
made extremely robust through the merger of biotechnology
and environmental science are poised to be incorporated into
the very fabric of site evaluation and remediation at the regu-
latory level.
Development of in situ reactive zones (IRZs) during the
mid-1990s was essentially an outgrowth of the efforts to
engineer the enhancement of the natural processes that con-
tribute toward degradation of many contaminants. Today, an
IRZ is defined as an aquifer or vadose zone segment that is
managed to chemically or biologically destroy, remove, or
transform contaminants through the injection of reagents.
An IRZ can also be sustained over a long time span, acting
as a contaminant migration barrier, in addition to being a
short-term treatment strategy for elimination of contaminant
source zones.
MNA—Monitored natural attenuation
16
TABLE 1.2
In Situ Reactive Zones for Metals Precipitation
Strategy Direct Precipitation
Biological Anaerobic biostimulation—Reduction
Anaerobic biostimulation—Sulfide precipitation
Chemical pH manipulation
Anion manipulation
Oxidation
Reduction
TABLE 1.3
In Situ Reactive Zones for Organics
Reaction Objective
Strategy Oxidation
Biological Aerobic and anaerobic biostimulation
Cometabolic aerobic biostimulation
Chemical Fenton’s reagent
Permanganate
Persulfate
Ozone
There are many possibilities for designing and operating
an engineered IRZ. They are as follows:
Based on the structure of the reactive zone:
• Mass/phase transfer zones
• Permeable reactive barriers
• Impermeable reactive zones
• Injected reagent systems (permeable zones)
• Large-scale circulatory reagent distribution systems
Based on the type of contaminant mass to be dealt with:
• DNAPL source mass removal zones
• Sorbed-phase mass desorption zones
• Interception zones within extended dissolve plumes
• In situ metals precipitation zones
Various configurations and implementation strategies of bio-
logical and chemical IRZs are presented in Tables 1.2 and 1.3.
It has been argued in the past that complex fate and transport
models are too cumbersome due to the complexity of the sites,
required levels of resolution, and the computational capacity
required to integrate the different parameters to provide much
real value to remediation practitioners. While this may have
been true in the past, advances in both the computational capa-
bility and hydrogeology concepts clearly indicate that new mod-
eling efforts are becoming useful in design and implementation
of in situ remediation systems. Modeling of fate and transport
of mixed contaminants, development of methods for scaling up
Remediation Engineering
Reaction Objective
Sorption/Coprecipitation
Iron sulfide incorporation
Iron oxide incorporation
Reduction
Anaerobic biostimulation
Anaerobically mediated abiotic reduction
Rhizodegradation (microbial reduction in plant root zone)
Zero-valent iron
Hydrolysis
from micromeasurements to field-scale prediction, and simula-
tion of remediation processes are becoming far more promising.
This computational power could be linked to the development
of improved methods for characterizing site conditions, for-
mulating conceptual models that represent system behavior,
parameterization and calibration of site-specific models, and
quantification of uncertainties in prediction. Modern computing
power can help ensure that more sophisticated numerical models
are well integrated with the biochemical, ecological, and geo-
chemical sciences sufficiently to provide the resolution needed
to improve the accuracy of model simulations and predictions
needed to advance remediation and risk reduction efforts.
1.3  REGULATORY FRAMEWORK
As environmental awareness increased over the years so did
the passage of the laws designed to protect human health and
the environment. One of the first federal environmental laws
was the River and Harbor Act of 1899 for establishing the legal
basis for banning the pollution of navigable waterways. The
Oil Pollution Act of 1924 prohibited oil discharges into coastal
waters. The Federal Water Pollution Control Act of 1948 autho-
rized the U.S. Public Health Service to work with other federal,
state, and local entities to develop comprehensive programs to
eliminate or reduce the amount of pollution discharged into
rivers, creeks, lakes, and other waterways. In the 1970s, major
environmental laws were enacted including the Clean Air Act
(1970), Clean Water Act (1972), and Safe Drinking Water Act
(1974). In addition, the USEPA was created in 1970.
Remediation Engineering
The Solid Waste Disposal Act of 1965, the first federal law
regarding solid waste management, established the minimum
federal guidelines for solid waste disposal. The Federal RCRA
of 1976 gave the USEPA authority to control hazardous waste
from “cradle to the grave.” This includes the generation, trans-
portation, treatment, storage, and disposal (TSD) of hazardous
waste. This law also sets a framework for the management of
nonhazardous waste and encouraged states to develop com-
prehensive solid waste management plans that would mini-
mize waste generation and increase recycling. It was amended
in 1991, and this amendment outlines strict requirements for
the location, design, operation, and closure of municipal solid
waste landfills and gave state and local governments responsi-
bilities the USEPA must authorize state programs.
The National Environmental Policy Act (1969) is one of
the first laws written to establish a broad national framework
for protecting the environment. The most visible require-
ments of the law, required of all federal agencies, are  envi-
ronmental assessments and environmental impact statements.
These reports analyze how a new major project or action will
most likely affect the environment and suggest a range of
options to the proposed action.
The CERCLA (1980) provides for a federally funded
“superfund” to cleanup uncontrolled or abandoned hazard-
ous waste sites as well as accidents, spills, and other releases
of contaminants into the environment. The law gives USEPA
the authority to locate the parties responsible for any release
and assures their cooperation in the cleanup. The law autho-
rizes two kinds of response actions: short-term removals,
where actions may be taken to address releases or threatened
releases requiring prompt response and long-term remedia-
tion response actions, which permanently and significantly
reduce the dangers associated with releases of hazardous sub-
stances that are serious, but not immediately life threatening.
These sites are listed on EPA’s national priority list.
In 1985, USEPA created the Office of Underground Storage
Tanks to carry out a congressional mandate to develop and
implement a regulatory program for UST systems. EPA
works with state and local governments to prevent and clean
up releases from USTs mostly containing petroleum products.
The mission of these regulations is to effectively regulate the
safe operation of USTs and to ensure appropriate investigation
and cleanup of releases from these tanks for the purpose of
protecting human health and the environment.
1.3.1 Evolving Regulatory Influence
While this book does not attempt to cover the range of envi-
ronmental regulations and issues that impact the world we live
in, it is important to consider the regulatory arena in which
the remediation work is being conducted. The degree of inter-
action required with the regulatory agencies will depend on
the regulations under which the project is being implemented,
complexity of the project, and the type of technologies being
used, whether conventional or innovative.
Although prescriptive cleanup standards generally must be
achieved at most contaminated sites, changes in these standards
17
in the overall process of site cleanup under RCRA, CERCLA,
State Voluntary Programs, and other regulations are becoming
increasingly common. The driver for some of these changes
is recognition of the limits of available technologies for site
cleanup and the realization that achieving existing baseline stan-
dards with existing technologies is not possible for certain types
of contamination at sites with complex geologic conditions. The
driver for other changes in regulatory practice is recognition of
the extremely high costs of cleanup using conventional methods.
Technologies that are unable to achieve baseline standards or
the ones the regulators rejected as insufficient in the past may be
acceptable for use in the new regulatory environment.
Most stakeholders will admit that the last 30 years of com-
mand and control regulatory structure has produced significant
improvements in the quality of our environment. Yet analysts
and practitioners have begun to recognize that this regulatory
structure, along with its institutional rigidity, may have become
increasingly out of step with the demands and realities of envi-
ronmental protection. Insulated from external pressures, so they
can focus on protecting the values they are mandated to safe-
guard, it becomes relatively easy for regulators to inform the
stakeholders about their procedural requirements than discuss
the inherent information gathering and decision-making require-
ments. The need to preserve consistency and predictability of the
process within a command and control regulatory structure is at
odds with the push for implementing innovative and cutting-edge
technologies without any proven track records.
In response to the tensions generated by traditional regula-
tions, a network of stakeholders, including academic institutions,
government agencies, and private sector industries has begun to
explore new institutional platforms that address the complexity
and uncertainty of reaching regulatory end points in remediation
projects. The hope today is that as the landscape within the reme-
diation industry changes, the regulatory architecture evolves
with a pragmatist philosophy. The instinct to seek consistency
and predictability of the process should be replaced with insti-
tutionalization of better ways of continuous improvement and
learning from the inevitable surprises that experience offers us.
The current relationship between responsible parties and the
regulatory institutions throughout the United States in certain
industries and agencies, on the state and federal level, resembles
the philosophy described earlier. The evolution of these rela-
tionships can be divided into three phases. The first phase is
conventional regulatory practices, more commonly known as
“command and control,” and the changes began after recogniz-
ing the importance of interaction and joint problem solving. The
second phase, a period of experimentation and coeducation was
marked by a deliberate dimension of the process of change. The
last phase is marked by the notion of learning as a central con-
cept in the process of developing new practices and institutional
frameworks. This is a healthy development within the overall
evolution of the remediation industry for the next few years.
1.3.2 Evolution of Cleanup Standards
A cleanup level is the concentration of a hazardous sub-
stance in soil, water, air, or sediment that is determined to be
18
protective of human health and the environment under speci-
fied exposure conditions. Cleanup levels, in combination with
points of compliance, typically define the area or volume of
soil, water, air, or sediment at a site that must be addressed by
the cleanup action. The first step in setting cleanup levels is
to identify the nature of the contamination, potentially con-
taminated media, current and potential pathways of exposure,
current and potential receptors, and current and potential land
and resource uses. A conceptual site model (CSM) must be
developed as part of this scoping process.
Cleanup standards are identified for the specific hazard-
ous substances at a site and the specific areas or pathways,
such as land and water, where humans and the ecosystem
can become exposed to these substances. Cleanup standards
consist of the following:
• Cleanup levels for hazardous substances present at
the site
• The locations where these cleanup levels must be
met (points of compliance)
• Other regulatory requirements that apply to the site
as a result of the type of action and/or location of the
site (applicable state and federal laws)
This approach provides a uniform method for identifying
cleanup standards, within each regulatory jurisdiction, and
requires that all cleanups under that structure meet these
standards. Setting cleanup standards also involves being
able to demonstrate that they have been met. This involves
specifying where on the site the cleanup levels must be met
(points of compliance) and how long will it take for a site
to meet cleanup levels. There are two general approaches
to setting up cleanup standards at specific hazardous waste
sites: (1) standards are set equal to state or federal uniform
numerical concentration limits, and (2) site-specific stan-
dards are based on evaluations of factors such as human
health and ecological risk, technical feasibility, and cost.
All noncancer health effects are assumed to have a dose
threshold. It is assumed that below some doses, there are no
health effects. A chemical can often produce many different
types of adverse health effects, each with its own threshold.
If the threshold for the most sensitive health effect can be
identified—the effect that occurs at the lowest dose—limiting
exposure to doses below that threshold should protect against
all of the adverse effects of the chemical. This concept is
the basis for the USEPA reference dose (RFD). The USEPA
examines toxicity data for a chemical, identifies the most
sensitive effect, and then determines a dose sufficiently low
enough to prevent the effect from occurring in the most sensi-
tive individuals. It is important to point out that the toxicity
values developed by the USEPA—the RFDs and cancer slope
factors (CSFs)—are developed conservatively.
Regulatory agencies view risks from carcinogens differently
from noncancer health effects. For most chemicals, carcinoge-
nicity is assumed not to have a threshold, and even very small
doses are assumed to pose some (albeit small) risk of cancer. In
this view, safety must be defined as some risk (i.e., probability)
Remediation Engineering
of cancer of small enough to be considered insignificant. A
lifetime excess cancer risk (probability) of 1 × 10−6 (one in a
million) is used for calculating cleanup target ­levels for carcino-
genic compounds. The USEPA has developed measurements of
cancer potency of carcinogens, which are termed “cancer slope
factors.” CSFs are calculated through various low-dose extrapo-
lation procedures and represent the increase in lifetime cancer
risk per unit dose, with the CSF units of 1/(mg/kg/day).
Surface soil contamination is a worldwide problem that
represents both human health and ecosystem risks. Often,
regulatory jurisdictions seek to limit these risks by specifying
the maximum amount of contaminant that may be present in
soil without prompting a regulatory response. There is no gen-
erally accepted terminology for the values used. In the United
States, they are often referred to as soil remediation levels,
risk-based screening levels, remediation goals, target levels,
or generic soil remediation standards. Elsewhere around the
world, they may be called “trigger values,” “intervention val-
ues,” “permissible concentrations,” “limit values,” or simply
as “regulatory guidance values” (RGVs).
In the United States, national RGVs are promulgated by
the USEPA, but most soil contamination falls under state or
local regulatory jurisdiction. All 50 U.S. states, the District
of Columbia, several cities, counties, and territories, and at
least eight autonomous Native American tribes have devel-
oped RGVs. Elsewhere around the world, there are at least 50
nations that have promulgated national RGVs, and in several
countries (Australia, Brazil, Canada, Denmark, Italy, Mexico,
New Zealand, Spain, and the United Kingdom), there are also
city, regional, and/or provincial values.18 Jurisdictions seldom
agree on the number of chemicals that should be regulated but
often agree on the most common pollutants.
Regulatory guidance models that vary over 5 or 6 orders
of magnitude for comparable exposures are problematic for
several reasons. This has been discussed elsewhere, but is
worth reiterating. Values that are too low lead to unjustifiable
remediation obligations. This is unjust for those who must
pay for remediation. Furthermore, when analyses yield val-
ues that span several orders of magnitude, one must question
the validity of the fundamental approach. RGVs are derived
using simple models applied to standard, conservative expo-
sure scenarios. If this approach is not capable of resolving the
values to within 6 orders of magnitude, it is difficult to see
how the approach is sufficiently protective of human health.
The two chlorinated solvents most typical of concern are
PCE, a chemical long used in dry cleaning, and TCE, used
mainly in cleaning and degreasing activities in manufactur-
ing. Now, the rules for remediating these two solvents will
be changing as a result of human health risk assessments
(HHRA) conducted by the EPA. Human health assessments
look at both the potential excess cancer and noncancer (such
as neurotoxic) risk related to a contaminant. EPA determined
that the cancer and noncancer risks related to TCE exposure
were greater than previously believed. As a result, it is antici-
pated that EPA will lower the cleanup standard for drinking
water to a more stringent level, and vapor intrusion screening
standards for TCE are also expected to go down.19
Remediation Engineering
EPA’s PCE human health assessment identified less cancer
risk, but more noncancer risk than previous assessments. The
combined information has prompted EPA to relax require-
ments for PCE sites by raising the Regional Screening Level
for PCE. It will be up to individual states whether or not to
adopt EPA’s new screening level; already, the regulated com-
munity is lobbying state agencies to take the new PCE risk
profile into account in evaluating screening and cleanup stan-
dards. It is not yet known whether EPA plans to change the
drinking water standard for PCE.20
1.3.3 Risk-Based Approaches
Virtually every aspect of life involves risk, and how we deal
with it depends largely on how well we understand it. The pro-
cess of risk assessment has been used to help us understand
and address a wide variety of hazards and has been an effec-
tive tool to the regulatory agencies, industry, academic com-
munity, and all other stakeholders in evaluating public-health
and environmental concerns. From protecting air and water
to ensuring the safety of food, drugs, and consumer products
such as toys, risk assessment is an important public-policy
tool for informing regulatory, technological, and corrective
action decisions and developing approaches for considering
the costs and benefits of regulatory policies and actions.
One of the most challenging and difficult aspects of envi-
ronmental management at contaminated sites is linking the
environmental risk assessment with remedial actions selected
to mitigate identified risks. Risk assessments, conducted
in conformance with guidance from regulators, provide an
understanding of environmental consequences that will persist
in the absence of any remedial action. They include HHRA
and ecological risk assessments (ERA), developed using simi-
lar but independent methods. While more risk management
decisions have been driven by human health risks, ecological
considerations can also be a major driving force and are of par-
amount importance to many stakeholders. The HHRA process
is better defined and more straightforward, while ERAs, which
can involve multiple receptors and contaminants, rely substan-
tially on a less prescribed weight-of-evidence approach.
However, risk assessment is at crossroads. Despite advances
in the field, it faces a number of substantial challenges, includ-
ing long delays in completing complex risk assessments, some
of which take decades to complete, lack of quality data, which
leads to important uncertainty in risk assessments, and the
need for toxicological data of many unevaluated chemicals
and emerging contaminants. The science of risk assessment
has become increasingly complex. Improved analytical tech-
niques have produced more data that lead to questions about
how to address issues of, for example, multiple chemical
exposures, multiple risks, and susceptibility in populations.
In addition, risk assessment is now being extended to address
broader environmental questions, such as life-cycle analysis
and issues of costs, benefits, and risk-benefit tradeoffs.
Decision-making based on risk assessment has also
become bogged down. Uncertainty, an inherent property of
scientific data continues to lead to multiple interpretations
19
and contribute to decision-making gridlock. Stakeholders
including community groups, environmental organizations,
industry, and consumers are often disengaged from the risk-
assessment process at a time when risk assessment is increas-
ingly intertwined with societal concerns. Disconnection
between the available scientific data and the information
needed by the decision-makers hinder the use of risk assess-
ment as a decision-making tool.
Addressing uncertainty and variability is critical for the
risk-assessment process. Uncertainty stems from lack of
knowledge, so it can be characterized and managed but not
eliminated. Uncertainty can be reduced by the use of more or
better data. Variability is an inherent characteristic of a popu-
lation, in as much as people vary substantially in their expo-
sures and their susceptibility to potentially harmful effects of
the exposures. Variability cannot be reduced, but it can be
better characterized with improved information.
A challenge to risk assessment is to evaluate risks in ways
that are consistent among chemicals that account adequately for
variability and uncertainty and that provide information that is
timely, efficient, and maximally useful for risk characteriza-
tion and risk management. Historically, dose-response assess-
ments have been conducted differently for cancer and noncancer
effects, and the methods have been criticized for not providing
the most useful results. Consequently, noncancer effects have
been underemphasized, especially in cost–benefit analyses.
A consistent approach to risk assessment for cancer and noncan-
cer effects is scientifically feasible and needs to be implemented.
From past experience, it is clear that developing risk assess-
ment toxicity criteria (e.g., RFDs or CSFs), even for more data-
rich chemicals (e.g., arsenic) with considerable epidemiological
and mechanistic data, is not necessarily clearer or easier than
for chemicals with less information. The refined testing meth-
ods and approaches will require that public health decision-
making consider more evidence-based approaches for dealing
with uncertainty. As our understanding of toxicity mechanisms
increases, so does our awareness of what we don’t know.
Toxicity testing has traditionally relied on studies of
adverse health outcomes observed in animals at high doses,
with subsequent extrapolations to expected human responses
at much lower doses. These approaches date back to the 1950s
when knowledge of the biology underlying toxic response
was primitive. However, current and anticipated scientific
advances can be expected to transform toxicity testing to
permit broader coverage of the universe of potentially toxic
chemicals to which humans may be exposed, using more
timely and more cost-effective methods for toxicity test-
ing.21 Greatly expanded use of high and medium throughput
in vitro screening assays, computational chemistry and toxi-
cology, systems biology, and pharmacokinetic models, along
with other emerging high-content testing methodologies such
as functional genomics and transcriptomics have enabled this
advanced vision of toxicity testing.22 Figure 1.10 illustrates
the linkage between the current risk assessment paradigm
and the future vision of toxicity testing.
In recent years, ERA methodologies to evaluate contami-
nant risks have been refined. EPA’s current guidelines23,24
20
Dose response
assessment
Chemical
characterization Mode of action
Affected
Compounds
pathways
Assess
biological
Perturbation
Measures
Metabolite of dose
(s)
in vitro
Hazard identification
Risk characterization
FIGURE 1.10  Toxicity testing and risk assessment. (From National Research Council (NRC), Toxicity Testing in the 21st Century: A
Vision and a Strategy, National Academy Press, Washington, DC, 2007.)
describe how to link management goals with assessment
end points and measures of effects. They support a tiered
approach wherein the studies conducted for each tier are
designed to reduce the uncertainty identified in the previous
tier. Incorporation of ecological considerations into decisions
about cleanup, restoration, and long-term stewardship, both
short term and long term, requires
• Understanding public perceptions of ecological val-
ues, including aesthetics and existence values
• Understanding contamination impacts within the
structure and functionality of ecosystems
• Developing bioindicators of ecological health
• Developing indicators of ecosystem functioning
• Developing and implementing a biomonitoring
plan before, during, and after corrective actions are
implemented
The impacts of high financial and public relation stakes of
risk management have placed unprecedented pressure on
risk assessors within regulatory agencies. But risk assess-
ment remains essential to regulatory agencies’ mission to
ensure protection of public health and the environment.
Much work is needed to improve the scientific status, util-
ity, and public credibility of risk assessment. Future empha-
sis should be on designing risk assessments to ensure that
they make the best possible use of available science, are
technically accurate, and address the appropriate risk-
management options effectively to inform risk-based deci-
sion-making. It is hoped that future recommendations and
proposed framework for risk-based decision-making will
provide a template for the future of risk assessment and
strengthen the scientific basis, credibility, and effectiveness
of future risk-management decisions.
Remediation Engineering
Population
based studies
Dose
response
analysis for Calibrating in
Exposure
perturbations vitro and human
guideline
of toxicity dosimetry
pathways
Human
exposure data
Exposure assessment
1.3.4 Technical Impracticability Considerations
Under both CERCLA and RCRA, required cleanup standards
for contaminated groundwater and soil can be waived in cases
where achieving these standards is not possible with existing
technologies. For example, CERCLA states that cleanup stan-
dards can be waived if cleanup is technically impracticable
from an engineering perspective.25 RCRA contains similar
conditions. Both statutes state that engineering feasibility and
reliability, rather than cost, should be the key considerations
in determining the practicality of a cleanup.
Although the USEPA guidance document is applicable
to all types of contaminants, it emphasizes DNAPLs. The
guidance document states, “As proven technologies for the
removal of certain types of DNAPL contamination do not
exist yet, DNAPL sites are more likely to require TI [techni-
cal impracticability] evaluations than sites with other types of
contamination.” It indicates that up to 60% of CERCLA sites
may contain DNAPLs, according to EPA surveys.
The key elements of the TI guidance document are its dis-
cussion of (1) the timing of decisions concerning the TI of
cleanup, (2) alternative remedial strategies where cleanup is
not possible, (3) long-term monitoring requirements for sites
where cleanup goals are waived due to TI, and (4) types of
data that must be provided to EPA to evaluate the technical
feasibility of achieving cleanup standards.
1.4  IMPORTANCE OF HEALTH AND SAFETY
The number of full-scale systems, implementing a wide range
of remediation technologies, has grown significantly during
the last three decades, in direct proportion to the growth of the
industry itself. Occupational health and safety considerations
associated with these projects have also kept pace during this
Remediation Engineering
time frame. Along with the many innovative remediation tech-
nologies, innovative solutions concerning chemical protective
clothing, air monitoring, sampling equipment, and the man-
agement of physical hazards have been introduced. However,
there is another school of thinking which implies that the
development of strategies to reduce health and safety risks at
hazardous waste sites have not kept pace with the develop-
ment of aggressive innovative remediation technologies.
The risks that hazardous waste sites pose to society have tra-
ditionally outweighed the perceived risks they pose to workers
partaking in remedial actions in the past. For without the soci-
etal drivers to initiate edicts to address these risks, the reme-
diation industry would certainly have never been established.
However, as Occupational Safety and Health Administration
(OSHA) and Environmental Health and Safety (EH&S) pro-
fessionals are obligated to protect workers regardless of their
occupational orientation, the protection of remediation work-
ers cannot be an afterthought of the greater environmental
and societal good when strategies exist to do both simultane-
ously. The complex interrelationships between multiple parties
involved in a remediation project sometimes make it difficult
to administer an effective health and safety program. To imple-
ment an effective, well-coordinated program all participants
must be made aware of the health and safety roles and respon-
sibilities of all parties involved in site remediation.
Much has been learned within the remediation industry
over the last 30 years. Today, it is understood that in order to
maintain quality operations and maintenance of remediation
systems in a safe manner, all aspects of the work process must
be carefully planned, budgeted, and executed. Importantly,
this includes effective management systems that integrate
health, safety, and environmental concerns into the daily rou-
tine. Project field staff and subcontractor employees face the
potential risk of exposure to hazardous chemicals and physi-
cal agents for much longer hours and at potentially higher con-
centrations than the general public. In order to minimize and
mitigate the risk to the employees and the public from such
exposure, management systems and programs that include
effective standard operating, and communication procedures
must be developed and implemented.
The remediation industry, during its early years, had to
address a broad range of health and safety transgressions
while employing interdisciplinary project teams. During the
last few years, the industry has improved its health and safety
mission to a significantly higher level due to both internal and
external pressures. Health and safety considerations at reme-
diation sites started to follow a strict and hierarchical meth-
odology beginning with the investigation process. Following
this step, development and implementation of comprehensive
work plans and health and safety plans to programmatically
protect workers through various engineering, administrative,
safe work practice and personal protective equipment (PPE)
control measures have become a routine practice.
Implementation of hazardous waste remediation projects
in close proximity to communities must be conducted in the
safest possible manner. Thus, it is important that the health
and safety planners take time to gain situational awareness
21
of the potential hazards in regard to the proximity of the site
location to the surrounding communities and stakeholders.
Health and safety professionals from the project team must
take the opportunity to take local emergency responders to a
site with highly complex operations and allow time for them
to walk the job site and be familiar with the hazards. The proj-
ect team has an obligation to establish a contingency plan and
an emergency action plan for the area of operational impact.
1.4.1 Awareness and Current Trends
A health and safety management system involves the intro-
duction of processes designed to decrease the incidence of
injury and illness during project implementation. Successful
implementation of the system requires the management’s
commitment, effective allocation of resources, and a high
level of employee participation. The scope and complexity of
a health and safety management system will vary according
to the size and type of workplace. The following elements are
the basic components of an optimal system and are very much
interdependent: management leadership and organizational
commitment, hazard identification and assessment, hazard
control, work site inspections, worker competency and train-
ing, incident reporting and investigation, emergency response
planning, and program administration.
Most of the traditional activity-based health and safety
programs focus on high-severity safety risks for large-scale
remediation system implementation or construction-related
activities. Such focus helps firms identify the high risk pro-
cesses so they may be targeted for improvement. However,
there is so little focus on quantifying safety risk at the routine
activity level or include low-severity, high-frequency risks that
contribute to a large portion of a total risk. General examples
of prudent practice include minimizing chemical exposures,
avoiding underestimation of risk, providing adequate ventila-
tion, focusing on chemical safety programs, and attention to
permissible exposure limits.
In recent years, there has been a shift in emphasis within
the remediation industry, away from individual level, activity-
based factors that might be responsible for accidents and inci-
dents, such as human error and noncompliance with safety
procedures, toward organizational factors such as behavior-
based safety climate. An important driver toward this shift is
the assumption that the relationship between safety climate
and system safety is significantly influenced by individual
safety behavior. It is also believed that an excellent safety cli-
mate has a beneficial impact on the knowledge, motivation,
and performance of individuals within the organization.
Safety climate is a specific form of organizational climate,
based on the behavior of the employees that describes indi-
vidual perceptions of the value of safety in the work environ-
ment. A range of factors has been identified as being important
components of a safety climate. These factors include man-
agement values (e.g., management concern for employee
well-being), management and organizational practices (e.g.,
adequacy of training, provision of safety equipment, quality of
safety management systems), communication, and employee
22
involvement in workplace health and safety. A range of stud-
ies have demonstrated that these factors predict safety-related
outcomes, such as accidents and incidents.26–28
This shift is taking place as a result of health and safety per-
formance within the remediation industry being identified as a
domain that was in need of large-scale and long-term behav-
ior change. For this to happen, however, a prominent paradigm
shift was required. It was realized that the standard command
and control activity-based enforcement approach to safety has
only a limited impact, as witnessed by the safety performance
plateaus experienced by our industry during the early years.
The behavior-based safety approach provides tools and pro-
cedures employees can use to take control of their own safety
performance, thereby enabling a bottom-up empowerment
approach to reducing occupational risks and preventing work
place injuries. Unlike the traditional safety culture, the focus is
not on compliance with OSHA safety rules, government stan-
dards, or company policy, but rather on how to get more people
involved in a behavior-based safety approach to proactive man-
agement of occupational health and safety risks.
1.4.2 Potential Hazards
Remediation systems, incorporating a single technology or
multiple technologies, have the potential to pose various levels
of hazards to workers. If these hazards are properly evaluated
and controlled, the systems can be operated safely. There is a
tendency for hazards associated with treatment technologies
to be overlooked, particularly during routine and maintenance
operations. Common health and safety hazards associated
with remediation system operation are listed in the follow-
ing. To minimize or eliminate the potential hazards, the proj-
ect team should evaluate each phase of unit operations such
as mobilization, installation, operation, maintenance, disas-
sembly, and demobilization. Health and safety professionals
should also evaluate how the equipment hazards may vary
with site-specific requirements and type of contaminants.
Common factors that should be evaluated when developing a
site-specific health and safety plan are as follows:
• Process chemicals
• Site contaminants
• Process waste materials
• Dust
• Ergonomic risks
• Thermal burns
• Confined space entry
• Corrosive materials
• Flying particles and falling material
• Slips, trips, and falls
• Elevated work surfaces
• Long duration tasks
• Electrical hazards
• Fire and explosion
• Mechanical equipment
• High pressure
• Noise
Remediation Engineering
• Moving vehicles
• Material handling
• Heavy equipment operation
• Building demolition
The development of a health and safety plan is required by Title
29 of the Code of Federal Regulations (29 CFR), promulgated
by the OSHA. 29 CFR 1910.120 specifically describes stan-
dards for employees engaged in hazardous material operations.
The provision, known as OSHA’s Hazardous Waste Operations
and Emergency Response, mandates the development of health
and safety programs for site remediation workers, emergency
responders, TSD facility personnel, and UST workers. Health
and safety programs require the designation of a safety coor-
dinator responsible for reviewing and approving the site safety
plan. A good program requires a written safety standard oper-
ating procedure for normal work and during an emergency,
sufficient employee training, employee medical monitoring,
proper safety clothing, monitoring devices, and other PPEs.
The health and safety plans are site specific and they are
designed to prevent injury and exposure to chemical, mechani-
cal, and work-related hazards. The plan should be prepared by
a qualified safety officer and reviewed and revised routinely. To
keep it current at a minimum, the site-specific health and safety
plan must contain the following components at a minimum:
• Evaluation of the health and safety risks associated
with the site and system operation
• Identification of key personnel and their alternates
responsible for site safety and emergency response
• Appropriate level of protection for site workers
• A site map based on the type of activity showing the
different zones
• Established emergency procedures
• Emergency medical care locations through prior
arrangements
• Implementation program for air monitoring and
medical monitoring
• Specified personnel and equipment decontamination
procedures
• Control procedures for site access
• Personnel training procedures
• Established communication setup
• Established evacuation routes
1.4.3 Incorporation of Health and
Safety into the Design Process
As new remediation technologies were being introduced into
the remediation industry at a hastened pace, the health and
safety risks posed on the field staff have historically been
addressed at the end of the technology development stages.
In order to address this concern, regulatory agencies and
design teams must consider worker health and safety earlier
in the design phase. Strategies to achieve this include identi-
fying and mitigating technology hazards from the onset, uti-
lizing process safety management techniques to thoroughly
Remediation Engineering
evaluate these technologies, and improved training efforts.
Design focus should be placed upon (1) new instrumentation
and innovations in health and safety aspects of technologies,
(2) controlling hazards before they appear through better pre-
pilot stage health and safety design, and (3) addressing health
and safety management elements such as physical hazards,
medical surveillance, and project team training. More details
on health and safety in design are provided in Chapter 3.
The overall goal of incorporating safety in the design process
is to eliminate loss incidents related to remediation projects by
promoting effective loss prevention planning during the engi-
neering design phase, rather than waiting to address them as
part of the task planning at the time of conducting construction
or operations and maintenance activities. The purpose should
be to fully integrate the best safety engineering design practices
into project-level activities. This approach will promote own-
ership, stewardship, and creativity in the implementation of
effective health and safety and loss prevention practices by the
project teams. This will provide a clear path from identification
of the tasks and associated project hazards to implementation of
engineering controls reflecting industry best practices, and shar-
ing of lessons learned from similar projects.
Safety design is an iterative continuous improvement pro-
cess that starts during a project’s conceptual and preliminary
design phases and continues through system implementation
(i.e., construction and operation). After engineered systems
are built, there should be an ongoing continuous improve-
ment process to optimize performance and effectiveness
(Figure  1.11). The incorporation of loss prevention into the
conceptual design should begin with industry and corpo-
rate best practices. Four categories of improvements to be
addressed during the design process are the following:
1.
System fail-safes—Analyze each engineered system
element (e.g., process, electrical, and mechanical)
within the overall system for potential issues that
may lead to accidents and losses, and use an appro-
priate hierarchy of engineering controls to imple-
ment best practices for loss prevention. Design an
appropriate level of redundant fail-safes to satisfy
project and client safety requirements.
2.
Regulatory requirements—Ensure that process safety
elements driven by local, state, and federal regulations
Design process
Conceptual design
System Health and safety
Final design Best practices
design elements
Field experience
Implementation
feeds back into
QA/QC and design
policies
FIGURE 1.11  Process for including health and safety consider-
ations during system design activities.
23
are incorporated in the design. This not only will
incorporate safe design elements but will also help
prevent costly project construction and startup delays
caused by a failure to design to regulatory-specific
requirements.
3.
Construction—Evaluate construction procedures to
determine whether inherent risks can be minimized,
or averted, by employing safe design best practices
during the design phase to ensure that construction
can be completed in the safest manner possible.
4.
Operation and maintenance (O&M)—Evaluate
design modifications, material substitutions, or pro-
cedures to prevent potential losses during routine
and nonroutine O&M and monitoring activities.
1.5  CURRENT TRENDS IN REMEDIATION
Ongoing and potential future occurrences of environmental
contamination due to industrial and other anthropogenic activi-
ties such as natural resources exploration are an area of concern
for environmental regulators and public health authorities. At
the same time, growing awareness regarding environmental
protection, pollution prevention, safer industrial ecology, and
cleaner manufacturing technologies have propelled tremendous
efforts toward eliminating pollution problems and protecting
human health and the environment. To better promote and sup-
port environmental protection and sustainable and responsible
remediation solutions, our industry has launched an organized
effort supported by multiple programs and initiatives. The main
aim of this effort is to integrate, coordinate, and engage the dif-
ferent ideas put forth by the various stakeholders. Evolutionary
developments in the expansion of remediation engineering are
presented in Figure 1.12.
Future advancements in the remediation industry have to
make sure our natural and built environments and brown and
green fields are safe and clean for future developments. These
responsibilities are extremely important to ensure that the
next generation will not have to deal with problems like how
our generation dealt with the legacies of past industrial and
anthropogenic activities. As the human population continues
to grow and industrial and property development continu-
ally expands, the task of protecting the environment becomes
even more complex. The focus of environmental protection
has shifted from regulating single chemicals to developing a
multimedia approach to understand the synergistic efforts of
contaminants distributed throughout the environment. Our
industry should continue to seek innovative environmental
solutions and to conduct research designed to address gaps in
scientific knowledge.
It has become increasingly clear that remediation of com-
plex sites to drinking water standards is not only impractical,
but also cost prohibitive to be completed within reasonable
time frames. Setting such goals is unrealistic and ultimately
fails to provide a fiscally responsible solution that is protective
of human health and environment. The potential barriers to
achieving restoration goals at these complex sites are due to
uncertainties in technology performance related to subsurface
24
Evolutionary phases of remediation engineering
Symbiosis of
multiple technical
disciplines
Ex situ focus
Excavation,
incineration, P&T
containment
Discovery
of wastes
Regulations
in place
1970s 1980s
FIGURE 1.12  Evolutionary developments in the expansion of remediation engineering knowledge base.
complexities and also the reluctance of some stakeholders to
accept the break through developments in scientific knowl-
edge. More often than usual, it is disappointing to note that
the best practices and knowledge gained from successful clo-
sure of different sites are not codified and scaled up across the
industry for the benefit of all stakeholders.
1.5.1 Sustainable (Green) Remediation
It is important for us to define what is a “sustainable commu-
nity” for the stakeholders before we discuss the importance and
future direction of sustainable or green remediation. In its most
basic form, a sustainable community is one that can continue in
a healthy way in the midst of uncertain natural and built envi-
ronments impacted by developmental or remediation activities.
More formally, a sustainable community reflects the interde-
pendence of economic, environmental, and social issues by
growing and prospering without diminishing the land, water,
air, natural, and cultural resources on which communities
depend (Figure 1.13). Infrastructure development, engineering,
and construction activities are managed in a way that protect
economic, ecological, and scenic values for the stakeholders to
experience the environment in their neighborhoods.
In this section, sustainable remediation is defined as a
remedy or combination of remedies whose net benefit on
human health, the ecosystem, and the environment is maxi-
mized through the judicious use of limited resources. There
is considerable debate among stakeholders regarding what is
sustainable and what is judicious. However, many concepts
are garnering the interest of remediation stakeholders who
are willing to identify and evaluate net benefit solutions to
complex remediation challenges on a project-by-project basis.
Remediation Engineering
Merger of water
supply and remediation
industry
Green
remediation
Enhanced investigation
techniques
advanced analytical
methods
Emerging contaminants
Anaerobic bioremediation
Metals precipitation
Focus on sediments
In situ focus contamination and NAPLs
In situ physical
technologies
aerobic bioremediation
1990s 2000s 2010s 2020s
Expansion of knowledge base
As stated previously, the selection of remediation tech-
nologies in the United States historically has been driven by
human health and environmental protection criteria, cost,
efficacy, technical practicability, and regulatory acceptance.
However, stakeholders have learned that these remediation
drivers do not necessarily result in a clean or closed site on a
timely basis and, depending on the perspective of the stake-
holder, could represent a net environmental loss to the larger
community. Accordingly, stakeholders have realized that the
selection of remediation technologies should also evaluate the
probability with which these and future projects will have a
net environmental and social benefit.
Generally, the stakeholders in the remediation process
belong to one of the following four groups: site owners, regu-
latory entities, the public, and remediation service providers.
The boundaries between these groups are, at times, indis-
tinct; however, each is represented in one form or another as
a stakeholder in the process. While sustainability may not
mean the same thing to all of these groups, it is through an
understanding of the perspectives of each of these groups that
the stakeholders can come to a mutually beneficial, project-
specific definition of sustainability.
Green remediation is the practice of considering environ-
mental impacts of remediation activities at every stage of the
remediation process in order to maximize the net environ-
mental benefit of a cleanup. It reduces the demand placed on
the environment during cleanup actions, otherwise known as
the “footprint” of remediation activities, and avoids the poten-
tial for collateral environmental damage. The best definition
for green and sustainable remediation is the site-specific
employment of products, processes, technologies, and pro-
cedures that mitigate contaminant risk to receptors while
Remediation Engineering
Environment
Social
equity
FIGURE 1.13  Concept of sustainable remediation.
making decisions that are cognizant of balancing community
goals, economic impacts, and environmental effects (Figure
1.13). Evaluation factors include selection of remedy, selec-
tion of materials used, energy requirements, waste generation,
emission of greenhouse gases, carbon footprint, efficiency of
on-site activities, and reduction of ecological impacts on sur-
rounding areas29 (Table 1.4). Emphasis should also be placed
on health- and safety-related activities. Presumptive thinking
always has been to contain and clean up environmental con-
tamination by focusing primarily on cost and technical effec-
tiveness. Furthermore, many of the presumptive remedies,
such as P&T systems, were designed and installed in an era
when energy was less expensive and sustainability consider-
ations were not part of the equation.
The sustainability movement (and the green remediation
concept) suffers from the ambiguities resulting from multiple
definitions. Some embrace narrow meanings and others more
multifaceted meanings under different contexts. The  reme-
diation industry is striving for a type of definition that col-
lectively involves net beneficial environmental impacts,
economic viability, and reduction in resource consumption
and the long-term benefits to the environment we live in.
However, increasing prominence of green remediation has
TABLE 1.4
Sustainable Remediation Indicator Categories
Environment Social
Emissions to air Human health and safety
Soil and ground conditions Ethics and equity
Groundwater and surface water Neighborhoods and locality
Ecology Communities and community involvement
Natural resources and waste Uncertainty and evidence
Source: Bardos, P., Remed. J., Winter, 23, 2014.
25
Ideal sustainable
solution
Economics
initiated the development of more appropriate frameworks
and tools that will provide both a guidance for a shift toward
sustainability and a quantitative measure of that shift. Due to
the diversity of the parameters that are usually the focus of
green remediation assessments, planning and evaluating the
progress toward sustainability inevitably becomes a compli-
cated task. In our view, these assessments have so far relied
on reductionist methodologies and tools with the recurring
appeal for keeping it simple.
There are many quantitative models available to capture
and aggregate the diverse set of parameters with different
units of measurement with a single scale of analysis. The com-
ponents of sustainability assessment should comprise clear
objectives for the assessment, clear boundaries, an agreed
scope (range) for sustainability indicators, and a methodology
for combining individual comparisons for particular indica-
tors into an overarching view of sustainability. The methodol-
ogy follows a procedure relying on initial quantification and
subsequent aggregation of the diverse sustainability elements
using a common currency and reliable supporting data. We
believe that this approach is the best approximation to under-
stand and describe the set of conditions to the stakeholders
toward informed decision-making.
Economic
Direct economic costs and benefits
Indirect economic costs and benefits
Employment and employment capital
Induced economic costs and benefits
Project lifespan and flexibility
26
How companies implement green remediation, and sus-
tainability in general is another area of growing importance
where linkage between the board room and operations is
critical. Placing green remediation activities within the wider
context of the corporate sustainability agenda creates the inev-
itable conflicts between the individual elements of the evalua-
tion and implementation process. There is an ever expanding
portfolio of objectives and initiatives at various management
levels within any organization. The governing, macro-level
sustainability criteria developed at the board level are very
qualitative in nature and, in most cases, conflict with the
measurable and quantifiable criteria assigned to remediation
project managers in the front lines of project implementa-
tion. The micro-level, threshold criteria, project managers
are tasked with, still revolves around cost effectiveness as the
primary factor. The senior-middle managers within organi-
zations are the primary stakeholders incentivized to imple-
ment green remediation activities for the right reasons. They
are judged by balancing criteria and metrics which enable
them to maintain the profile of green remediation in front of
all stakeholders, encourage appropriate technologies into the
market, ensure the development of standard competencies in
green remediation within our industry, and ensure that regula-
tions will be proportionate in the future.
One potential reason many companies do not actively
address sustainability despite the attention paid to it by the
media, consumers, and investors is that many have no clear
definition of it. Overall, 20% of executives say their compa-
nies don’t have a definition.31 Among those that do, the defini-
tion varies: 55% define sustainability as the management of
issues related to the environment (e.g., greenhouse gas emis-
sions, energy efficiency, waste management, green-product
development, and water conservation); 56% of all executives
define sustainability in two or more ways, including manage-
ment of governance issues, and most companies incorporate
sustainability as a reputation-building effort.
1.5.2 Emerging Contaminants
Population growth, drought, and increased industrial demands
for water are creating more pressure on limited groundwa-
ter resources. This pressure is heightened in populated and
industrialized areas as common chemicals including solvents,
petroleum, agricultural chemicals, and heavy metals have dete-
riorated our freshwater supplies. As most potable aquifers are
highly transmissive, resulting contaminant plumes can be miles
in length and render water supply wells unusable or costly to
treat. In addition to these common pollutants, new chemicals
continue to be identified as contaminants of emerging concern,
which are compounds or classes of compounds characterized
by a perceived, potential, or real threat to human health or the
environment, or by a lack of published health standards.
The definition of an emerging contaminant is still a bit elu-
sive, because what is emerging is a matter of perspective as well
as timing. Once a compound is deemed an emerging contami-
nant, the longevity of its emerging status is largely determined,
and rightfully so, by whether the compound of concern is
Remediation Engineering
persistent and/or has potentially deleterious human or ecotoxi-
cological effects. Alternatively, new observations or information
on contaminants can spur the reconsideration of a well-known
contaminant as a (re)emerging contaminant.32 Emerging con-
taminants do not necessarily mean newly introduced chemicals
but can also include naturally occurring compounds with previ-
ously unrecognized adverse effects on ecosystems.
Better analytical methods and technology advances have
allowed for the low level detection of most emerging contami-
nants. At present, regulatory communities are placed in a reac-
tive, rather than proactive, position with respect to identifying
and regulating emerging contaminants and addressing public
concern. This position is exacerbated when chemical data are
not available and no efforts or only sporadic and piecemeal type
of efforts are invested to fill the data gaps. It is often the case
that emerging contaminants have actually been present in the
environment for some time (in some cases, decades), but they
are discovered through a wider search of potential contami-
nants or through the use of advanced analytical techniques.
Under the Safe Drinking Water Act, EPA has implemented
its Unregulated Compounds Monitoring Rule (UCMR) since
2001 to evaluate the frequency and occurrence of emerging con-
taminants in public water supplies. Notable examples include
perchlorate, methyl tertiary butyl ether, flame retardants, and
pesticides. More recent additions include 1,4-dioxane,1,2,3-
trichloropropane and per-/poly fluoroalkylated substances and
dechlorination/disinfection by-products—all of which persist
in the environment. Increased attention on the identification,
characterization, and remediation of these contaminants has
served to reopen a review of surface water and groundwater
utilized for public purposes. Because the emerging contami-
nants are by definition an emerging issue, cost-effective resto-
ration and treatment methods are not readily available.
One of the recent trends that serves as a challenge to clean-
ing up emerging contaminants is that EPA and regulatory risk
analysis programs base their health advisory levels on drinking
water end use, as opposed to adopting a federal MCL. Individual
states therefore develop drinking water and other health-based
standards that vary widely, are very low, and change over time—
which results in a patchwork of standards that are both difficult
to understand and hard for compliance. Inconsistent regulation
fosters inconsistent monitoring and represents a considerable
cost risk for municipalities and the industry. Municipalities face
an immediate challenge where emerging contaminants might
not be treated using existing water treatment technologies, and
the industry must respond with new pretreatment methods or
invest new capital in achieving compliance standards. The
implication is particularly significant as demands for balanced
aquifer storage and recharge/replenishment increase.
Concerns from emerging contaminants continue to be a
driving force for innovation in environmental technologies
research. Just by the definition of these emerging contami-
nants, little is known about their production volumes, their
physical/chemical properties, and the risks they pose on
humans and the environment. The properties and character-
istics of what makes some contaminants emerging continues
to remain elusive: are they emerging in their identification,
Remediation Engineering
emerging in the challenges they present, emerging in concern,
or emerging in interest? The difficulty in forming a consensus
definition reflects the concern that many contaminants are,
and will continue to be, off the radar for a while.33 The prog-
ress made with respect to managing the concerns stemming
from different emerging contaminants that had attracted the
attention of the regulators is discussed in Chapter 11.
1.5.3 Mine Reclamation
During the early development of our country, one of the major
concerns of the established industrial complex was to utilize
our natural resources to provide raw materials to advance the
industrial revolution. It was not a major concern of industry,
at that time, to consider the environmental consequences of
mining or of the effects of other heavy industry. The mining
industry has made significant progress in environmental pro-
tection since that time, but much remains to be done.
Mining is a temporary activity, with the operating life of
a mine lasting from a few years to several decades. Mine clo-
sure occurs once the mineral resource at a working mine is
exhausted, or operations are no longer profitable. Mine closure
plans are required by most regulatory agencies worldwide
before a mining permit is granted and must demonstrate that
the site will not pose a threat to the health of the environment
or society in the future. Depending on the site, the mine may
be repurposed for other uses or restored to its premining use
following closure. Financial assurance is increasingly required
by regulators as a guarantee that the funds required for mine
closure will be available in the event that the responsible com-
pany is unable to complete the closure as planned.
Mine closure is the process of shutting down mining
operations on a temporary or permanent basis. It typically
takes 2–10 years to shut down a mine, but it can take longer
if long-term water monitoring or treatment is required. Mine
closure activities typically consist of several steps: shutdown,
decommissioning, remediation/reclamation, and postclo-
sure activities. Reclamation typically involves a number of
activities such as removing any hazardous materials, reshap-
ing the land, restoring top soil, and planting native grasses,
trees, and/or ground cover. Monitoring programs are used to
assess the effectiveness of the reclamation activities until they
are completed. Long-term care and maintenance after mine
closure may include activities such as ongoing treatment of
mine discharge water, periodic monitoring and maintenance
of tailings containment structures, and monitoring of ongoing
remediation technologies such as constructed wetlands.
1.5.3.1  Mine Tailings
Disposal of mine tailings and their impact on water usage and
environmental issues is one of the more important concerns
for any mine during its lifecycle. The challenge today in the
management of tailings, whether they be copper, aluminum,
zinc, gold, or iron ore, is how to dispose of tailing materials
such that it is contained and stable while maximizing water
reuse and minimizing surface footprint. Significant pressure
is placed on mining projects in developed countries, such as
27
the United States and Canada, to conform to stringent water
conservation and environmental standards in their disposal
of tailings. An increasing number of countries are start-
ing to institute significant steps to require water reuse and
mitigate environmental damage during mining operations.
Management of mining operations in developing or emerg-
ing countries requires more efficient options for water recla-
mation and stiffer environmental regulations to minimize or
eliminate environmental impacts on local populations.
Today, the preparation and planning of mine reclamation
activities occur prior to a mine being permitted and are a
standard part of modern mining practices. During the hard-
rock mining process, tailings impoundments and rock stock-
piles are typically generated. Tailings are the sandy residual
sediments that remain after extracting mineral of economic
value from the ore. After the mineral has been removed, the
remaining materials are discharged to a storage area called a
“tailings impoundment” or “storage facility” on the surface
near the mine. Rock stockpiles (including mine overburden)
may contain low concentrations of sulfide and/or oxide miner-
als and are managed for possible future mineral recovery, but
may also be suitable for reclamation or other projects depend-
ing on economics and technological improvements.
A variety of environmental problems including air, land,
and water pollution arise from mining activities. The detri-
mental impact of mining has been a topic of concern for many
years. Abandoned mine tailings from a wide variety of indus-
tries are found around the world. The chemical composition
of tailings depends on the minerals mined and the extraction
technique. For example, cyanide compounds have been used
in some gold operations. Concentrated sodium hydroxide is
used in the extraction of aluminum from bauxite ore. These
processes add to the potential reclamation difficulties at these
sites. Chemicals reaching tailings ponds may undergo further
reaction over an extended period of time and thus changing
their characteristics. Alleviation of the chemical and physical
impacts of tailings followed by reclamation of the tailings and
the associated landscapes are challenging tasks.
Mining reclamation can take on various forms and achieve
different objectives in an attempt to mitigate environmental
impacts of mining and restore land that has been mined to a
natural or seminatural state. In some cases, existing drainages
are incorporated into the reclamation plan to receive clean
stormwater runoff from reclaimed mine facilities. Dormant
habitats are being reestablished. New landscapes also open up
the potential for future recreation opportunities. Reclamation
sometimes involves removing old mining facilities, including
mineral processing plants, shops, and other structures, in addi-
tion to conducting additional technical studies to further refine
mine closure/closeout activities. To address safety concerns, old
mine openings such as shafts or adits that were created decades
ago as early miners explored for metals are closed properly.
Once tailings facilities and rock stockpiles are no longer
needed in an operation, they can be reclaimed. Reclamation
takes into account surface water, groundwater, air quality, and
erosion concerns from stormwater, revegetation of suitable
plant species, and provision of wildlife and aquatic habitats.
28
The reclamation process generally includes resloping and
contouring of the impacted areas, ensuring drainage channels
are created to divert stormwater and limit percolation, and
establishing points for stormwater to discharge into existing
drainages. In addition, capping the area with soil and reseed-
ing with native grasses and shrubs to encourage revegetation
and promote wildlife habitat are normal activities during
mine reclamation.
1.5.3.2  Acid Mine Drainage
Contamination of streams and groundwater by acidic drain-
age, commonly called “acid mine drainage,” is created by
the chemical reaction of surface water and groundwater with
rocks containing sulfur. The product of this reaction is sulfu-
ric acid, which then leaches metals (iron, copper, zinc, man-
ganese, cadmium, and lead) from mineralized rock and keeps
the metals dissolved in the water. This acidic metal-laden
drainage can adversely impact aquatic and human health
when it enters the surface water and groundwater systems.
Elevated levels of metals can cause fish and other aquatic life
to be impacted and drinking and agricultural water sources to
be contaminated. Acid mine drainage (AMD) can also form
in mines and in water percolating through waste rock dumps
and mill tailings piles.
AMD causes environmental pollution that affects many
locations having historic or current mining operations.
Preventing the formation or the migration of AMD from its
source is generally considered to be the preferable option,
although this is not feasible in many locations. In such cases,
it is necessary to collect, treat, and discharge the mine water.
AMD effluents sometimes can be extremely acidic and can
pose additional risks by the fact that they contain elevated
concentrations of metals (iron, aluminum, manganese, and
other possibly heavy metals) and metalloids such as arsenic.
It is estimated that thousands of miles of streams and rivers
and thousands of acres of lakes and surface water bodies are
impacted worldwide by mine effluents. The true scale of envi-
ronmental pollution caused by mine water discharges is dif-
ficult to assess accurately.
In brief, the major cause for the origin of acidic metal-
rich mine drainage waters is the accelerated oxidation of iron
pyrite (FeS2) and other sulfidic minerals resulting from the
exposure of these minerals to both oxygen and water, as a
result of the mining and ore processing activities. There are
various options available for remediating AMD, which may
be divided into those that use either chemical or biological
mechanisms to neutralize AMD and remove metals from solu-
tion. These systems can be implemented for source control
or migration control of AMD. Given the practical difficulties
entailed in inhibiting the formation of AMD at source, often,
the only alternative is to minimize the impact on the environ-
ment via migration control measures. Quite often these can be
divided into active and passive processes. The former gener-
ally (not exclusively) refers to the continuous application of
alkaline materials to neutralize AMD precipitate metals, and
the latter to the use of natural and constructed wetland sys-
tems and permeable reactive barriers.
Remediation Engineering
1.5.3.3  Mining Habitats
Sediments related to mining and milling activities may con-
sist of small particles that often contain high concentrations
of heavy metals. Because of the hazardous nature of these
sediments, plants do not readily grow on it, and as a result, it
is easily removed and transported by water and wind. Mining-
related sediments can contaminate streams, rivers, wetlands,
and other riparian areas. Heavy metals in the sediments are
released into the water in streams and ponds, impacting fish
and other aquatic life. The mill tailings particles can also
impact aquatic habitats by covering the stream bottom and
stressing the aquatic life by filling in locations that serve as
fish habitat. Contaminated sediments can also affect suitabil-
ity of available water resources for human uses such as agri-
culture and drinking water.
Mining sites can be dismantled, reclaimed, and integrated
with the surrounding environment. Most mine sites are usu-
ally returned to their premine uses, which for the majority
of mines are wildlife habitats or forestry. However, the new
concept of sustainability and its growing inclusion in mine
closure plans have resulted in the collaboration of mining
companies, regulators, land-use planners, investors, and local
communities to identify the most beneficial use of a mine site,
leading to the creative and successful reuse of a number of
decommissioned mine sites across the world. Repurposing
mine sites can take advantage of existing infrastructure and
contribute to the local economy by developing museums, edu-
cation or scientific centers, recreational areas, parks, or farms.
1.5.4 Current Thinking on LNAPL Management
The presence of petroleum light nonaqueous phase liquids
(LNAPLs) has been and continues to be one of our most diffi-
cult challenges in cleaning up contaminated sites. Practitioners
understand the complexities of bringing LNAPL sites to regu-
latory closure based on decades of experience in remediat-
ing petroleum sites. An increased understanding of LNAPL
behavior in porous media, a connection between LNAPL
composition and its risk to human health and/or ecological
receptors and a new awareness of the rate at which petroleum
depletes in the subsurface has changed our perspective on how
to address LNAPL impacts. This new perspective, coupled
with a similar change in regulatory perspective and policy,
has recalibrated our investigation, assessment, and remedia-
tion approaches for petroleum sites. This approach allows us
to make better remedial decisions as to when to deploy active
recovery remedies and when to manage the LNAPL in place
because it presents an acceptable risk. Our technical tools will
continue to evolve and improve, and the regulatory landscape
will continue to accept the developments in scientific knowl-
edge. These developments collectively will have a consider-
able bearing on how we approach petroleum site assessment
and remediation in the future.
The evolution of industry knowledge on the topic has
resulted in a change in how we assess and remediate LNAPL
sites. The perspective has changed from a singular focus on
the thickness of LNAPL in wells as a remedial end point to
Remediation Engineering
Oxygen transport
Oxygen transport
Biodegradation
Methane offgasing Volatilization
Mobile or residual LNAPL
Electron
acceptor Dissolution and Biodegradation
flux
Groundwater flow
FIGURE 1.14  Conceptual model of light nonaqueous phase liquid depletion mechanisms that collectively depict natural source zone
depletion (NSZD). The NSZD rates in both the saturated and vadose zones are quantified as part of a comprehensive NSZD assessment.
At sites where NSZD evaluations were completed, the contribution of vadose zone depletion was greater than 90% of the total NSZD
rate. (Adapted from Interstate Technology Regulatory Council (ITRC), Evaluating LNAPL remediation technologies for achieving project
goals, Published 2009; Interstate Technology Regulatory Council (ITRC), Evaluating natural source zone depletion at sites with LNAPL,
Published April 2009.)
evaluating the risk associated with the LNAPL, the mobility
and recoverability of the LNAPL, and the rate at which the
LNAPL is being naturally depleted. This change in perspec-
tive and understanding realistic expectations has prompted
a shift toward a more accurate and detailed site assessment.
Improvements in our sampling methodology have shed new
light on the dynamics of LNAPL mobility and the limitations
of the 0.01 ft thickness standard.
The accumulation of LNAPL in a monitoring well is not a
reliable indicator of its presence in the subsurface. This shift
in management perspective and increased characterization
methodology has enabled the collection of better site data to
develop comprehensive LNAPL CSMs (LCSMs) that allow
us to make more informed site management decisions. In
many cases, new site assessment data are being collected at
legacy LNAPL sites where remediation activities have failed
to support more complete LCSMs and refine long-standing
remedies or petition for closure.
A comprehensive LCSM is built from all relevant site infor-
mation including the nature of the spill, the geologic setting of
the site, and the physical and chemical properties of the LNAPL.
Determining the stability of the LNAPL plume is a key piece of
the LCSM. A demonstration that the LNAPL plume is stable
and will not expand provides assurance that receptor exposure
pathways will not change in the future due to LNAPL migration
into previously non-impacted areas. As such, LNAPL mobility
assessments are a core component of contemporary LNAPL
site management strategies. LNAPL recoverability assessments
have also become a key part of the LCSM framework.
Petroleum LNAPLs are a complex mixture of hydrocar-
bon compounds, and it is well known that LNAPLs weather
following release to the subsurface. These weathering pro-
cesses entail dissolution, volatilization, and biodegradation
of individual LNAPL constituents and result in a change
in LNAPL properties over time. It is now apparent that the
29
Observed NSZD
contribution
90%–99%
Electron Dissolved
acceptor plume 1%–10%
depletion
rate of LNAPL depletion in the subsurface has been greatly
underestimated. The key piece missing in traditional electron
acceptor-driven mass balance models was a complete under-
standing of LNAPL depletion in the vadose zone and the role
of methanogenesis (Figure 1.14). The mass loss due to bio-
degradation can be substantial (more than 90% of total mass
removed) when the petroleum mass resides at a site where a
fluctuating water table routinely exposes the LNAPL mass
to oxygen-rich soil gas. In those settings, the vadose zone
effectively serves as a large-scale bioreactor. The LNAPL
constituents partition into pore water and soil bacteria readily
consume the hydrocarbons.
The change in how we view LNAPL behavior and risks has
recalibrated our investigation and assessment approach for
petroleum sites and allowed us to apply more rigorous think-
ing on developing appropriate LNAPL treatment remedies.
We recommend that LCSMs be developed for all LNAPL
sites, regardless of the applicable remediation requirements,
to facilitate informed site management by remediation prac-
titioners across the industry.34,35 At many sites, an LCSM can
be built primarily using existing data augmented with small
investments in new data collection. Often the exercise results
in a new perspective on the site and an immediate return asso-
ciated with a change in direction for future actions.
1.5.5 Protection of Water Resources
Freshwater is one of the most important natural resources for
society, and water supply systems belong to the critical infra-
structure of most population centers. Reduced access to fresh-
water will lead to a cascading set of consequences, including
impaired food production, the loss of livelihood security,
large-scale migration from population centers, and increased
economic and geopolitical tensions and instabilities. The term
“security” is often used to connote conflict, but in this context
30
it has a much broader meaning encompassing physical safety,
livelihoods, human health and welfare, and overall state of a
country’s economy.
Groundwater is a critical component of the nation’s water
resources. Globally, groundwater resources dwarf surface
water supplies and, since they are hidden in the subsurface, are
often forgotten or misunderstood. Nearly all of rural America,
as well as large metropolitan areas, use groundwater-supplied
water supply systems. In addition, the percentage of total irri-
gation withdrawals from groundwater increased from 23% in
1950 to 42% in 2000.36 Even with this vast resource beneath
our feet, many parts of the country are experiencing regional
and local declines in water levels in aquifers, saltwater intru-
sion along the coastline, and declining water quality due to
over pumping and contamination due to human activities.
Water has long been a scarce and valuable resource in
the south western United States, particularly in California,
mainly because a sizable portion of this part of our coun-
try is arid—some of it dessert. Even a temporary decrease
in rainfall during the rainy season can strain water reserves.
When the annual rainfall is well below the historical average,
as has been the case for years, a water problem can become
a water crisis. Streams, lakes, and reservoirs have shriv-
eled up in many parts of the state, and now the groundwater
aquifers—always a backup source during the region’s peri-
odic droughts—are being pumped away at rates that scientists
say are both historic and unsustainable. Aquifers provide us
freshwater that makes up for surface water lost from drought-
depleted lakes, rivers, and reservoirs.
Plans have to be developed in the arid west to meet three
broad objectives: more reliable water supplies, restoration of
the groundwater aquifer in terms of quality and quantity, and
a more resilient sustainably managed water resources system.
Groundwater accounts for more than one-third of the water sup-
ply in California—much more in dry years, when other sources
are cut back. It is a fact that millions of Californians rely, at least
in part, on contaminated groundwater as a potential resource
for their drinking water. Similarly, contaminated groundwater
may pose a potential risk to the sustainability of potable water
supplies to many metropolitan areas. While most water purvey-
ors blend or treat water to meet public health standards, many
disadvantaged communities cannot afford to do so.
In general, U.S. groundwater quality remains good, but
industrial and nonpoint source pollution has affected the
resource when impacts were not controlled. For example, in
California, perchlorate has been detected in multiple public
supply sources and an equally large number of private home
owner wells. Agricultural chemicals impact groundwater
quality in many parts of the country. Contamination of nitrate
from fertilizers and animal waste is common. Naturally
occurring constituents, such as arsenic, chloride, and tan-
nins, render some groundwater unusable for drinking or other
purposes without treatment. Many emerging contaminants,
pesticide breakdown products and pharmaceutical agents,
are being found in groundwater at trace levels. Our ability to
detect constituents in water at lower and lower concentrations
Remediation Engineering
also presents new challenges. Analytical detection techniques
are often outpacing our toxicological understanding of what
the findings in parts per billion or trillion mean to the suitabil-
ity and use of groundwater for specific purposes.
In light of this situation, great interest has developed in
using the contaminated groundwater treated by P&T systems
for beneficial purposes that contribute toward meeting the
water supply needs in many metropolitan areas. This could
be addressed by using on-demand (e.g., well head) treatment
of the contaminated groundwater or by treating the extracted
groundwater in a centralized treatment plant. Hence, P&T sys-
tems will continue to play a critical role in long-term manage-
ment of contaminated mega plumes. Efforts to optimize the
operational cost effectiveness of such systems should include
consideration of their beneficial impacts on the reclamation of
local water resources.
Traditional assumptions need to change dramatically to
achieve a sustainable water future. A broadened understand-
ing to water supply and governance must evolve to create gov-
ernance structures that enable sustainable approaches using
diverse water supply resources. In the United States, regulatory
frameworks for water governance are somewhat disjointed. For
example, there are drinking water regulations, wastewater reg-
ulations, requirements for remediation systems and reuse water
regulations. Often, the jurisdiction and implementation of these
regulations are in the hands of different agencies. Consequently,
a holistic and sustainable view of managing our water resources
is difficult to achieve due to the fragmented oversight.
1.5.5.1 Environmental Concerns from
Unconventional Energy Exploration
Exploration and production from unconventional natural gas
reservoirs have substantially increased due to recent tech-
nological advances. Horizontal drilling and high-volume
hydraulic fracturing have opened vast new energy resources
such as low-permeability organic rich shale formations and oil
sands. This increase in energy exploration has been broadly
distributed across the United States but densely distributed
within specific shale basins, thus altering the domestic energy
landscape. However, this recent rise in natural gas exploration
activities has triggered an intense public debate regarding the
potential environmental and human health effects stemming
from hydraulic fracturing.
Public concern about fracking has grown in the last few
years; an unconventional oil and gas development has become
more visible throughout many regions within our country.
Fracking is a drilling method that uses millions of gallons of
water mixed with sand and a blend of proprietary chemicals
to release oil or gas trapped in rock. The technique has been
linked to methane contamination of drinking water wells, air
pollution, and induced earthquakes associated with under-
ground disposal of fracking wastewater.
There could be few potential risks associated with natural
gas exploration activities to the environment, specifically to
the surrounding water resources if precautions are not taken
during exploration activities. The first risk is the potential
Remediation Engineering
contamination of shallow aquifers in areas adjacent to shale
gas development through stray gas leaking from improperly
constructed or failing gas wells. Over a longer period, the
groundwater quality could potentially be impacted by both
leaking of saline water and hydraulic fracturing fluids and
aquifers where stray gas has been identified. Evidence of stray
gas contamination could be an indicator of long-term water
quality degradation by secondary processes induced by the
high concentration of methane in the groundwater.
Another potential risk arises from the need for safe dis-
posal of large volumes of oil and gas wastewater. Oil and gas
wastewater composes of drilling fluids, hydraulic fracturing
flowback fluids, and produced waters. The safe disposal of
this stream is a major challenge given their large volumes and
typically high levels of contaminants. Oil and gas wastewater
is typically managed through recycling of the wastewater for
shale gas operations, injection into deep disposal wells, treat-
ment at publicly owned wastewater treatment plants or com-
mercially operated industrial wastewater treatment plants, and
spreading on roads for dust suppression and deicing. When
complete removal of the contaminants fails to take place, the
water quality of the discharged effluents will have deleterious
impacts on the surface waters, groundwater, and stream sedi-
ments of the nearby environment.
Other potential risks include the accumulation of metals
and radioactive elements on stream, river, and lake sediments
in the vicinity of wastewater effluent discharge sites or spill
sites.37 This poses a long-term risk of slowly releasing haz-
ardous elements and radiation to the environment around the
impacted areas. Another long-term impact is on the overall
water balance within the area of gas exploration through with-
drawals of valuable freshwater and overexploitation of limited
or diminished water resources.
Studies need to be conducted to evaluate the environmen-
tal impacts from the entire hydraulic fracturing water cycle.
This includes acquisition of water for drilling, the mixing
and use of fracturing fluids, the return to the surface of a
mix of injected water and highly saline produced water from
geologic formations, and wastewater treatment and disposal.
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 2 Contaminant Characteristics
2.1 INTRODUCTION
The basic elements controlling the overall fate and transport
of contaminants in the subsurface are the physicochemi-
cal and biological properties of the contaminants and the
physical structure and geochemical composition of the soil
and groundwater in which contaminants reside. Nonreactive
or recalcitrant chemicals will move through the subsurface
with hydrodynamic groundwater processes and will not be
affected by abiotic or biotic transformation processes that may
be active. Conversely, the behavior of reactive contaminants
will depend on the nature of the subsurface and the potential
for biological or chemical processes to facilitate contaminant
degradation and sequestration. Accordingly, while reactive
chemicals have the potential to be affected during groundwater
transport, the contaminant property and appropriate subsurface
conditions must exist to transform the contaminant. The goal
of this chapter is to provide an overview of subsurface and
contaminant properties that may affect the behavior and par-
titioning of the contaminants in the subsurface.
The factors that affect the subsurface behavior and partition-
ing of contaminants are abiotic processes, biotic processes,
soil and groundwater geochemical composition, and the geo-
logic architecture and associated hydrodynamic environment.
Abiotic processes affect contaminant transport by facilitating
interaction between the contaminant and the subsurface soil
and groundwater materials (e.g., adsorption, volatilization,
and ion exchange) or via direct chemical interactions that
transform the contaminant via oxidation or reduction reac-
tions. Biotic processes can affect contaminant transport via
degradation and metabolic contaminant utilization as a car-
bon source, as a nutrient for growth, or by immobilizing the
dissolved contaminant to reduce its mobility. Hydrodynamic
processes including advection, dilution, diffusion, and to a
lesser extent, dispersion, all control contaminant mobility (or
sequestration) in groundwater systems.
Understanding contaminant distribution in the subsurface
is a critical step for scientists and engineers practicing reme-
diation engineering to ensure that the total mass, distribution,
and dominant transport mechanisms are well understood
prior to implementing remedial technologies. The arsenal
of investigative techniques continues to expand with real-
time high-resolution sampling methods available to support
rapid, cost-effective, and remediation-focused site assess-
ment. Attention must be placed on the development of com-
prehensive conceptual site models to understand contaminant
distribution in both the vadose and saturated zones, the mech-
anisms of release and mass flux in groundwater, and to ensure
that all human health and environmental exposure pathways
can be addressed. For volatile contaminants, an understand-
ing of contaminant depth and vadose zone soil architecture is
also imperative to ensure that subsurface vapor transport does
not result in vapor intrusion risks to human receptors.
The variety of contaminants that can be released to the
subsurface and cause an adverse impact include organic
­
contaminants (e.g., petroleum hydrocarbons or halogenated
organics), inorganic contaminants (e.g., nitrogen or sulfur sub-
stituted compounds or perchlorate), and metals. Contaminants
also include compounds that adversely impact the native geo-
chemistry (e.g., acids or bases) that can adversely affect natu-
ral geochemical conditions and liberate native minerals. Each
contaminant or mixture of contaminants will have its own
distinct set of physicochemical characteristics that ­govern
contaminant behavior and the nature of transport mecha-
nisms. In general, contaminants exist in four main phases:
(1)  nonaqueous-phase liquid (NAPL), (2) sorbed phase, (3)
dissolved phase, or (4) vapor phase. The distribution of con-
taminants into these different phases is ultimately dependent
on the total contaminant mass, their physical properties, and
the subsurface soil and groundwater environment in which
they reside (Figure 2.1).
2.2  MOLECULAR STRUCTURE OF COMPOUNDS
A contaminant molecule’s behavior in the environment is
controlled by its underlying composition. The specific atoms,
chemical bonds, and elements included as part of the contam-
inant molecule all have a bearing on its overall nature and
reactivity. When describing the chemistry of a compound, the
elemental composition has to be specified. It should be noted
that most of the contaminants, organic or inorganic, are a
combination of only a few elements: carbon (C), hydrogen (H),
oxygen (O), nitrogen (N), sulfur (S), phosphorous (P), and the
halogens (Cl, F, Br, or I). As an example, a chlorinated hydro-
carbon will contain chlorine, hydrogen, and carbon atoms in
its molecular structure. The molecular formula is then used
to annotate how many atoms of each of these elements are
present in the molecular structure (CH4 for methane, C2HCl3
for TCE), which allows calculation of the molecular weight
for any given compound. The exact connection of each atom
within the molecule is referred to as the molecular structure.
Electrons move around the nucleus of an atom in orbital
clouds, which lie in a series of concentric energy level shells.
Each shell has a maximum number of electrons that it can
hold and electrons in outer orbitals have more energy than
those in inner shells. Electrons fill the innermost shells of an
atom first, then the outer shells. The atom’s energy level is
lowest when all of its orbitals are filled, and an atom’s reactiv-
ity depends on how many electrons it needs to complete its
outermost orbital. The noble gases, helium (He), neon (Ne),
argon (Ar), and radon, are nonreactive since all electrons
within their orbitals are “filled.”
33
34
Total mass
1,300,000 lb
Soil vapor
67,000 lb
Sorbed phase
230,000 lb
Dissolved phase
55,000 lb
FIGURE 2.1  Conceptual distribution of mass in a dense NAPL (DNAPL) source zone. Distribution reflects orientation of drainable
NAPL; residual NAPL; zones with elevated sorbed and dissolved phase concentrations, containing primarily dissolved phase; and result-
ing soil gas concentrations overlying the impacted area.
Core electrons are those electrons that are never utilized
in chemical bonding. Their high ionization energies and con-
tracted nature mean that they are not perturbed by the orbit-
als of neighboring atoms. In general, core electrons may be
defined as all those electrons in orbitals, which are associated
with the noble gas before that element in the periodic table.
The first orbital holds only 2 electrons (He structure) and the
second shell holds 8. The third can hold 18, but a stable config-
uration is reached when the shell is filled with 8 (Ar structure).
Understanding the quantity of electrons present in the outer-
most shell (called valence electrons) determines the chemical
characteristics of an element. All valence electrons do not nec-
essarily become involved in bonding in all the possible com-
pounds containing that element. For example, chromium (Cr),
arsenic (As), and manganese (Mn) do not form any compounds
in the oxidation state corresponding to the utilization of all
electrons in their outer shells. They do, however, form com-
pounds in only a couple of oxidation states. Examples include
Cr3+ and Cr6+, As3+ and As5+, and Mn7+ and Mn4+.
The primary intermolecular forces that occur between mol-
ecules are summarized in the following sections. Fortunately,
an understanding of a few governing rules about the nature
of these elements and chemical bonds enables us to under-
stand important relationships between the structure of a com-
pound, its properties and reactivities, and thereby predict the
compound’s likely behavior in the environment. If the relative
forces between the molecules within a biogeochemical system
can be predicted, then we can also predict the potential reac-
tions and behavior within that system.
2.2.1 Covalent Bonds
As discussed earlier, the outermost orbital of each atom has
a characteristic number of electrons, which readily form
Remediation Engineering
810
800
790
Elevation (feet above mean sea level)
Residual NAPL
890,000 lb 780
770
Drainable NAPL 760
110,000 lb
750
740
730
720
covalent bonds with other atoms. As a rule, each type of atom
forms a characteristic number of covalent bonds with other
atoms. For example, a hydrogen atom, with one electron in
its outer shell, forms only one bond, such that its outermost
orbital becomes filled with two electrons. A carbon atom
has four electrons in its outermost orbital; it usually forms
four bonds, as in methane (CH4), in order to fill its outermost
orbital with eight electrons. The single bonds in methane that
connect the carbon atom with each hydrogen atom contain
two shared electrons, one donated from the C and the other
from the H, and the outer (s) orbital of each H atom is filled by
the two shared electrons (Figure 2.2a).
Nitrogen and phosphorus each have five electrons in their
outer shells, which can hold up to eight electrons. Nitrogen atoms
can form up to four covalent bonds. In ammonia (NH3), the
nitrogen atom forms three covalent bonds; one pair of electrons
around the atom (the two dots on the right) is in an orbital not
involved in a covalent bond. In the ammonium ion (NH4+), the
nitrogen atom forms four covalent bonds, again filling the outer-
most orbital with eight electrons (Figure 2.2b). Phosphorus can
form up to five covalent bonds, as in phosphoric acid (H3PO4).
The H3PO4 molecule is actually a “resonance hybrid,” a struc-
ture between the two forms shown in the following text in which
nonbonding electrons are shown as pairs of dots (Figure 2.2c).
The difference between the bonding patterns of nitrogen
and phosphorus is primarily due to the relative sizes of the
two atoms: the smaller nitrogen atom has only enough space
to accommodate four bonding pairs of electrons around
it without creating destructive repulsions between them,
whereas the larger sphere of the phosphorus atom allows more
electron pairs to be arranged around it without the pairs being
too close together.
Both oxygen and sulfur contain six electrons in their outer-
most orbitals. However, an atom of oxygen usually forms only
Contaminant Characteristics 35

H H H
H
H C H or H C H
109.5°
H H H C H C
H
(a)
(a) H H H

H H H
H H H H
H N H or H N H N+ H C–
–C or C C
H H H H
H H H (b)
(b)
H C C H or H–C–
–C–H
H (c)

O –
δ– δ–
H O P+ O H O O or O —
— O O Dipole
moment δ– δ+ δ–
(d) + +
(c) O δ δ O C O
H 104.5° H +
(d) (e)
O
O
H FIGURE 2.3  (a) Molecular shape of methane. (b) Molecular struc-
O S H O S O H
ture of ethene with a C═C double bond. (c) Molecular structure of
H S
ethyne with a ─C≡C─ triple bond. (d) The water molecule with two
O O
polar O─H bonds and a net dipole moment. (e) Molecular structure
(e) of CO2 without a net dipole moment.

FIGURE 2.2  (a) Structure of CH4 molecule with its four covalent
bonds. (b) Molecular structure of NH3 and NH4+. (c) Molecular struc-
ture of phosphoric acid (H3PO4). (d) Structure of the O2 molecule.
(e) Structures of hydrogen sulfide (H2S), sulfur trioxide (SO3), and
sulfuric acid (H2SO4).
two covalent bonds, as in molecular oxygen, O2 (Figure 2.2d).
Primarily, because its outermost orbital is larger than that of
oxygen, sulfur can form as few as two covalent bonds, as in
hydrogen sulfide (H2S), or as many as six, as in sulfur trioxide
(SO3) or sulfuric acid (H2SO4) (Figure 2.2e).
Covalent bonds tend to be very stable because the energies
required to break or rearrange them are much greater than the
thermal energy available at room temperature (25°C) or the
ambient temperatures under which we encounter these com-
pounds. For example, the thermal energy at 25°C is less than
4 kJ/mol (kcal/mol), whereas the energy required to break a
C─C bond in ethane is about 348 kJ/mol.
When two or more atoms form covalent bonds with another
central atom, these bonds are oriented at precise angles to
one another. The angles are determined by the mutual repul-
sion of the outer electron orbitals of the central atom. These
bond angles give each molecule its characteristic shape. In
methane, for example, the central carbon atom is bonded to
four hydrogen atoms, whose positions define the four points
of a tetrahedron, so that the angle between any two bonds is
109.58 (Figure 2.3a). Like methane, the ammonium ion also
has a tetrahedral shape. In these molecules, each bond is a sin-
gle bond, a single pair of electrons shared between two atoms.
When two atoms share two pairs of electrons—for exam-
ple, when a carbon atom is linked to only three other atoms—
the bond is a double bond (Figure 2.3b). In this case, the
carbon atom and all three atoms linked to it lie in the same
plane. Atoms connected by a double bond cannot rotate freely
about the bond axis, while those in a single bond generally
can. The rigid planarity imposed by double bonds has enor-
mous significance for the shape of large biological molecules
such as proteins and nucleic acids. In triple bonds, two atoms
share six electrons, such as ethyne, and are rare in biological
molecules (Figure 2.3c).
All outer electron orbitals, whether or not they are involved in
covalent bond formation, contribute to the properties of a mol-
ecule, in particular to its shape. For example, the outer shell of
the oxygen atom in a water molecule has two pairs of nonbond-
ing electrons; the two pairs of electrons in the H─O bonds and
the two pairs of nonbonding electrons form an almost perfect
tetrahedron. However, the orbitals of the nonbonding electrons
have a high electron density and thus tend to repel each other,
compressing the angle between the covalent H─O─H bonds to
104.58 rather than the 109.58 in a tetrahedron (Figure 2.3d).
2.2.2 Polar Covalent Bonds
In certain cases, the bonded atoms in a covalent bond exert
different attractions for the electrons of the bond, resulting in
unequal sharing of the electrons. The power of an atom in a
molecule to attract electrons to itself, called electronegativity,
is measured on a scale from 4.0 (for fluorine, the most electro-
negative atom) to a hypothetical zero (Table 2.1). Knowing the
electronegativity of two atoms allows us to predict whether
a covalent bond can form between them; if the differences
in electronegativity are considerable—as in sodium and
chloride—an ionic bond, rather than a covalent bond, will
form. Atoms located to the upper right in Table 2.1 tend to
36
TABLE 2.1
Electronegativity Values of Some Atoms
H 2.2
Li 1.0 Be 1.6 B 2.0 C 2.6
Na 0.4 Mg 1.3 Al 1.6 Si 1.4
K 0.8 Ca 1.3 Ga 1.6 Ge 2.0
Rb 0.8 Sr 1.0 In 1.8 Sn 2.0
Cs 0.8 Ba 0.9 Te 2.0 Pb 2.3
Source: Lodish, H. et al., Molecular Cell Biology, W.H. Freeman & Company, New York, 2000.
have high electronegativity, fluorine being the most electro-
negative. Elements with low electronegativity values, such as
the metals lithium, sodium, and potassium, are often called
electropositive. Since the inert noble gases (He, Ne, etc.)
have complete outer shells of electrons, they neither attract
nor donate electrons, rarely form covalent bonds, and have no
electronegativity values.
In a covalent bond in which the atoms either are identical
or have the same electronegativity, the bonding electrons are
shared equally. Such a bond is said to be nonpolar. This is the
case for C─C and C─H bonds. However, if two atoms differ
in electronegativity, the bond is said to be polar. The electro-
negativities of several atoms abundant in chemical compound
molecules differ enough that they form polar covalent bonds
(e.g., O─H, N─H) or ionic bonds (e.g., NaCl2). One end of a
polar bond has a partial negative charge (δ−), and the other end
has a partial positive charge (δ+). The symbol δ represents a
partial charge, a weaker charge than the one on an electron or
a proton. In an O─H bond, for example, the oxygen atom, with
an electronegativity of 3.5, attracts the bonded electrons more
than does the hydrogen atom, with an electronegativity of 2.2.
As a result, the bonding electrons spend more time around the
oxygen atom than around the hydrogen. Thus, the O─H bond
possesses an electric dipole, a positive charge separated from
an equal but opposite negative charge. We can think of the
oxygen atom of the O─H bond as having, on average, a charge
of 25% of an electron, with the H atom having an equivalent
positive charge. The dipole moment of the O─H bond, defined
as a measure of the nonuniform charge separation, is a func-
tion of the size of the positive or negative charge and the dis-
tance separating the charges. The dipole moment is equal to
the magnitude of positive and negative charges at each end of
the dipole multiplied by the distance between the charges.
In general, if the electronegativity difference between two
bonded atoms is zero, they will form a nonpolar covalent bond.
Examples are the molecules of O2, H2, and N2. If the electro-
negativity difference between two atoms is between 0 and 1.7,
they will form a polar covalent bond. Examples are NO and
CO. If the electronegativity difference between two atoms is
greater than 1.7, they will form an ionic bond. Examples of
such a bond are NaCl, HF, and KBr. Because electronegativ-
ity differences can vary continuously between 0 and 4, bond
character also can vary continuously between nonpolar, cova-
lent, and ionic.
Remediation Engineering
He
N 3.0 O 3.5 F 4.0 Ne
P 2.2 S 2.6 Cl 3.2 Ar
As 2.2 Se 2.6 Br 3.0 Kr
Sb 2.1 Te 2.1 I 2.7 Xe
Bi 2.0 Po 2.0 At Rn
Polarizability is a measure of how easily the electron
distribution can be distorted by an electric field—that is,
how easily a dipole moment can be induced in an atom or a
molecule. Large atoms and molecules have more electrons
and larger electron clouds than small ones. In large atoms
and molecules, the outer shell electrons are farther from the
nuclei and, consequently, are more loosely bound. The elec-
tron distributions can be more easily distorted by external
charges. In small atoms and molecules, the outer electrons
are closer to the nuclei and are more tightly held. Electron
charge distributions in small atoms and molecules are less
easily distorted.
Therefore, large atoms and molecules are more polarizable
than small ones. Since atomic and molecular sizes are closely
related to atomic and molecular weights, we can general-
ize that polarizability increases with increasing atomic and
molecular weights. The greater the polarizability of atoms
and molecules, the stronger the intermolecular dispersion
forces between them. Molecular shape also affects polariz-
ability. Elongated molecules are more polarizable than com-
pact molecules. Thus, a linear alkane is more polarizable than
a branched alkane of the same molecular weight.
In a water molecule, both hydrogen atoms are on the same
side of the oxygen atom. As a result, that side of the molecule
compared with the other side has a slight net positive charge
and the other side has a slight net negative charge. Because
of this separation of positive and negative charges, the entire
molecule has a net dipole moment (Figure 2.3d). Some mol-
ecules, such as the linear molecule carbon dioxide (O═C═O),
have two polar bonds. Because the dipole moments of the two
carbonyl C═O bonds point in opposite directions, they cancel
each other out, resulting in a molecule without a net dipole
moment (Figure 2.3e). Similarly, if any molecule is symmetri-
cal in a way that the bond polarity vectors add to zero, then
the molecule is nonpolar, although it contains polar bonds.
Knowing whether a molecule is polar or not helps predict
its water solubility and other properties. Nonpolar molecules
invariably have low water solubility. A molecule with no polar
bonds cannot be a polar molecule. Thus, all diatomic mol-
ecules where both atoms are the same, such as H2, O2, N2, and
Cl2, are nonpolar because there is no electronegativity differ-
ence across the bond. Carbon dioxide, carbon tetrachloride,
and hexachlorobenzene are all symmetrical and nonpolar,
although all contain polar bonds.
Contaminant Characteristics
δ– δ–
O bonding valence electron pairs. Although chlorine and sulfur
+ have similarly high electronegativities and contain nonbond-
δ+ H H δ
Additive dipole
moments
FIGURE 2.4  Water molecule showing a high net dipole moment as
a result of the two O–H bonds.
Water is a particularly important polar molecule. Its bond
polarity vectors add to give the water molecule a high polarity
(i.e., dipole moment) (Figure 2.4). The dipole–dipole forces
between water molecules are greatly strengthened by hydro-
gen bonding, discussed in the following text, which contribute
to many of water’s unique characteristics. These character-
istics include relatively high boiling point and viscosity, low
vapor pressure, and high heat capacity.
All molecules are attracted to one another because of elec-
trostatic forces. Polar molecules are attracted to one another
because the negative end of one molecule is attracted to the
positive ends of other molecules, and vice versa. Attractions
between polar molecules are called dipole–dipole forces.
Similarly, positive ions are attracted to negative ions.
Attractions between ions are called ion–ion forces. If ions and
polar molecules are present together, as when sodium chloride
is dissolved in water, there can be ion–dipole forces, where
positive and negative ions (e.g., Na+ and Cl–) are attracted to
the oppositely charged ends of polar molecules (e.g., H2O).
However, nonpolar molecules also are attracted to one
another, although they do not have permanent charges or
dipole moments. Evidence of attractions between nonpolar
molecules is demonstrated by the fact that nonpolar gases
such as methane (CH4), oxygen (O2), nitrogen (N2), ethane
(CH3CH3), and carbon tetrachloride (CCl4) condense to liq-
uids and solids when the temperature is lowered sufficiently.
This attraction is caused by the transitory dipole movements
due to the interaction between the electron clouds caused by
the collision of the molecules.
2.2.3 Hydrogen Bonds
Normally, a hydrogen atom forms a covalent bond with only
one other atom. However, a hydrogen atom covalently bonded
to a donor atom, D, may form an additional weak association,
the hydrogen bond, with an acceptor atom, as shown in Figure
2.5. In order for a hydrogen bond to form, the donor atom
must be highly electronegative, so that the covalent  D─H
bond is polar. The acceptor atom also must be electronega-
tive, and its outer shell must have at least one nonbonding pair
of electrons in its valence shell that attracts the δ+ charge of
δ + δ+ δ– δ– δ + δ+
D – H + :A D – H + ····· –A
FIGURE 2.5  Formation of a hydrogen bond.
37
the hydrogen atom. Fluorine, oxygen, and nitrogen are the
smallest and most electronegative elements that contain non-
ing valence electron pairs, they are too large to consistently
form hydrogen bonds (H bonds). Because hydrogen bonds are
both strong and common, they influence many substances in
important ways.
Hydrogen bonds are very strong (10–40 kJ/mol) com-
pared to other dipole–dipole forces (from less than 1 to 5 kJ/
mol). The hydrogen atom’s very small size makes hydrogen
bonding so uniquely strong. Hydrogen has only one electron.
When hydrogen is covalently bonded to a small, highly elec-
tronegative atom, the shift of bonding electrons toward the
more electronegative atom leaves the hydrogen nucleus nearly
bare. With no inner core electrons to shield it, the partially
positive hydrogen can approach very closely to a nonbond-
ing electron pair on nearby small polar molecules. The very
close approach results in stronger attractions than with other
dipole–dipole forces.
Because all covalent N─H and O─H bonds are polar,
their H atoms can participate in hydrogen bonds. By contrast,
C–H bonds are nonpolar, and hence these H atoms are almost
never involved in a hydrogen bond. Water molecules provide
a classic example of hydrogen bonding. The hydrogen atom
in one water molecule is attracted to a pair of electrons in
the outer shell of an oxygen atom in an adjacent molecule.
Not only do water molecules hydrogen bond with one another,
they also form hydrogen bonds with other kinds of molecules,
as shown in Figure 2.6a. The presence of hydroxyl (─OH)
or amino (─NH2) groups makes many molecules soluble in
water at high concentrations due to the ability to form sev-
eral hydrogen bonds (methanol [CH3OH] and methylamine
[CH3NH2]). In general, molecules with polar bonds that easily
form hydrogen bonds with water can dissolve at high concen-
trations in water and are said to be hydrophilic. In addition to
the hydroxyl and amino groups, peptide and ester bonds are
other examples (Figure 2.6b).
Because of the strong intermolecular attractions, hydrogen
bonds have a strong effect on the properties of the substances
in which they occur. Compared with non-hydrogen-bonded
compounds of similar size, hydrogen-bonded substances have
relatively high boiling and melting points, low volatilities,
high heats of vaporization, and high specific heats. Molecules
that can form hydrogen bonds with water are highly soluble in
water. In liquid water, each water molecule apparently forms
transient hydrogen bonds with several others, creating a fluid
network of hydrogen-bonded molecules.
The mutual attraction of its molecules causes water to
have melting and boiling points at least 100°C higher than
they would be if water was nonpolar; in the absence of these
intermolecular attractions, water on Earth would exist pri-
marily as a gas. The exact structure of liquid water is still
unknown. It is believed to contain many transient, maximally
hydrogen-bonded networks. Most likely, water molecules are
in rapid motion, constantly making and breaking hydrogen
bonds with adjacent molecules. As the temperature of water
38 Remediation Engineering

H
H H H H
O H
O H ......... O H ......... O H O ......... H

.........
.........

.........

.........
H H
H H H H
O H ......... N CH3
H O ......... H O ..... ..... O H ......... O CH3
H

.....

.....

.....
(a) Water–water Methanol–water Methylamine–water

O H O
C N C O
Peptide Ester
(b)

FIGURE 2.6  (a) Water readily forms hydrogen bonds. (b) Other examples of molecular structures that can form hydrogen bonds.

increases toward 100°C, the kinetic energy of its molecules δ–

becomes greater than the energy of the hydrogen bonds con- H H
O
necting them, and the gaseous form of water appears.
H
H
2.2.4  Ionic Bonds δ–
O
H δ–
O
In some compounds, the bonded atoms are so different in δ– O
electronegativity that the bonding electrons are never shared: H δ– Mg2+
H
H
these electrons are always found around the more electroneg- H δ–
O
ative atom (Table 2.1). In sodium chloride (NaCl), for exam- H
O
ple, the bonding electron contributed by the sodium atom is H δ– H
H O H
completely transferred to the chlorine atom. Even in solid
crystals of NaCl, the sodium and chlorine atoms are ionized, δ– H
K+ O
so it is more accurate to write the formula for the compound O
H δ–
as NaCl2. Because the electrons are not shared, the bonds
(a) H (b) H
in such compounds cannot be considered covalent. They are
ionic bonds (or interactions) that result from the attraction of
a positively charged ion (a cation) for a negatively charged FIGURE 2.7  (a) Ionic interaction between a cation and water. (b)
ion (an anion). A shell of water surrounding a cation in aqueous solution.
Unlike covalent or hydrogen bonds, ionic bonds do not
have fixed or specific geometric orientations because the elec- Most ionic compounds are quite soluble in water because
trostatic field around an ion—its attraction for an opposite a large amount of energy is released when ions tightly bind
charge—is uniform in all directions. However, crystals of salts water molecules. This is known as the energy of hydration.
such as NaCl2 do have very regular structures because that is Oppositely charged ions are shielded from one another by the
the energetically most favorable way of packing together posi- water and tend not to recombine. Salts like NaCl2 dissolve
tive and negative ions. The force that stabilizes ionic crystals in water because the energy of hydration is greater than the
is called the lattice energy. The lattice energy is the energy lattice energy that stabilizes the crystal structure. In contrast,
required to convert one mole of a solid ionic compound in its certain salts, such as Ca3(PO4)2, are virtually insoluble in
usual lattice structure at absolute zero into its gaseous ions. water; the large charges on the Ca2+ and PO43− ions generate
In aqueous solutions, simple ions of biogeochemical sig- a formidable lattice energy that is greater than the energy of
nificance, such as Na+, K+, Ca2+, Mg2+, and Cl−, do not exist hydration.
as free, isolated entities. Instead, each is surrounded by a Most dissolved inorganic compounds are present in
stable, tightly held shell of water molecules. An ionic interac- groundwater in an ionic form. These include dissolved metals
tion occurs between the ion and the oppositely charged end such as Fe2+, Mn2+, Ni2+, Cr6+, and Pb2+ and nonmetal species
of the water dipole, as shown in the following text for the K+ such as Cl−, CN−, F−, NO3−, SO42−, S2−, CO32−, and HCO3−.
ion (Figure 2.7a). In the case of a magnesium ion (Mg2+), six Some of these ions are considered to be contaminants, while
water molecules are held tightly in place by electrostatic inter- others play important and significant roles in the biogeo-
actions between the two positive charges on the ion and the chemical systems within groundwater systems. Important
partial negative charge on the oxygen of each water molecule parameters such as pH (concentrations of H+ ions), electron
(Figure 2.7b). acceptors (NO3−, SO42−, CO32−, etc.), alkalinity, and acidity
Contaminant Characteristics
(concentration of HCO3−, CO32−, OH−, and H+), which strongly
influence remediation processes and contaminant transforma-
tion behavior, depend on the presence or absence of these ions
within the biogeochemical system.
2.2.5 Van der Waals Interactions
When any two atoms approach each other closely, they cre-
ate a weak, nonspecific attractive force that produces a van
der Waals interaction, named for Dutch physicist Johannes
Diderik van der Waals (1837–1923), who first described it.
These nonspecific interactions result from the momentary
random fluctuations in the distribution of the electrons of any
atom, which give rise to a transient unequal distribution of
electrons, that is, a transient electric dipole. If two noncova-
lently bonded atoms are close enough together, the transient
dipole in one atom will perturb the electron cloud of the other.
This perturbation generates a transient dipole in the second
atom, and the two dipoles will attract each other weakly.
Similarly, a polar covalent bond in one molecule will attract
an oppositely oriented dipole in another.
These van der Waals interactions, involving either tran-
sient induced or permanent electric dipoles, occur in all types
of molecules, both polar and nonpolar. In particular, van der
Waals interactions are responsible for the cohesion between
molecules of nonpolar liquids and solids, such as heptane,
CH3 ─(CH2)5─CH3, which cannot form hydrogen bonds or
ionic interactions with other molecules. When these stronger
interactions are present, they override most of the influence of
van der Waals interactions. Heptane, however, would be a gas
if van der Waals interactions could not form.
The strength of van der Waals interactions decreases rap-
idly with increasing distance. If atoms get too close together,
they become repelled by the negative charges in their outer
electron shells. When the van der Waals attraction between
two atoms exactly balances the repulsion between their two
electron clouds, the atoms are said to be in van der Waals con-
tact. Each type of atom has a van der Waals radius at which
it is in van der Waals contact with other atoms. The van der
Waals radius of an H atom is 0.1 nm, and the radii of O, N,
C, and S atoms are between 0.14 and 0.18 nm. Two covalently
bonded atoms are closer together than two atoms that are
merely in van der Waals contact. For a van der Waals interac-
tion, the internuclear distance is approximately the sum of the
corresponding radii for the two participating atoms. Thus, the
distance between a C atom and an H atom in van der Waals
contact is 0.27 nm, and between two C atoms is 0.34 nm. In
general, the van der Waals radius of an atom is about twice as
long as its covalent radius. For example, a C─H covalent bond
is about 0.107  nm long and a C─C covalent bond is about
0.154 nm long.
The energy of the van der Waals interaction is about l kcal/
mol, only slightly higher than the average thermal energy of
molecules at 25°C. Thus, the van der Waals interaction is even
weaker than the hydrogen bond, which typically has energy
of 1–2 kcal/mol in aqueous solutions. The attraction between
two large molecules can be appreciable. If they have precisely
39
complementary shapes, they make many van der Waals con-
tacts when they come into proximity. These van der Waals
interactions, as well as other noncovalent bonds, mediate the
binding of many enzymes with their specific substrates (or the
substances on which an enzyme acts).
2.2.6 Hydrophobic Bonds
Nonpolar molecules do not contain ions, possess a dipole
moment, or become hydrated. Because such molecules are
insoluble or almost insoluble in water, they are said to be hydro-
phobic (“water fearing”). The force that causes hydrophobic
molecules or nonpolar portions of molecules to aggregate
together rather than to dissolve in water is called the hydro-
phobic bond. This is not a separate bonding force; rather, it is
the result of the energy required to insert a nonpolar molecule
into water. A nonpolar molecule cannot form hydrogen bonds
with water molecules, so it distorts the usual water structure,
forcing the water into a rigid cage of hydrogen-bonded mol-
ecules around it. Water molecules are normally in constant
motion, and the formation of such cages restricts the motion
of a number of water molecules. The effect is to increase the
structural organization of water which is energetically unfa-
vorable because it decreases the randomness (entropy) of the
population of water molecules.
The opposition of water molecules to having their motion
restricted by forming cages around hydrophobic molecules or
portions thereof is the major reason molecules such as hep-
tane are essentially insoluble in water and interact mainly
with other hydrophobic molecules. Nonpolar molecules can
also bond together, albeit weakly through van der Waals
interactions. The net result of hydrophobic and van der Waals
interactions is a very powerful tendency for hydrophobic mol-
ecules to interact with one another, and not with water.
Small hydrocarbons like butane (CH3 ─CH2 ─CH2 ─CH3)
are somewhat soluble in water, because they can dissolve
without disrupting the water lattice appreciably. However,
1-butanol (CH3 ─CH2 ─CH2 ─CH2OH) mixes completely with
water in all proportions. The replacement of just one hydrogen
atom with the polar ─OH group allows the molecule to form
hydrogen bonds with water and greatly increases its solubil-
ity. Simply put, like dissolves like. Polar molecules dissolve
in polar solvents such as water, while nonpolar molecules dis-
solve in nonpolar solvents such as hexane.
2.2.7 Dispersion Forces
Molecules that have no permanent dipole still have their elec-
trons in movement. Although the time-averaged distribution
of electrons is symmetrical, at any instant the electrons are not
uniformly distributed, so the molecule has a small instanta-
neous dipole, m. This instantaneous dipole can polarize elec-
trons in a neighboring molecule, giving a small dipole in the
neighbor, and the dipole–dipole interaction results in attrac-
tion between the molecules. This is the dispersion attraction
responsible for molecules sticking together. These dispersion
forces (sometimes called London forces after the theoretician
40
Fritz London) are the weakest of all intermolecular forces.
If the distance between two molecules is r, the dispersion
interaction energy is proportional to l/r, so dispersion forces
only operate over very short ranges. The van der Waals forces
comprise the repulsive forces between electrons and nuclei on
adjacent molecules, as well as the dispersion attractions.
All molecules, including nonpolar molecules, are attracted
to one another by dispersion forces. The larger the molecule,
the stronger the dispersion force. Nonpolar molecules, large or
small, have low solubilities in water because the small-sized
water molecules have weak dispersion forces, and nonpolar
molecules have no dipole moments. Hence, there are neither
dispersion nor polar attractions to encourage solubility.
2.3  CONTAMINANT TYPES
It is essential to have a fundamental understanding of the prop-
erties and behavior of various classes of contaminants to under-
stand their overall fate and transport within the subsurface.
These properties are founded on the forces and interactions
described in the preceding sections, and this understanding
provides a framework for understanding their tendency to dis-
solve in and migrate with ambient groundwater flow, sorb to
soil matrices volatilize into soil gas or to the atmosphere, or
degrade via abiotic or biotic mechanisms. While individual
compounds have their own unique physicochemical properties,
contaminants with similar functional groups, bonding struc-
ture, and properties can often be grouped together and expected
to behave and react similarly in soil and groundwater.
The following discussion serves to highlight examples of
the primary anthropogenic contaminant families encountered
in remediation practice. While contaminants can be classi-
fied together based on their individual properties, it should
be noted that considerable variability in fate and transport
behavior exists even within chemically similar compounds.
Vapor pressure
Soil gas
(air phase)
Va
Henry’s law constant
po
r
y
lit
bi
u
ol
S
Groundwater
(aqueous)
Partition coefficient
FIGURE 2.8  Partitioning of a contaminant among air, water, soil, and free product phases when spilled in a subsurface environment.
(Adapted from Wilson, J.T. and Wilson, B.H., Appl. Environ. Microbiol., 49, 242, 1985.)
Remediation Engineering
2.3.1 Organic Contaminants
By definition, organic contaminants contain mixtures of
carbon and hydrogen atoms. There are thousands of both
naturally occurring and anthropogenic organic compounds
present in both natural and polluted environments, with 2,857
identified in recent counts1 and up to 104 –105 measured com-
pounds estimated.2 Typical organic contaminants of interest
include hydrocarbons associated with petroleum refining and
distribution, chlorinated and nonchlorinated solvents used as
degreasers, raw materials used or generated during manufac-
turing processes, and other unique compounds used as addi-
tives or building blocks for all of the above. As technology
and manufacturing processes continue to advance, it is likely
that currently unregulated or unknown organic contaminants
will continue to be generated and require mitigation.
The fate and transport of organic contaminants is
highly dependent on their physical and chemical proper-
ties. Depending on their size, substitution, solubility, and
volatility, organic contaminants can exist in all four phases
within the subsurface (Figure 2.8). As manufactured, many
historic organic contaminants exist as a NAPL and exhibit
unique behaviors when released into the natural environ-
ment. Compounds with a higher specific gravity than water
(e.g., chlorinated solvents) will exist as a DNAPL and have
a tendency to sink within the saturated zone. Compounds
with a lower specific gravity than water (e.g., petroleum)
will form light NAPL (LNAPL) and, depending on volume,
will either spread laterally or depress the groundwater sur-
face. While NAPL materials can remain as a separate phase
for considerable durations, the distribution of the NAPL and
its decay is tied to the specific NAPL compound(s) and the
relative solubility, volatility, and susceptibility to chemical
transformation. Organic contaminants are segregated into
different contaminant classes that are grouped according to
Contaminant as free
product (separate phase)
Partition coefficient
Pr
es
su
re
Soil matrix
(solid phase)
Contaminant Characteristics
their chemical structure and function groups that affect their
behavior when released in the environment. Examples of
some of the primary organic contaminant classes that drive
remediation activities are provided in the following text.
2.3.1.1  Halogenated Organics
2.3.1.1.1  Chlorinated Alkenes and Alkanes
Extensive use of chlorinated aliphatic solvents (e.g., chlori-
nated methanes, ethenes, and ethanes) in numerous industries
has resulted in the release of bulk raw materials, effluent or
discharge from process streams, and disposed waste products
containing mixtures of both the solvents and other materials
with which they were used (e.g., aromatics, petroleum hydro-
carbons). Based on both widespread use and their relative
recalcitrance, chlorinated solvents represent four of the top
nine most commonly observed VOCs in public supply wells.3
The most common contaminants include chlorinated ethenes,
ethanes, and methanes. The four primary chlorinated alkenes
and alkanes used historically as solvents include carbon tet-
rachloride, tetrachloroethene (PCE), trichloroethene (TCE),
and 1,1,1-trichloroethane (1,1,1-TCA). Carbon tetrachloride
production in the United States was initiated concurrent with
World War I and was later followed by PCE and TCE produc-
tion in the 1940s. Production of these materials increased con-
siderably over the course of the next several decades (Figure
2.9) until more stringent emission controls were required
under the 1970 Clean Air Act.4,5 Between 1970 and 1980,
many industrial operations then shifted to 1,1,1-TCA, which
offered equivalent solvency and was a less toxic replacement.
While not used at the same scale, multiple other chlorinated
aliphatics (1,2-dichloroethane, chloroform, methylene chlo-
ride, etc.) were widely used and are present in the environment
today. In general, chlorinated solvents are characterized by
1400
CTC
1200
PCE
TCE
Millions of pounds produced
1000 TCA
800
600
400
200
0
1920 1930 1940
FIGURE 2.9  Historic solvent manufacturing trends in the United States and relevant regulatory decisions. (Adapted and modified from
Doherty, R.E., J. Environ. Forensics, 1, 69, 2000; Doherty, R.E., J. Environ. Forensics, 1, 83, 2000.)
41
their limited solubility and densities greater than water, with
variations in individual vapor pressures and reactivity attrib-
uted to their degree of substitution and presence or absence
of double bonds. Many chlorinated solvents are carcinogenic
and can result in adverse health impacts to the central nervous
system and reproductive systems as well as to the liver and
kidney.6 In addition to the aforementioned, a number of dif-
ferent degradation intermediates (e.g., cis-1,2-dichloroethene,
1,1-dichloroethene, and vinyl chloride) are generated during
biotic or abiotic dehalogenation reactions, are frequently colo-
cated in groundwater with their parent species, and in some
cases can be of greater risk than the original materials.
Chlorinated solvents can be addressed via a number of
different remedial applications. Their volatility allows for
their removal via vapor extraction or thermal remediation
techniques, and their solubility allows for capture via ground-
water extraction systems. Depending on the solvent material,
multiple in situ remedies are also viable including enhanced
biological degradation, chemical oxidation, or direct abiotic
reduction that serve to transfer the parent species through
daughter products to inert end products.
2.3.1.1.2  Chlorinated Aromatics
Chlorinated aromatics consist of single-ringed (e.g., chloro-
benzenes) or multiringed molecules (e.g., polychlorinated
biphenyls [PCBs]) that exhibit a wide variety of substitution
and physicochemical properties. Most chlorinated aromat-
ics were widely used in electrical, heat transfer, or hydraulic
processes due to their high degree of physical and chemical
stability. Many single-ringed chlorobenzenes were also used
as intermediates in chemical production operations and as
solvents for degreasing applications. PCBs consist of a fam-
ily of anthropogenic compounds comprising molecules with
Clean TCA MCL
water act established
Clean air
act
1950 1960 1970 1980 1990 2000
Year
42
two fused aromatic rings and between 1 and 10 chlorine
atoms. With 209 individual PCBs identified,7 the compound-
specific nomenclature (e.g., Aroclor 1242) is often derived by
the quantity of chlorine atoms (in this case 12) and/or rela-
tive weight percentage of chlorine/biphenyl (42%). PCBs have
low vapor pressure, are strongly adsorptive, and have lim-
ited aqueous solubility.8 While PCB manufacturing and use
ceased in 1977,9 their recalcitrance and limited degradability
within the subsurface have resulted in their continued pres-
ence within the environment. PCBs have received increased
attention due to their ability to bioaccumulate within the food
chain and behavior in disruption of human endocrine and ner-
vous system processes.
Due to their solubility and susceptibility to oxidation
and biological degradation, chlorobenzene species can be
addressed via multiple extraction-based or in  situ treatment
mechanisms. Considerable research has been conducted
around development of noninvasive (i.e., excavation) remedia-
tion strategies for PCB treatment, with some limited practi-
cal benefit. Multiple microbial species have been identified
that can remove individual chlorines from the biphenyl group
and serve to generate less toxic intermediates, but extensive
deployment of these remedies has been limited by the overall
slow rates of biodegradation.
2.3.1.1.3  Fluorinated Organics
Fluorinated organic compounds include chlorofluorocarbons
(CFCs), and perfluorinated carboxylic and sulfonic acids are
soluble in water, have low volatility and vapor pressure, and
due to the electronegativity of the fluorine atom and result-
ing strength of the carbon–fluorine bond exhibit consider-
able resistance to both abiotic and biotic degradation. CFC
use in aerosols and release to the atmosphere since the 1940s
have been well documented, but most CFCs encountered in
considerable quantities at impacted environmental sites are
derived from their use in manufacturing operations or as
refrigerants. Commonly used per- or polyfluoroalkyl sub-
stances (PFASs) include C8 compounds perfluorooctane sul-
fonate and perfluorooctanoic acid, which are more widely
known, but PFAS compounds include any molecule gener-
ally containing two or more carbons in which all hydrogen
atoms have been replaced with fluorine, with the exception
of selected hydrogen atoms with functional group substi-
tutions. PFAS compounds all contain at least one perfluo-
roalkyl moiety C nF2n+1 and are currently defined under 42
different families of compounds.10 These compounds include
straight-chain aliphatic compounds in addition to their vari-
ous homologues, precursors, and other fluorotelomers. PFAS
compounds were used in manufacturing a variety of house-
hold and commercial products, industrial coatings, flame
retardants, and commercial fire-fighting foams. PFAS chem-
ical structures include a lipophilic fluorine–saturated carbon
chain with an ionic end group (e.g., carboxylic acid, sulfonic
acid, sulfonamide) that allow bioaccumulation within fatty
tissues as well as covalent binding with proteins in liver
and blood plasma.11 While detailed assessment of their risk
to human health is still ongoing, PFASs are an emerging
Remediation Engineering
contaminant due to their high degree of aqueous mobility,
recalcitrance, and degree of use.
2.3.1.2 Ketones
Regulated organic compounds also used as solvents or in
manufacturing and process operations include acetone,
methyl ethyl ketone, and methyl isobutyl ketone, which can
result in potential risk to human and ecological receptors
when released into the environment. Compared to chlori-
nated solvents, these compounds are generally highly soluble
in water and are less sorptive to subsurface soil matrices.
As a result, these compounds have the ability to travel sig-
nificantly farther than chlorinated solvents under ambient
groundwater conditions. While they exhibit the potential to
migrate with groundwater flow, based on the similarity of
their chemical structure to organic acids used in microbial
respiration, many of these compounds are susceptible to bio-
logical degradation and replacement reactions around either
the carbonyl or acetyl groups.
2.3.1.3  Petroleum Hydrocarbons
Refined petroleum products are generally complex mix-
tures of organic compounds with minor fractions of organic
and inorganic additives that fall into a number of chemical
classes. Petroleum hydrocarbons are, for the most part, less
dense than water and will exist as LNAPLs that float on top
of groundwater or reside in soils and within the upper satu-
rated zone. Most petroleum species are sparingly soluble in
water and have vapor pressures and volatility that generally
decrease with overall molecular weight. The risk associated
with petroleum materials is highly variable based on their
original use, degree of refinement, and discrete composition.
Benzene, toluene, ethylbenzene, and xylene additives in gaso-
line are all volatile and have higher relative solubilities, while
lube oil contains few contaminants that are soluble in water
and can be generally immobile in the subsurface. As shown
on Figure 2.10, gasoline, kerosene, diesel fuel, and waste oils
have individual constitutions with different physical proper-
ties, all of which affect their behavior in the subsurface and
their potential risk to human health and the environment. As
the individual compounds present in petroleum materials
(e.g., benzene, ethylbenzene, toluene, xylene, naphthalene)
often drive considerations regarding risk and mobility, these
are more strenuously regulated as individual contaminants.
In addition to the characteristic differences in product con-
stitution, the same refined products (e.g., gasoline) can often
vary as a function of the crude oil source from which it was
manufactured, the facility in which it was refined, the geo-
graphic area in which it is to be used, and the individual
manufacturer’s formulation. Coupled with this product het-
erogeneity, petroleum materials will also weather with time
as more soluble and volatile species are lost to groundwater
and soil vapor. Compositional changes in petroleum LNAPLs
will therefore have a bearing on the relative solubility of indi-
vidual contaminants within the material. These tendencies
all add complexity to the development of characterization
and petroleum remediation strategies.
Contaminant Characteristics
69°C 126°C 218°C
156°F 258°F 421°F
Gasoline
Naphthas
Stoddard solvent
Jet fuel/kerosene
JP-4
Diesel fuel/middle distillates
C2 C3 C4 C5 C6 C7 C8 C9 C10 C11 C12 C13 C14 C15 C16 C17 C18 C19 C20 C21 C22 C23 C24 C25 C26 C27 C28 C29 C30
FIGURE 2.10  Approximate carbon content and boiling ranges for different petroleum products. (Adapted from Gustafson, J. et al.,
Selection of Representative TPH Fractions based on Fate and Transport Considerations, Total Petroleum Hydrocarbon Criteria Working
Group (TPHCWG), Amherst Scientific Publishers, Amherst, MA, 1997.)
2.3.1.4  Polynuclear Aromatic Hydrocarbons
Polynuclear aromatic hydrocarbons (PAHs) are complex fused
aromatic ring compounds that can be naturally occurring or
of anthropogenic origin. They have generally high molecular
weight, are readily adsorbed and sparingly soluble, and have
low volatility. PAHs originate from incomplete combustion of
fossil fuels and wood and a variety of industrial processes (e.g.,
coal gasification, petroleum refining, coking). Naturally, they
are sourced to the environment via volcanic activity or fire.
PAH compounds of pyrogenic origin are detectable in soil and
river sediments throughout the inhabited world. PAH molecules
with fused ring numbers from two (naphthalene) to six (coro-
nene) that are bonded in either linear, angular, or clustered struc-
tures.12 While some PAH compounds are more biodegradable
than others, they typically exhibit half-lives on the order of years
to decades under both aerobic and anaerobic conditions.
2.3.1.5  Fuel Oxygenates
Fuel oxygenates have been used in fuel refining and blend-
ing activities since 1979, when they replaced tetraethyl lead
as the primary antiknock agent in gasoline to improve engine
combustion efficiency and minimize negative emissions asso-
ciated with volatile organic compounds and nitrogen and sul-
fur oxides in exhaust. The most widely used fuel oxygenate
was methyl tertiary butyl ether (MTBE), but others include
di-isopropyl ether and tertiary amyl methyl ether (TAME).
Oxygenated additive use in petroleum blending operations has
varied widely in both duration and location and was almost
entirely replaced by ethanol as of 2006. While often exclu-
sively present at sites with comingled petroleum hydrocarbon
release, the variability in use does not imply that they are
present in all sites in which petroleum release has occurred.
Each of these constituents entails either five or six carbon
molecules arranged on either side of an ether group. Fuel
43
343°C 402°C 449°C
849°F 750°F 840°F
Fuel oils
Lube oil, motor oil, grease
oxygenates have relatively low boiling points and high aqueous
solubility (26 g/L for MTBE). As a result, it was historically
believed that sites impacted with fuel oxygenates would exhibit
larger impacted groundwater footprints for oxygenates com-
pared to the petroleum materials with which they were codis-
posed. More recent review of data from hundreds of existing
hydrocarbon sites indicates that fuel oxygenate distribution is
generally consistent with that of soluble gasoline components.13
While all three primary oxygenates are biodegradable under
aerobic conditions, the anaerobic biodegradation of MTBE
commonly results in the formation of tert-butyl alcohol (TBA).
Due to the presence of elevated hydrocarbon availability at
sites with historic release(s), TBA is frequently observed within
close proximity to historical areas of petroleum discharge
where abundant organic carbon has supported consumption of
available electron acceptors (e.g., oxygen, nitrate, ferric iron,
sulfate) and enabled the transformation of MTBE to TBA.
Based on the regional variability in use and negative
water quality effects associated with taste and odor issues in
groundwater—opposed to immediate risk to human and envi-
ronmental health—maximum contaminant levels for each of
these constituents are not always available or applied.
2.3.2  Inorganic Contaminants
2.3.2.1 Metals
Metal contaminants originate from both direct anthropogenic
(e.g., chromium, copper, zinc, lead) release or via indirect
mobilization and dissolution from subsurface soils as a result of
shifts in geochemistry (e.g., iron, manganese, arsenic). Despite
its widespread use, the term “heavy metal” does not have a rig-
orous scientific basis or a chemical definition. Although many
of the elements listed as “heavy metals” have high specific
gravities, major exceptions to this rule remain. A summary of
44 Remediation Engineering

the heavy metals representing a significant environmental con- extraction technologies or immobilized via biotic and abi-
cern and a comparison of commonly occurring light alkali and otic oxidation–reduction (redox) or complexation mecha-
alkali earth metals is presented in Table 2.2. nisms. The fate and transport of metal contaminants in
The fate and transport of metal contaminants are controlled the subsurface are therefore directly tied to an individual
by their different oxidation states and complexation behavior metal’s behavior based on the subsurface geochemistry. The
in the subsurface. The reactivities, ionic charges, and solubili- level of acidity, metal oxidation state, and its speciation and
ties of these metals in water vary widely. For their short- and tendency to form complexes ultimately affect the behavior of
long-term impacts, the maximum permissible concentra- metals, their transport with advective groundwater flow, or
tions of these heavy metals in drinking water and groundwa- their sequestration within soil matrices. Prior to developing
ter are closely regulated through legislation. As many heavy engineered remedial applications to address metal contami-
metals are also required as key micronutrients (with the nants, practitioners should have a detailed understanding of
exception of cadmium, mercury, and lead), the toxicity and both the behavior of individual metals and the permanence
inhibitory effects of these elements are largely related to their of the remedial solution to design and implement remedies
concentration.14 to restore environmental quality. While traditional reme-
Remediation applications do not result in destruc- dial technologies entail groundwater extraction and metals
tion of metals; they are either directly removed via removal via sorption applications, numerous in situ remedial
technologies have emerged that serve to condition aquifer
geochemistry and cost-effectively facilitate metal precipita-
tion and sequestration.
TABLE 2.2
2.3.2.2  Nitrogen Compounds
Commonly Occurring Heavy Metals, Light Alkali,
The natural nitrogen cycle is a complex and dynamic pro-
and Alkali Earth Metals cess that includes both atmospheric and biotic processes
Western Eastern (Figure 2.11) and results in nitrogen cycling between ammo-
United United Lindsay nia, nitrate, and nitrogen gas species. The commercialization
States States (1979) of synthetic fertilizer in the 1940s and subsequent widespread
Metal Specific Averageb Averageb Average expansion of use in agricultural production resulted in a dis-
Species Gravitya (mg/kg) (mg/kg) (mg/kg) ruption of the natural nitrogen cycle by increasing the total
Regulated heavy metals amount of nitrogen (N) mass present in the environment. As
a result of these activities, nitrate is frequently the most com-
Cr 7.19 41 33 100
Co 8.9 7.1 5.9 8
mon anthropogenic pollutant that exceeds water quality cri-
Ni 8.9 15 11 40
teria in drinking water wells in agricultural regions. When
Cu 8.96 21 13 30 consumed in drinking water, nitrate is converted to nitrite
Zn 7.13 55 40 50 during the digestion process and can react directly with hemo-
Ag 10.5 — — 0.05 globin in the blood to produce methemoglobin, which actively
Cd 8.65 — — 0.06 destroys the ability of red blood cells to transport oxygen.
Hg 13.6 0.046 0.081 0.03 Nitrite is rapidly metabolized in healthy adults, but this con-
Ti 11.9 2,200 2,800 4,000 dition is especially serious in babies under three months of
Pb 11.4 17 14 10 age and causes a condition known as methemoglobinemia or
Regulated metalloids “blue baby syndrome.”
As 5.78 5.5 4.8 5 The nitrate impacts currently observed in many shallow
Se 4.79 0.23 0.3 0.3 aquifers are often a result of decades-old fertilizers, which
Sb 6.69 0.47 0.52 — served to load nitrogen into the shallow soil column. In aero-
Commonly occurring light metals
bic soils, the hydrolysis and nitrification of these materials
(e.g., anhydrous ammonia, ammonium nitrate, urea, diam-
Na 0.47 9,700 2,500 6,300
monium phosphate) result in their transformation to nitrate,
Mg 1.74 7,400 2,100 5,000
which then percolates downward to the water table.15 While
K 0.86 18,000 12,000 8,300
Ca 1.55 18,000 3,400 13,700
nitrate is often the sole contaminant monitored in ground-
Al 2.7 58,000 33,000 71,000 water, these other nitrogen compounds can often be over-
looked and serve as a long-term source of leachable nitrate to
Other relevant metals
groundwater. Given the increased attention to regional nitrate
Fe — 21,000 14,000 38,000
issues and associated impacts to community water systems,
Mn — 380 260 600
stronger requirements for remediation and source control
a Sen Gupta (2002). (e.g., fertilizer storage and distribution facilities) are being
b Smith and Huyck (1999). enforced by oversight agencies to reduce overall nitrogen
flux into the natural environment.
Contaminant Characteristics 45

Atmospheric
nitrogen (N2)
δ15N (0%)

Denitrification
Ammonification Lightning
∆17O Denitrifying
Nitrogen-fixing bacteria
bacteria ε15N (up to –20%)
ε15N (–1 to –5%) Animals Plants
Anaerobic
Assimilation ammonium
oxidation
Nitrates (NO3–)
Decomposers (aerobic Annamox
Industrial fixation and anaerobic bacteria
(e.g., urea, fertilizers) bacteria and fungi)
ε15N (–1%) Nitrifying bacteria
(nitrobacter)
Nitrification

Nitrifying bacteria
Nitrites (NO2–)
Ammonia (NH3) (nitrosomas)
+
Hydrolysis Ammonium (NH4 )

FIGURE 2.11  The advanced nitrogen cycle showing industrial nitrogen fixation processes and transformation pathways. Unique isotopic
fractionation shifts in the nitrogen or oxygen isotope ratios can be observed depending on the processes involved.

2.3.2.3 Perchlorate signature or to represent a qualitative indication of similar

While existing naturally in select regional mineral depos-
its, potash ores, or within the atmosphere,16 the majority of
perchlorate encountered within remediation sites is derived
from anthropogenic release during explosive production
and disposal or manufacturing operations. Containing
one chlorine anion and four oxygen anions (ClO 4 −), the
most common perchlorate salts for industrial use include
ammonium perchlorate, sodium perchlorate, and potas-
sium chlorate. In addition to these, other anthropogenic
sources are associated with experimental, medicinal, or
agricultural use (e.g., perchloric acid, chemical reagents,
and fertilizers).16 While perchlorate salts are highly reac-
tive with organic and reduced materials, the perchlorate
anion in the natural environment is highly soluble in water,
exhibits low volatility and sorption, and is highly stable.
Based on its physicochemical parameters, perchlorate is
highly mobile within natural groundwater flow systems.
While generally not degraded via abiotic mechanisms,
many naturally occurring microorganisms can utilize per-
chlorate as an electron acceptor in the presence of natural
organic carbon electron donors. As a result, many engi-
neered remediation applications entail either direct in situ
delivery of organic carbon reagents or ex  situ treatment
within bioreactors.
2.3.3 Other Bulk Parameters
Several bulk parameter measurements bear some dis-
cussion as a useful method of identifying contamination
extent, serving to provide an indication of geochemical
behaving compounds as one bulk response. While certain
bulk parameters are regulated under both primary and sec-
ondary water quality standards, others are used in engi-
neering applications as key rules of thumb to guide both
investigation and treatment operations. While bulk param-
eters can serve as a broad snapshot of existing conditions,
however, specific attention should be paid to evaluate the
significance and impact of the individual compounds that
constitute the total mixture.
2.3.3.1  Total Petroleum Hydrocarbons
During investigation and assessment of subsurface petro-
leum contamination, lump parameter total petroleum
hydrocarbon (TPH) measurements can be used to quantify
the extent of contamination associated with nonregulated
hydrocarbon compounds or provide a general indication
of whether LNAPL or residual LNAPL is present. TPH
measurement captures a wide array of compounds present
in petroleum products with total carbon atoms extending
up to 40 atoms (tetraoctane; C40H82). TPH analyses can be
used to assess the general signature of a petroleum mixture,
and individual sampling spectra can be related to known
banks of standards to identify whether the contamination
consists of one or more of gasoline, diesel fuel, fuel oil,
jet fuels, kerosene, or miscellaneous lubricants, and waxes.
Gas chromatography column elution times can be tailored
to the known petroleum mixture or can be used to provide
a broad response for the materials present. As an example,
gasoline range TPH analysis (TPH-g) is used to quantify
the total magnitude of hydrocarbon (C6 ─C12) associated
46
with a known historical gasoline release. Similarly, the
magnitude of hydrocarbon materials associated with a
diesel gasoline release (C10 ─C28) can be assessed utilizing
diesel range TPH (TPH-d) analyses. As individual hydro-
carbon compounds have a greater tendency to volatilize
or dissolve into groundwater, the presence or absence of
select compounds (e.g., BTEX constituents) can also be
reviewed relative to the analytical response from a new or
fresh gasoline release to assess the degree of hydrocarbon
weathering or depletion, which can be useful in assessing
the age of impacts.
While TPH measurement provides a broad indication
of the overall quantity of hydrocarbon materials present,
they are often paired with other more specific analytes
(e.g., benzene, naphthalene) that are more carcinogenic
and explicitly regulated. Understanding the magnitude of
both the primary risk-driving contaminants as well as the
broader subset of TPH materials is integral to proper reme-
dial system design. The broader TPH spectrum serves as a
sink for chemical oxidants and electron acceptors injected
for in  situ treatment of select target contaminants. The
relative ratio of BTEX constituents to the total LNAPL
or residual LNAPL mixture impacts the relative solubil-
ity and limits their availability for treatment or removal
in the aqueous phase. TPH materials contribute to gran-
ular activated carbon loading during ex  situ treatment.
TPH materials are consumed by native microbial species,
which generate dissolved and vadose zone methane within
petroleum release areas. Accounting for these materials is
therefore a necessity as part of any investigation and reme-
diation design to make sure treatment specifications are
appropriate.
2.3.3.2  Total Organic Carbon
Total organic carbon (TOC) analyses serve as a bulk indica-
tor of dissolved, suspended, or colloidal carbon materials
that are present in groundwater or surface waters. As all
natural waters contain some carbonaceous material, under-
standing the differences in organic carbon attributed to
natural background availability and attributed to contami-
nant concentrations can be important in assessing whether
impacts associated with anthropogenic release are pres-
ent. Most laboratory analytical methodologies entail the
detection of total carbon dioxide following reaction of the
specific sample with an oxidant (e.g., persulfate) and, as a
result, capture a broad response that can be correlated to
other more specific analyses such as the presence of indi-
vidual organic contaminants present within the sample.
While TOC represents a relatively nonspecific analyses,
this parameter is often used in many rule-of-thumb esti-
mates associated with remedial design and operation, with
notable examples including assessment of the presence or
absence of organic electron donors used during in situ bio-
remediation, the natural abundance of organic matter that
can affect sorption on to soil matrices, influent loading on
ex  situ treatment systems, or potential sinks for chemical
oxidants applied in situ.
Remediation Engineering
2.3.3.3  Total Dissolved Solids
The amount of dissolved solids are useful indicators of the
presence of dissolved compounds including inorganic salts
and metallic ions, organic materials, and other dissolved
ionic species (SO42−, Cl−, NO3−) present in groundwater.
Total dissolved solid (TDS) concentration is also important
in models used to characterize soil–water interactions with
regard to mineral and ionic activity (e.g., Debye–Hückel and
Davies equations), as these classical geochemical models are
not applicable at elevated TDS concentrations, and alterna-
tives must be used (i.e., Pitzer model).17 Similar to other bulk
parameters used in assessing water quality, TDS measure-
ments should be coupled with more detailed analyses of major
aqueous cations and anions to supplement characterization
efforts and correlate response. Further, in remediation sites
utilizing TDS response as an investigative technique, sample
collection should include a comparison of the site-specific
background response relative to the area of known or sus-
pected impact.
2.4  PROPERTIES OF CONTAMINANTS
As noted previously, the behavior of contaminants in the
environment is influenced to a great extent by the physi-
cochemical properties of the contaminant and the con-
taminant mixture. These properties govern the extent of
which they partition, migrate, or degrade when present in
bulk quantity, in dilute concentration, or in the subsurface
as gases.
2.4.1 Solubility
The fate and transport of an organic or inorganic contaminant
beyond the point in which it is released is primarily controlled
by its aqueous solubility. The aqueous solubility represents
the maximum aqueous-phase concentration of chemical per
unit volume, while the solution is in equilibrium with the pure
compound in its actual aggregation state (gas, liquid, solid) at
a specified temperature and pressure. Above this concentra-
tion, multiple phases will exist in the solvent–solute equilib-
rium system.
In general, the solubility of organic contaminants var-
ies widely (between approximately 1 and 200,000 mg/L)
and controls the amount of solute that can partition into the
aqueous phase for natural groundwater transport. Fully-
miscible (infinitely soluble) or near-miscible organics include
alcohols, ketones, aldehydes, ethers, and carboxylic acids.
These compounds do not form a persistent separate liquid
phase (NAPL) when spilled into the subsurface and encoun-
ter groundwater. Many of these compounds are also poorly
sorbed on solid-phase organic matter and mineral surfaces
in the aquifer matrix. Hydrophobic organics are consider-
ably less soluble and form NAPLs with a potential to serve
as persistent dissolved-phase contaminant sources to ground-
water. These compounds exhibit a wide range of densities,
from very low relative to water (e.g., benzene, ρ = 0.6) to
very high relative to water (e.g., PCE, ρ = 1.6). Hydrophobic
Contaminant Characteristics
organics are generally susceptible to sorption on organic sol-
ids and colloids, as well as mineral surfaces in aquifers, so a
large portion of the mass of these contaminants may reside
outside the aqueous phase under normal physical–chemical
conditions.
While solubilization to the aqueous phase is governed
by typical equilibrium processes, many environmental
reactions are not occurring under a steady-state condition.
That is, solubility relationships typically assume that the
relationship between the contaminant and the environ-
ment remains consistent with time. As most natural envi-
ronmental conditions are dynamic in nature, with the fate
of contaminants controlled by a combination of volatiliza-
tion, adsorption, diffusion, advective transport, and degra-
dation mechanisms, the term “steady state” is often used
to refer to the collective balance of these processes in the
absence of active remediation programs. Steady-state solu-
bility relationships are therefore a reflection of the instan-
taneous equilibrium of a given contaminant. In this sense,
a dynamic state in remediation practices typically implies
that engineered techniques are being applied to manipulate
the natural fate and transport conditions.
For pure compounds, the aqueous solubility is a direct
reflection of molecular structure and electrochemical char-
acteristics and serves as a fundamental physical constant
that governs contaminant partitioning. Environmental con-
taminants have aqueous solubilities that can range over sev-
eral orders of magnitude from highly soluble compounds
that are completely miscible in water (e.g., alcohols such
as methanol or ethanol) to levels of saturation that are so
low that the concentration can scarcely be detected (e.g.,
benzo(a)pyrene, PCBs). For mixtures of contaminants (e.g.,
mixed waste solvents, petroleum hydrocarbons), solubility
is a general function of the mole fraction of the individual
constituents within the mixture.18–20 The concentration of
an individual compound in water at equilibrium with the
contaminant mixture can be expressed according to the fol-
lowing equation:
Ci* = Ci0 Xi g i (2.1)
where
Ci* is the equilibrium solute concentration for component
i in the mixture
Ci0 is the equilibrium solute concentration for component i
as a pure compound
Xi is the mole fraction of compound i in the contaminant
mixture
γi is the activity coefficient of compound i in the contami-
nant mixture
The activity coefficient of a specific compound in water (γw)
represents the overall dissimilarity between the solute and
solvent (i.e., water) that is associated with structural and polar
differences that affect the enthalpy and entropy of the con-
taminant in the aqueous phase. The aqueous solubility of a
solute is sometimes defined as equal to the reciprocal of its
47
aqueous activity coefficient, as represented in the following
equation:
log Cw = - log g w (2.2)
where
Cw is the aqueous solubility of a compound
γw is the activity coefficient of the compound in water
Another aspect that can affect the solution composition and
solubility of organic chemicals involves the presence of other
aqueous organic compounds that are codissolved and can act as
cosolvents to increase the overall solubility of a particular sol-
ute in water. In cases in which the codissolved species is both
miscible in water and present at elevated concentrations (>10%
by volume), these constituents can act as solvents and result
in preferential dissolution as part of a dual-solvent system. In
cases in which codissolved contaminants are not miscible with
water but are present at elevated concentrations (e.g., waste oil
LNAPL present at the groundwater surface), dissolution of con-
taminants between multiple separate-phase fluid bodies will be
proportional to the relative solubility of the contaminant and
will control partitioning within the dual-solvent system.
2.4.2 Vapor Pressure
A compound’s vapor pressure is a parameter that estimates the
extent of which a given compound can volatilize and partition
into the gaseous phase. The vapor pressure is defined as the pres-
sure exerted by the vapor of a compound at equilibrium with its
pure condensed phase, either liquid or solid, at a given tempera-
ture. Vapor pressure is typically expressed in either millimeters
or inches of mercury or in atmospheres. The vapor pressure of a
pure compound is equal to 1 atm at its boiling point temperature.
Similar to solubility, the vapor pressures of organic com-
pounds vary widely between compounds based on structural and
molecular interaction differences. Vapor pressure is an important
parameter in determining the behavior of contaminants in the
subsurface environment and represents the tendency of a com-
pound to volatilize from either aqueous, solid, or sorbed and/or
NAPL phase into vadose zone soil gas. The physical parameters
that have the greatest effect on vapor pressure are temperature
and the nature of the compound itself (e.g., critical temperature,
critical pressure, and heat of vaporization). For mixtures of com-
pounds, the composition of the mixture also has a bearing on the
vapor pressure according to the following relationship:
Pi* = Xi g i Pi 0 (2.3)
where
Pi* is the equilibrium partial pressure of component i
Xi is the mole fraction of compound i in the contaminant
mixture
γi is the activity coefficient of compound i in the contaminant
mixture
Pi 0 is the vapor pressure of pure compound i
48
Vapor pressures of selected compounds of frequent environ-
mental concern are widely available in the literature.
2.4.3 Henry’s Law Constant
The solubility and vapor pressure of volatile contaminants
are interrelated and control the extent of air–water partition-
ing. This relationship is typically expressed via a contami-
nant’s Henry’s law coefficient, which quantifies the escaping
tendency of a compound to the vapor phase as opposed to
remaining dissolved in water. Henry’s law is an expression of
the partitioning equilibrium between a solute and water when
the solute is at dilute aqueous concentrations. The Henry’s law
constant (KH) is expressed as the ratio of a compound’s abun-
dance at equilibrium between the gas and aqueous phases,
expressed as
Pi
KH = (atm × m 3 /mol) (2.4)
Cw
where
Pi is the partial pressure of a compound in the gas phase
(atm)
Cw is the aqueous solution as a molar concentration (mol/m3)
The units of KH are dependent on the choice of measures. If
the abundance of a compound in air is expressed as moles per
cubic meter of air (Ca), the dimensionless Henry’s law (K ¢H )
constant can be obtained via the following equation:
Ca
K ¢H = (mol/(m 3a × mol) × m 3w ) (2.5)
Cw
KH and K ¢H may be related to one another by applying the
ideal gas law for converting partial pressure in atmospheres
to moles per cubic meters. The dimensionless K ¢H can also
be related to KH using the ideal gas law via the following
relationship:
KH
K ¢H = (2.6)
RsT
where
T is the temperature of water in degrees K
Rs is the ideal gas constant (8.20575 × 10 –5 atm · m3/mol · K)
Based on this equation, it is obvious that compounds with
high vapor pressures and low solubility in water should parti-
tion appreciably from water to air. However, compounds with
high vapor pressure and very high solubility (e.g., acetone,
ethanol) do not partition easily from water.
Henry’s law constant relationships are used extensively as
part of vapor intrusion and fate and transport models to eval-
uate the partitioning of compounds from soil moisture and
groundwater into soil gas. It is also integral for the design of
air stripping and vapor extraction systems.
Remediation Engineering
2.4.4 Density
The density of a compound is expressed as the ratio of its
mass to its volume. The property varies not only with molecu-
lar weight but also with molecular interactions and the associ-
ated chemical structure. As an example, primary and tertiary
butyl alcohols have the same molecular weight but their den-
sities at 20°C are 0.8098 and 0.7887 g/mL. In environmental
remediation, density relationships are important in determin-
ing whether a gaseous contaminant is heavier or lighter than
air and determining whether separate-phase liquids will float
or sink in groundwater. Density relationships are also impor-
tant in evaluating whether different solute concentrations will
result in density-driven groundwater flow patterns. Examples
of this arise in assessing the aqueous transport of concentrated
brines discharged during petroleum recovery and refining
processes or assessing the transport of concentrated injection
reagents following injection into groundwater.
Units of density express a mass to volume ratio. For liq-
uids, the units can be expressed in g/mL or mol/mL and for
solids g/cm3. Vapor densities are typically expressed in units
of g/L or mg/m3.
Densities for pure refined petroleum products range from
0.75 g/mL for automotive gasoline to 0.97 g/mL for no. 6 fuel
oil. In contrast, most chlorinated solvents have densities that
range from 1.1 g/mL for chlorobenzene to 1.63 g/mL for PCE.
When present above its aqueous solubility, the characteriza-
tion of a contaminant’s tendency to behave as a LNAPL or
DNAPL is determined by its relative density (lower or higher,
respectively) to water at a given temperature.
2.4.5 Liquid Viscosity
The viscosity of a liquid is a measure of the cohesive forces
between molecules of a similar substance that work to resist
shear. A liquid’s viscosity has an important bearing on the
movement and recovery of bulk fluids from the subsurface.
NAPL transport in soil matrices (or resistance to) is con-
trolled by NAPL adhesion to soil surfaces and whether suf-
ficient shear can be applied to overcome the cohesive forces.
Under natural conditions, gravity and advective groundwater
flow serve as the two primary forces to induce shear on an
NAPL body. Similar to flow in a conduit, bulk fluid velocity
within the soil pore space is highest at the midpoint between
the adjacent soil surfaces. Between the center of the soil pore
conduit and the soil particle surface, a decreasing velocity
gradient develops to the essentially immobile21 adsorbed frac-
tion of NAPL that forms the soil wetting layer. Within the
microscale conduits that make up most soil matrices, a fluid’s
viscosity has a considerable bearing on the development of
the velocity profile between the center of the soil pore and the
particle surface. For low viscosity fluids, less fluid cohesion
allows transport even under conditions with limited shear.
For high viscosity fluids, however, natural environmental pro-
cesses may not be sufficient to overcome both soil adhesion
and NAPL cohesion and may result in very low or near zero
fluid velocities (Figure 2.12).
Contaminant Characteristics 49

z΄

Flow axis

2πrσ
z θ
(a)

z΄ Radius, r
Pn–w Pw

1
2 Nonwetting Wetting fluid
Flow axis
center line
dvx dvx
dz dz

z
0 vmax
(b) Velocity (L/T)

FIGURE 2.12  Fluid velocity profiles of two fluids in a simple conduit. Curve 1 represents the lower viscosity, relative to the fluid in curve
2, with each fluid subject to identical shear stress (force per unit area, parallel to the flow axis). (a) Orientation of a cross-sectional transect,
perpendicular to the flow access. (b) Velocity profiles along the transect, y–y′. Wetting of the conduit wall leads to a zero-velocity static
layer at the side wall for each fluid. Movement of the fluids through the conduit requires continuous shearing, which exerts a drag on their
movement. The slope of the velocity gradient within the conduit is greater for high-viscosity fluids. (From Payne, F.C. et al., Remediation
Hydraulics, CRC Press, Boca Raton, FL, 2008.)

The force (F) of a fluid moving in a conduit can be deter-
mined based on the fluid viscosity (µ), the area of the conduit
(A), the fluid velocity (v), and the relative distance to the flow
axis (z) via the following relationship:
v transmissivity in the soil matrices as well as its extractability
F = m A (2.7)
z
The fluid force determined in this equation can be used to
relate the fluid viscosity to the shear stress applied and the
velocity gradient via the following relationship:
F /A
m= (2.8)
dvx /dz
While an aquifer soil matrix has considerably more hetero-
geneity than the simple conduit highlighted in Figure 2.12, the
application of these flow concepts remains valid to develop
empirical mobility estimates. Knowledge of a NAPL viscos-
ity is required in formulas for calculating NAPL mobility and
and flow into an extraction well. For refined petroleum prod-
ucts that consist of a complex mixture of organic compounds,
the NAPL viscosity will vary based on the relative quantity
and the associated molecular weights of compounds present
in the product. Similar to their associated density differences,
the viscosity of automotive gasoline is significantly lower than
that of no. 6 fuel oil. Similarly, chlorinated solvent DNAPLs
have lower viscosities than coal tar, creosote, and PCBs.

where
μ is the fluid viscosity (dyne ∙ s/cm2)
F is the force of the fluid (dynes)
A is the area of the conduit (cm2)
dvx/dz is the change in velocity with distance from the flow
axis (cm/s/cm)
Viscosity is commonly reported in units of centipoise
(cP),  and the units presented in the previous relationship
(dyne ∙ s/cm2) are equivalent to one Poise (P) or one millipas-
cal second (mPa ∙ s). Values of viscosity for organic liquids
generally range from 0.3 to 20 cP.18 The viscosities of mixed
DNAPLs are generally in the range of 10–100 cP, which
are significantly greater than TCE (0.444 at 20°C), benzene
(0.647 cP at 20°C), PCE (0.844 cP at 20°C), and water (1 cP
at 20°C).
2.4.6 Fluid Properties
A liquid’s chemical composition plays a defining role in its
subsurface interactions with air, soil surfaces, and other flu-
ids. The interfacial tension between an organic liquid, water,
and air affects the processes related to the formation and
­dispersion of NAPL droplets, the creation of stable emulsions,
and the resistance of contaminants to flow through ­soil capil-
laries. When two immiscible or partially miscible liquids are
brought into contact, the interface between the fluids possesses
free surface energy that is dictated by the physicochemical
properties of the two fluids. This surface energy ­represents
the interfacial tension and is controlled by the unique relation-
ship between the two fluids.
Liquids exhibit both cohesive (liquid–liquid) and adhe-
sive (liquid–solid) interactions within the subsurface,
which, depending on the fluid, include a combination of
50
both van der Waals forces and hydrogen bonding.21 Within
a fluid, individual molecules are surrounded by other simi-
lar molecules, and intermolecular attraction is balanced on
all sides. At a fluid’s surface area, intermolecular forces are
arranged parallel with the surface and toward the center of
the fluid body, which result in a greater inward attraction
away from the surface. The energy required to overcome
these intermolecular forces and deform or increase the flu-
id’s surface area is the surface tension.
Van der Waals forces, particularly relevant to organic com-
pounds, are weak bonds that form between the electrons of
one molecule and the nucleus of another. The sum of the van
der Waals forces increases in magnitude with the total number
of atoms and results in increased attraction and higher boiling
and melting points as organic compounds increase in molec-
ular weight. Hydrogen bonds exist as both intermolecular
bonds connect different molecules and intramolecular hydro-
gen bonds connect similar molecules. The angular chemical
structure of a water molecule and the polarity between the
O and H atoms allow extensive hydrogen bonding capacity
with other water molecules (cohesion) and adhesion with
negatively charged soil surfaces.21 Stronger than van der
Waals forces but approximately 20 times lower than covalent
bonds,22 hydrogen bonds allow water to resist deformation but
enable easy dissociation of polar or ionic solutes. Solute dis-
solution into water also plays a role in changing these relation-
ships and decreasing its overall surface tension. As discussed
in the following section, unique surface energies of different
contaminants result in different transport behavior and inter-
action between the contaminant and water and the soil surfi-
cial interface.
2.4.7 Sorption and Desorption Processes
The extent of which organic and inorganic contaminants can
migrate in the aqueous phase is controlled by their tendency
to adhere to or be retarded by the soil matrix through which
they migrate. There are three broad categories of sorption
occurring in porous media that influence contaminant distri-
bution: (1) ionic adsorption and exchange, especially cation
exchange; (2) organic absorption, also known as partition-
ing; and (3) organic adsorption. In each of these processes,
dissolved-phase molecules or ions migrate into nonaqueous-
phase media including mineral surfaces (ionic adsorption),
mineral crystal lattices (cation exchange), solid-phase soil
organic matter (organic absorption and adsorption), and col-
loidal and liquid-phase organic matter (organic absorption).
An organic contaminant’s tendency to absorb or adsorb is
related to whether the contaminant exhibits a solute–solvent
relationship (absorption) or is bound via direct intermolecular
forces (adsorption).
In fate and transport evaluations, sorption equilibrium
reactions promote the reduction of aqueous-phase contami-
nant concentrations as contaminants present in groundwater
partition into or are retained on natural soil materials. As
a consequence of their partitioning, the transport of dis-
solved contaminants is slowed or retarded relative to natural
Remediation Engineering
groundwater flow. If the equilibrium between adsorbed and
dissolved compounds occurs sufficiently rapidly and if the
concentration on the soil particles is proportional to aque-
ous concentration (i.e., a linear sorption isotherm exists), the
expressions for the transport of a compound can be readily
modified by a retardation factor (R) to describe the behavior:
Dissolved (mobile) compound concentration
+ Sorbed compound concentration
R= (2.9)
Dissolved (mobile) compound concentration
or
Adsorbed concentration
R = 1+ (2.10)
Dissolved concentration
The rate at which the center of mass of a compound in equilib-
rium with the soil matrix travels in an aquifer is equal to the
seepage velocity (υ) divided by R. As an example, if the retar-
dation factor for a compound is 5, a plume of the dissolved
compound will advance only one-fifth as fast as a parcel of
water. An understanding of contaminant sorption is a criti-
cal element of groundwater modeling activities, predicting
plume transport behavior, and assessing the benefits of treat-
ment applications. As a considerable fraction of the overall
contaminant mass within aquifers resides in the sorbed phase,
consideration of both dissolved and sorbed phase is important
in understanding the total contaminant mass and whether it is
accessible to a given remediation technology.
2.4.7.1 Adsorption
Adsorption processes occur for both inorganic and organic
compounds and may occur at mineral surfaces or on the sur-
faces of solid-phase organic matter in the soil. Adsorption
processes occur more slowly than absorption processes and
are sometimes referred to as kinetic sorption, in contrast to
the more rapid partitioning process, which is referred to as
equilibrium sorption. The adsorption process has also been
termed irreversible, but this is a misnomer.
The relationship between aqueous- and solid-phase con-
centrations is described by equations called isotherms.
Two examples are the Langmuir and Freundlich isotherms.
Equation 2.11 shows the Freundlich isotherm, which is non-
linear except in the special case in which the exponent, b,
equals 1.0. In that case, the distribution follows the Langmuir
isotherm, as shown in Equation 2.12.
Csoil = K d ´ Caq
b
(2.11)
Csoil = K d ´ Caq (2.12)
For both isotherms, the concentration units are mg/kg for
soil and mg/L for aqueous phase. The distribution coeffi-
cient, Kd, has units of L/kg. If the adsorption isotherms fol-
low the Langmuir equation (2.12), the adsorption capacity and
Contaminant Characteristics
binding coefficients can be determined graphically, using the
following equation:
Caq 1 C
= + aq (2.13)
Csoil b1b2 b2
where
β1 is a constant that reflects the adsorption binding energy
β2 is the capacity of the adsorbing matrix
The slope of the plotted line equals 1/β2, and the binding
energy constant equals the slope of the line, divided by the
y-intercept.
Two key aspects of adsorption processes are the fact that
there is a maximum capacity due to a limited availability of
adsorption sites and that the adsorption process is associated
with a binding energy. The adsorption of key contaminants is
an exothermic process, and the adsorption process is expected
to proceed more quickly than the desorption process. The
slower reverse reaction (desorption) leads to the adsorption
process being described as irreversible, which is not the case.
Adsorption is also a competitive process. Molecules or ions
that have been adsorbed can be displaced by others that have
a higher binding energy.
2.4.7.2 Absorption
The absorption, or equilibrium partitioning process, occurs
rapidly and is generally the dominant sorption process for
hydrophobic organics in many aquifers. Aqueous-phase con-
centrations are related to sorbed-phase concentrations by the
following partition equation, which is essentially the same as
the Langmuir equation earlier:
Csorbed = K d ´ Caq (2.14)
where
Csorbed is the sorbed-phase soil contaminant concentration
in mg per kgsoil
Caq is the groundwater contaminant concentration in mg/L
Kd is the distribution coefficient in L/kg
The distribution coefficient is calculated from the soil organic
carbon fraction, ƒoc, and the organic carbon partition coef-
ficient, Koc, as follows:
K d = K oc ´ ƒoc (2.15)
The units for Koc are L/kgorg, and the units for ƒoc are kgorg/
kgsoil. Combining the results of Equations 2.14 and 2.15, we
can have
Csorbed = K oc ´ ƒoc ´ Caq (2.16)
Values for the organic carbon partition coefficient, Koc, are
available for many compounds and are available from a
number of sources. There is significant variability between
51
measured Koc values, which is related to differences in the
nature of the sorbing organic matter, experimental tem-
peratures, or other factors that affect observed partitioning.
Values of organic carbon partition coefficients are periodi-
cally updated by the U.S. EPA23 based on reported geometric
means of observed values from multiple sources to reflect an
ever-expanding data set. Values for many of the compounds
not listed in the U.S. EPA references can be obtained from
Welkom and Montgomery.24 Values for organic carbon parti-
tion coefficients for a variety of contaminant compounds are
also available in the literature.
The previous equations are often integrated with all rele-
vant media to estimate the total mass of a given contaminant.
The total sorbed mass is determined from the sorbed-phase
concentration and the soil bulk density (ρbulk) in conjunction
with Equations 2.14 and 2.15, as follows:
Masssorbed = Csorbed ´ rbulk (2.17)
Dissolved-phase mass can be expressed in terms of the aque-
ous-phase concentration (Caq) and the total soil pore water
content (θ) as follows:
Massaqueous = Caq ´ q (2.18)
The results of Equations 2.17 and 2.18 are both expressed in
units of mass per volume and can be summed to determine a
total mass using both sorbed and aqueous phases:
Masstotal = Massaqueous + Masssorbed (2.19)
Dividing Equation 2.17 by Equation 2.19 enables determina-
tion of the fraction of total aquifer contaminant mass that will
reside in aqueous phase as a function of the organic carbon
fraction for the aquifer soil:
Masssorbed Caq ´ K oc ´ foc ´ rbulk
= (2.20)
Masstotal Caq ´ K oc ´ foc ´ rbulk + (Caq ´ q)
The results of Equation 2.20 have been plotted for a variety
of common contaminants as a function of soil organic car-
bon in Figure 2.13. These plots demonstrate that compounds
with high Koc values (e.g., toxaphene, naphthalene, PCE)
will reside primarily in sorbed phase when the soil organic
carbon fraction is high. The partitioning effects observed in
Figure  2.13 become very significant as the carbon fraction
climbs from 0 to 0.005, corresponding to aquifer soil organic
matter contents from 0 to 5000 mg/kg.
2.4.7.3  Multicompartment Sorption Models
The sorption behavior of hydrophobic organic compounds
in aquifers suggests that multiple sorption processes occur,
leading researchers to suggest what are termed multicom-
partment models of the sorption process. These models
typically have a rapid-equilibration component that reflects
52 Remediation Engineering

100
Toxaphene
Naphthalene
80
PCE
1,1,1-TCA

Percentage sorbed
60
TCE
Benzene

40 cis-DCE

Vinyl chloride

20
Tetrahydrofuran

1,4-Dioxane
0
0.000 0.002 0.004 0.006 0.008 0.010
Organic carbon fraction ( foc )

FIGURE 2.13  Relationship between sorbed-phase and total contaminant mass per unit aquifer volume, as a function of soil organic matter
content, as measured by the organic carbon fraction foc.
1st
partitioning absorption as expressed in Equation 2.14 and a The values of Equation 2.22 are expressed in mg/L. The K oc
slower-maturing adsorption component like that embodied in value is the conventional organic carbon partition coefficient.
the Freundlich isotherm (Equation 2.11). Luthy et al.25 provide The second compartment is calculated as follows:
a comprehensive review of the geosorbents found in aquifers
and the nature of their interactions with hydrophobic organic 2nd
K oc ´ foc ´ f ´ qmax
2nd
´ Caq (2.23)
q 2nd =
compounds. However, methods that characterize the various f ´ qmax + K oc ´ qmax ´ Caq
2nd 2nd 2nd

geosorbents described by Luthy et  al. are not available for
routine analysis of aquifer soils. Without that breakdown, where
the analysis of TOC provides a basis for estimating partition-
ing equilibrium behavior (which is expected to dominate the

2nd
K oc = 105.92 ± 0.16 (2.24)
sorbed mass in most circumstances), and a smaller-scale, lag-
ging desorption can be expected to occur as a result of adsorp-
and
tion processes, the magnitude or duration of which cannot be
quantified.
æ K 1st ö
Chen et  al.26 provided an empirically derived two- 2nd
qmax = foc ´ ç oc ´ Csat ÷ (2.25)
compartment model that combined a rapid partitioning process è 0.63 ø
with a slower, capacity-limited adsorption process. Termed
the dual-equilibrium desorption (DED) model, the sorption The variable ƒ in Equation 2.23 represents the fraction of the
behavior is described by the summation of the partitioning and second compartment that is saturated upon exposure. Chen
adsorbing processes as shown in the following equation: et al. assume the value for ƒ is 1.0 in their calculations. The
2nd
value for K oc in Equation 2.24 was empirically determined
q = q1st + q 2 nd (2.21) from a population of 41 samples considered by Chen et al. Kow

is the octanol–water partitioning coefficient for the hydropho-
where bic organic and Csat is the aqueous-phase solubility of that
q is the total soil concentration compound. The exponent in Equation 2.25 was also empiri-
q1st is the soil concentration predicted by partitioning cally determined by Chen et al.26
equilibrium Combining terms, the result can be
q2nd is the soil concentration predicted by a linear adsorp-
tion isotherm 2nd
K oc ´ foc ´ qmax
2nd
´ Caq
q = K oc
1st
´ ƒoc ´ Caq + (2.26)
qmax + K oc ´ foc ´ Caq
2nd 2nd

All values are mg/kg. The first compartment is calculated

according to Equation 2.16, using the DED terminology:
At low values of Caq, Equation 2.26 reduces to a Langmuir
isotherm, and at high values of Caq, the equation reduces to
Ctotal
Caq = (2.22) an equilibrium partitioning model. Equation 2.26 provides a
( K oc ´ foc ) + (qW /rbulk ) “bridge” between the adsorption- and absorption-dominated
Contaminant Characteristics
100
10
Soil concentration (mg/kg)
1
0.1
A
0.01
0.001
0.0001
1e–5
FIGURE 2.14  Dual-equilibrium desorption calculation for PCE, using the model described by Chen et al.26 The value for Csat was assumed
as 110 mg/L, the Koc was 265, and the aquifer soil organic carbon fraction was 0.001 (1000 mg/kg TOC). Curve segment A shows the portion
of the dual-equilibrium desorption model dominated by the Langmuir isotherm, segment B shows the transition zone between desorption
models, segment C is the zone dominated by partitioning equilibrium, and segment D shows the sorption relationship predicted by “classic”
equilibrium partitioning.
sectors of the overall sorption process and calls our atten-
tion to the bimodal nature of sorption behavior that can be
expected for hydrophobic organic compounds in aquifers.
Figure 2.14 provides a graphic display of the aqueous phase–
sorbed phase relationship for PCE predicted by the dual-
equilibrium desorption model. For PCE, the model suggests
that the sorbed fraction significantly exceeds predictions of
the “classic” partitioning equilibrium model at concentrations
from 0.001 to 10 mg/L. Because the adsorbed fraction reacts
more slowly than the partitioned phase to changes in aqueous-
phase concentrations, desorption processes will occur much
more slowly under this model, particularly at lower aqueous-
phase concentrations.
One aspect of the DED model that might be controver-
2nd
sial is the assertion that K oc can be represented by a single
value for a wide range of hydrophobic organic compounds.
For comparison, Suthersan and Payne27 examined the appar-
ent Koc for a PCE sorption compartment that resisted oxida-
tion in bench trials. In that case, the apparent Koc value was
104,000 L/kg for the oxidant-resistant fraction, compared to
an apparent value of 2,600 L/kg for the oxidized fraction.
Both values far exceeded the EPA-published value for the Koc
of perchloroethylene, and the Koc for the oxidant–resistant
fraction was 5.5-fold lower than the low end of the range of
values suggested by Chen et al.26 Nonetheless, the DED model
appears to provide an order-of-magnitude approximation of
field-observed sorption behaviors.
2.4.7.4  Cation Exchange Capacity
Soil minerals and organic matter can bind cations in com-
petitive adsorption. The strength of the binding increases with
53
MCI
C
B
D
1e–4 1e–3 1e–2 1e–1 1e+0 1e+1 1e+2 1e+3
Groundwater concentration (mg/L)
valence number and mass of the cations. The following are
common groundwater cations, shown in order of decreasing
exchangeability (increasing binding strength):
Na+ > K+ > Mg2+ > Ca2+ (2.27)
If the calcium and sodium concentrations in aqueous phase
are equal and no other cations are present in solution, calcium
is likely to displace sodium that may reside on adsorption
sites in the aquifer matrix mineral and organic matter. Metal
cations, particularly multivalent transition metals such as
hexavalent chromium (Cr6+), are likely to be strongly sorbed
to cation exchange sites.
Because cation exchange is a competitive process, the
cations on any soil can be displaced by flooding the aqueous
phase with competing cations. For example, sodium displaces
calcium and magnesium ions bound to cation exchange res-
ins in water softeners during the recharge cycle, in which the
exchange resin is flooded with a saturated sodium chloride
solution. During the operational phase, calcium and magne-
sium, which are more strongly bound and present at higher
concentrations in influent water, displace sodium cations on
the exchange resin. If aqueous-phase chromium is added to
groundwater, it is expected to displace a portion of the native
calcium, magnesium, and other cations adsorbed to the aqui-
fer matrix.
The magnitude of cation exchange capacity depends on the
soil particle size distribution (smaller particles, with higher
surface area per volume, have a higher exchange capacity than
large particles) and the mineral composition (clays have high
exchange capacities, sands have lower exchange capacities),
54
both of which control the cation exchange capacity. The cat-
ion exchange capacity is expressed as charge equivalents (the
sum of exchangeable cation molarities, multiplied by their
respective ion charges) per unit soil mass:
CEC = å ([ A] ´ z A + [ B] ´ zB …) (2.28)
where
CEC is the cation exchange capacity
[A], [B], etc., are the molarities
z A, z B, etc., are the charges of all cations in aqueous phase
The cations are measured in a solution of a displacing cation
such as ammonium chloride, NH4Cl, which has been used
to flood a soil sample and displace all the cations other than
ammonium, NH4+.
Cation exchange capacity is not often measured in aqui-
fer soil samples, but it may be an important determinant in
the mobility of contaminant cations, such as transition met-
als. In source areas, where high-concentration solutions
flood an aquifer matrix, transition metal ions will displace
native calcium, magnesium, and potassium. When aque-
ous-phase concentrations of the transition metals decline
through groundwater flushing, the competitive replacement
of transition metals by native cations can drive a persistent,
low-concentration leaching of the transition metals back into
the groundwater. During periods of high contaminant metal
concentrations in groundwater, the cation exchange process
acts as a scavenger. During later periods of low-contaminant
metal concentrations, adsorbed material becomes a low-level
source.
2.5 TRANSPORT, MOBILIZATION, AND
PARTITIONING IN THE SUBSURFACE
2.5.1 Nonaqueous-Phase Liquids
NAPLs are, by definition, immiscible with water. To form
persistent fluid bodies within an aquifer, a fluid must meet
two basic criteria: (1) its solubility must be exceedingly small
so that the water surrounding the separate-phase fluid is at, or
near, the solubility limit for all the fluid’s components (other-
wise, the NAPL would be lost entirely to the aqueous phase),
and (2) the interfacial tension at the NAPL–water interface
must be sufficient to prevent easy mixing of the fluid masses.
Persistent NAPL masses are observed for fluids that generate
an interfacial tension greater than 25 dynes/cm in contact with
water.21
Compounds that form DNAPLs are defined by their low
aqueous solubility and densities greater than water. Typical
DNAPL-forming contaminants include chlorinated solvents,
chlorinated benzenes, PCBs, coal tar, creosote, and some
pesticides. Subsurface DNAPL behavior is categorized by
their tendency to sink via gravity to depths well below the
water-level surface. DNAPLs exhibit absorption behavior
and are preferentially retained in carbon-rich soil strata.
Remediation Engineering
With gravity being a primary driver for DNAPL migration,
DNAPLs migrate downward via the path of least resistance
until they encounter confining or impermeable strata that
prevent or limit further transport. Similar to aqueous-phase
contaminant transport, DNAPL migration is controlled by
hydraulic conductivity differences and relative changes in
soil permeability. In addition, DNAPL migration is also con-
trolled by the specific DNAPL physical properties and vol-
ume, as downward pressure applied by a DNAPL body must
be sufficient to enable it to be squeezed into and through
soil pores. As a result, differences in permeability between
soil strata and the presence or absence of confining layers
strongly affects both the vertical and horizontal distribution
of DNAPLs in the subsurface.
LNAPL materials comprise compounds that are lighter and
immiscible in water. Commonly encountered contaminants
may include benzene, toluene, ethylbenzene, and xylenes; all
of which may also be associated with multicomponent petro-
leum LNAPLs released during fuel refining and distribution
activities. Similar to DNAPL transport, LNAPLs will sink via
gravity toward the groundwater surface following which they
mound and migrate horizontally via bulk fluid migration or
capillary transport.
Governed by solubility constraints and equilibrium par-
titioning, the slow dissolution of NAPLs will contribute to
ongoing dissolved-phase plume formation over an extended
period of time. Individual compounds will dissolve up to
their solubility limit, or their relative solubility if they exist
as a mixture, at a given groundwater temperature. As a result,
the identification and characterization of NAPL materials
at remediation sites are of utmost importance as part of site
characterization to ensure that remedial designs can appro-
priately address and eliminate NAPL source mass during
remedial implementation. Improvements in rapid character-
ization techniques have allowed practitioners to rapidly and
cost-effectively conduct high-resolution mapping and real-
time characterization techniques that enable cost-effective
assessment of NAPL distribution in advance of remedial
selection. These techniques are presented in additional detail
in Chapter 3 and can provide considerable value in reducing
the life-cycle cost of remediation.
2.5.1.1  NAPL Architecture
NAPL architecture refers to the distribution and retention of
either LNAPL or DNAPL materials with the soil and ground-
water in which they reside. Intuitively, NAPL behavior is
strongly controlled by the total NAPL volume and the nature
of release (e.g., one catastrophic event, reoccurring discharge
over multiple years). As NAPLs migrate downward through
soils, they exhibit a slight loss in overall volume as a fraction
of NAPL is retained and immobilized within the soil pores
through which it migrates. Gravity-driven NAPL transport
continues until the bulk fluid reaches less permeable or imper-
meable soil strata (both LNAPL and DNAPL) or the ground-
water interface (LNAPL). Being lighter than water, LNAPL
materials descend downward until they reach the groundwa-
ter surface, mound, and travel horizontally (Figure 2.15a).
Contaminant Characteristics
UST
(a)
UST
(b)
FIGURE 2.15  Conceptual distribution of LNAPL (a) and DNAPL
(b) distribution and resultant dissolved-phase plume evolution.
(Adapted and modified from Kueper, B.H. and Davies, K.L.,
Assessment and delineation of DNAPL source zones at hazard-
ous waste sites, GroundWater Issue, United States Environmental
Protection Agency, Washington, DC, 2009; Interstate Technology
and Regulatory Council, Evaluating natural source zone depletion
at sites with LNAPL, Washington, DC, April, 2009.)
Increased LNAPL volumes will also displace groundwater
vertically downward, which can result in trapped LNAPLs in
soil strata beneath the groundwater surface and be retained on
soils within the saturated zone. Once deposited, subsequent
migration of LNAPL is primarily controlled by the volume
of LNAPL, hydrodynamic processes associated with ground-
water surface gradients (horizontal migration), and seasonal
fluctuations in surface elevation (vertical migration).
While DNAPLs released in bulk quantities can form per-
sistent fluid bodies in the subsurface, gravity-driven migra-
tion through porous media results in DNAPL distribution as
extended ganglia or as disconnected globules that can fol-
low circuitous pathways as they move downward through the
more permeable soil strata (Figure 2.15b). This can result in
DNAPL residence in subsurface intervals that are not imme-
diately below the original point of release. Once distributed,
dissolution and absorption mechanisms result in the penetra-
tion of contaminants within less porous soil strata where they
can be retained for considerable durations.
2.5.1.2  NAPL Saturation and Mobility
As described earlier, NAPL architecture encompasses the
bulk distribution of NAPL as pooling fluid bodies or as
residual NAPL that exists as interconnected ganglia, discon-
nected globules and droplets. The term “NAPL source zone”
is used to refer to the spatial distribution over which collective
55
pooled and residual NAPL is encountered, with the bulk
retention capacity accounting for the total NAPL volume
retained.28 An NAPL’s mobility or immobility is controlled
by its overall saturation within the soil strata, and NAPLs
will not be encountered when the volume of contaminant is
below the soil saturation limit as calculated via the following
relationship29–32:
æ q + K oc,i × foc × rs + Hi × qa ö
Csat , soil , i = Si × ç w ÷ (2.29)
è rs ø
where
Csat, soil, i is the soil saturation limit for chemical i (mg/kg)
Si is the pure chemical aqueous solubility limit for chemi-
cal i (mg/L)
θw is the soil water content (cm3-water/cm3-soil)
Koc,i is the organic carbon/water partitioning coefficient for
chemical i (L-water/kg-oc)
foc is the mass fraction of organic carbon in soil (g-oc/g-soil)
ρs is the dry soil bulk density (g/cm3)
Hi is Henry’s law coefficient for chemical i (cm3-water/
cm3-air)
θa is the soil air content (cm3-air/cm3-soil)
The value of Csat,soil in this calculation represents the concen-
tration at which the contaminant is present above its aqueous
solubility limit and equilibrium saturation is achieved within
both soil pore water and vapor phases. While the previous
calculation assumes a pure compound NAPL, this method
overestimates the value of Csat,soil in multicomponent NAPL
mixtures. Modifications to the previous calculation can be
made to account for the vapor pressure and solubility limits
for individual components using available methods29,30,33–35 to
more accurately predict Csat,soil values.
Determining the concentration at which NAPL is immo-
bile can be critical to understanding contaminant fate and
transport and determining whether the contaminant source
will continue to migrate or remain stationary. When present
in volumes that exceed Csat,soil, residual NAPL will be pres-
ent but not necessarily mobile. In general, free-flowing NAPL
is not encountered when the volume present exists at quanti-
ties that are greater than the value of Csat,soil but are less than
the residual NAPL soil concentration (Cres,soil). The value of
Cres,soil can vary widely between 5% and 30% of the soil poros-
ity28 depending on the soil makeup (e.g., fraction of organic
carbon, grain size, moisture content), the structure of the soil
strata (e.g., porosity, heterogeneity), and the physicochemical
composition of the NAPL or NAPL mixture (e.g., density,
surface tension, interfacial tension, viscosity). At these con-
centrations, residual NAPL remains trapped within individual
soil pores and the fluid entry pressure exerted by the NAPL is
not sufficient to exceed the capillary pressure of the water wet-
ted soil pores. At concentrations below Cres,soil, the magnitude
of the collective capillary forces (i.e., water surface tension,
van der Waals, Coulombic forces) acting on the NAPL body
exceeds the force of gravity by several orders of magnitude.29
56 Remediation Engineering

The following equations can be used to generate a conserva- complete NAPL removal is nearly impossible to achieve as
tive estimate for the specific NAPL concentration at which it fractions of residual NAPL will remain immobile in smaller
will remain immobile29: pore spaces within the soil matrix.
At volumes in excess of Cres,soil, NAPLs agglomerate, pool,
æ q ×r ö and are transmissive as separate fluid bodies. At these concen-
Cres,soil = ç o o ÷ × 106 mg/kg (2.30) trations, pooling NAPLs can account for anywhere between
è rs ø
30% and 80% of the total soil porosity,28 and the force of grav-
ity exceeds that of the capillary forces that otherwise limit
qo = Si × qT (2.31) mobility at values below Cres,soil (Table 2.3).
Understanding the tendency of LNAPL to accumulate
where and flow under natural hydrogeologic conditions is critical to
θo is the residual nonaqueous-phase volume fraction determining its ability to migrate within the subsurface or its
(cm3-res/cm3-soil) susceptibility to bulk removal via engineered extraction tech-
ρo is the density of chemical residual NAPL (g-res/cm3-res) niques. While the methodology earlier establishes a frame-
ρs is the dry soil bulk density (g-soil/cm3-soil) work for evaluating whether an NAPL will remain mobile
θT is the soil porosity (cm3-void/cm3-soil) or immobile within the subsurface, a more comprehensive
Sr is the fraction of residual NAPL-filled void (cm3-res/ assessment for determining LNAPL and DNAPL mobility is
cm3-void) described in Chapter 3.

It should be noted that while capillary forces restrict NAPL
migration at values less than Cres,soil, engineered forces (pneu-
matic forces associated with vapor extraction, groundwater
pumping) applied on the NAPL body or surfactants used to
increase its transmissivity can work to overcome these forces
and induce migration. Even in these instances, however,
2.5.1.3  NAPL Weathering
Following release to the subsurface, NAPL materials are
weathered via multiple mechanisms: (1) sorption on to the soil
matrix through which it travels, (2) volatilization to soil gas,
(3) dissolution into groundwater and natural soil moisture,
and (4) biodegradation. These processes collectively result in

TABLE 2.3
Example of Nonaqueous-Phase Liquid Concentration Values in Soil Matrices
NAPL Soil Type Sr (cm3/cm3) 1000 × θo (cm3/cm3) Cres,soil (mg/kg) Csat,soil (mg/kg) Ref.
Gasoline Coarse sand 0.15–0.19 61–87 24,954–31,609 106 a
Gasoline Medium sand 0.12–0.27 48–109 19,797–44,476 106 a
Gasoline Fine sand 0.19–0.6 79–240 31,065–98,100 106 a
Gasoline Graded fine-coarse sand 0.46–0.59 184–236 80,500–103,250 106 a
Mineral oil Ottawa sand 0.11–0.235 39–82 20,116–42,975 3 b
Mineral oil Glacial till 0.15–0.28 30–56 13,500–25,200 3 b
Mineral oil Glacial till 0.12–0.21 24–42 10,800–18,900 3 b
Mineral oil Alluvium 0.19 95 61,071 3 b
Mineral oil Loess 0.49–0.52 240 154,000–163,800 3 b
Trichloroethene Medium sand 0.12 78 70,448 1045 c
Trichloroethene Fine sand 0.15–0.2 65–86 62,344–83,125 1067 c
Trichloroethene Loamy sand 0.08 33 30,713 1057 d
Tetrachloroethene Fine/medium beach sand 0.002–0.2 1–82 830–83,025 195 e
O-Xylene Coarse sand 0 3 1,936 143 f
Gasoline Sandy loam 0.42–0.59 189–266 94,500–132,750 — g
Tetrachloroethene Sandy loam 0.85 383 413,000 — g
Trichloroethene Sandy loam 0.75–0.92 338–412 328,000–401,208 — g

Source: Brost, E.J. and DeVaull, G.E., Soil and Groundwater Research Bulletin, 9, 1–9, June 2000.
Note: Assumed 50:50 mixture diesel and gasoline to estimate Csat,soil; —, not estimated; Italicized values represent calculated terms.
a Hoag and Marley (1986).36

b Pfannkuch (1984).37

c Lin et al. (1982).38

d Cary et al. (1989).39

e Poulsen and Kueper (1992).40

f Boley and Overcamp (1998).41

g Zytner et al. (1993).42

Contaminant Characteristics
LNAPL and DNAPL compositional changes and yield devel-
opment of dissolved contaminant groundwater plumes. NAPL
weathering processes are controlled by the physical proper-
ties, including the contaminant solubility, recalcitrance, and
degradability, and the hydrodynamic mechanisms that work
on the NAPL body. As groundwater flows past, through, and
around the NAPL body, constituents dissolve into the aque-
ous phase based on their solubility. The steady-state influx of
unimpacted groundwater from upgradient of the NAPL body
results in a constant rate of NAPL weathering as equilibrium
partitioning occurs between the NAPL body and groundwater.
As a result, NAPL weathering processes are strongly linked
to the location of the NAPL body and whether it resides at or
below the groundwater interface.
The tendency of LNAPLs to reside at the groundwater
interface yields multiple mechanisms that all contribute to its
weathering. For petroleum LNAPLs, the variety of organic
compounds with a wide range in both vapor pressure and
aqueous solubility results in considerable compositional
changes over time. In multicomponent LNAPL mixtures (e.g.,
petroleum), an individual contaminant’s maximum aqueous
equilibrium concentration, or effective solubility, is deter-
mined by both its specific mole fraction within the LNAPL
and the solubility of the contaminant in the pure phase43:
Sie = Xi × Si (2.32)
where
Sie is the effective solubility of an individual LNAPL con-
stituent (mg/L)
Xi is the unitless mole fraction of the individual constituent
within the NAPL
Si is the solubility of constituent in the pure phase (mg/L)
The weathering process results in the loss of lower-molecular-
weight constituents in petroleum LNAPLs that are both more
volatile and more soluble (e.g., benzene, toluene, ethylben-
zene, xylenes) than other petroleum hydrocarbon compounds,
which results in increasing LNAPL viscosity as heavier-
molecular-weight constituents are left behind. Based on the
relationship presented earlier, this process results in an overall
decrease in effective solubility of these lighter compounds and
a reduction of dissolved-phase contaminants partitioning to
groundwater that resides in direct contact with the LNAPL.
The migration of DNAPLs to depths beneath the water
table results in increased surface areas for contaminant mass
transfer from the NAPL to the aqueous phase. The existence
of highly heterogeneous DNAPL ganglia and/or globules
increases the overall DNAPL surface area to further enhance
aqueous partitioning. While complete DNAPL dissolution
may often take decades to centuries for highly impacted
source zones,28,44 the combination of DNAPL physical trans-
port behavior (e.g., via circuitous, heterogeneous flow path-
ways) and dissolution processes often results in DNAPL
saturations that are below the value of Cres,soil, and pooling
DNAPL is often not encountered even in cases where the col-
lective contaminant volume is considerable.
57
In conjunction with the vapor- and aqueous-phase parti-
tioning, biodegradation processes in the vapor, aqueous, or
NAPL phase can often serve as a primary weathering mecha-
nism. The extent of biodegradation is generally dependent on
the recalcitrance of the contaminant and the availability of
natural electron donors and electron acceptors that support
microbial metabolism. Hydrocarbons present in petroleum
LNAPLs or in organic solvents (e.g., alcohols, ketones) serve
as viable carbon electron donors for biological oxidation pro-
cesses in which they are directly consumed in the presence
of naturally occurring dissolved oxygen, ferric iron, nitrate,
and sulfate electron acceptors within many subsurface sys-
tems. Similarly, chlorinated solvent DNAPLs can be utilized
as electron acceptors in the presence of naturally occurring
organic carbon or humic electron donors. Biodegradation of
individual NAPL constituents depresses the aqueous con-
centration of the contaminant and promotes additional mass
transfer from the NAPL body to the aqueous phase. In the
case of highly degradable contaminants, this process also
controls or reduces the overall extent of dissolved-phase con-
taminant migration along the length of groundwater plumes.
2.5.2 Hydrodynamic Transport Processes
The field of remediation hydrogeology has evolved over the
last decade as practitioners, and academics have reexamined
the solute transport process. The conventional understanding
of groundwater transport at a macroscale has been refined for
the purposes of characterizing, modeling, and remediating
contaminants that are controlled by more discrete and local-
ized hydrogeologic conditions. The result has been a revision
in the overall scale at which we evaluate both groundwater
and contaminant transport, with a focus on accounting for
discrete transport pathways. This shift has changed how we
conceptualize soils and groundwater flow pathways and their
influence on contaminant plumes and concentrations. As
described in greater detail in Chapter 3, the transport of dis-
solved contaminants in saturated porous media is controlled
by advection, molecular diffusion, and mechanical disper-
sion. Conventional hydrogeologic principles placed increased
importance on the influence of transverse dispersion, but
plume delineation and characterization activities have consis-
tently demonstrated that plumes develop along focused flow
pathways and are most strongly controlled by both advection
and diffusion.
Advection is the bulk movement of solute at a velocity
equal to the “mean velocity” of flow within an aquifer system.
While many classical hydrogeologic equations are appropriate
for and have been used extensively in support of water supply
well design, these methods cannot account for contaminant
transport through heterogeneous soil architecture and local-
ized geologies at the scale of most remediation sites. As lithol-
ogies comprising multiple or even single soil types can have
hydraulic conductivities that vary by multiple orders of mag-
nitude (i.e., or clay versus sand, or coarse-grained sand versus
fine-grained sand, respectively), the mean velocity unique to
individual soil types and specific lithologic intervals should
58
be determined to adequately evaluate their contribution to
contaminant transport.
Diffusive mass transport has garnered considerable attention
over the course of the past decade as remediation practitioners
and responsible parties have grappled with elongated cleanup
time frames and observed contaminant rebound following
engineered treatment applications. While primary contami-
nant transport occurs via advection, contaminants migrating
through the more permeable pathways will diffuse into the
surrounding less permeable soils over time. This relationship
is often described as dual domain and is represented as a two-
compartment system: one mobile that represents the portion of
an aquifer where most of the water movement and hence advec-
tion occurs and one immobile that represents the portion of
an aquifer where the pore fluid is essentially stagnated. While
differences in the rate of contaminant transport via advection
or diffusion can vary up to 5–6 orders of magnitude,45 plume
maturation occurring over multiple decades can result in con-
siderable contaminant storage along the sidelines of advective
transport pathways. The end result is that stored diffuse con-
taminants within an aquifer can diffuse back into the primary
advective pathways once they are clean or remediated.
Dispersion is the spreading of a solute as it moves
through a  porous media. Dispersion can be characterized at
macroscopic and microscopic scales and has been histori-
cally defined by longitudinal dispersion (in the direction of
flow) and transverse dispersion (perpendicular to flow).
Longitudinal dispersion is correlated with differences in rela-
tive soil permeabilities and the associated variance in advec-
tive transport that occurs along the length of plume transport.
Transverse dispersion was historically believed to contribute
to “lampshade” plume development characterized by the fan-
ning spread of contaminants migrating away from a source
via porous media (Figure  2.16), but the effects of trans-
verse dispersion have been refuted21 supported by a greater
f1
18
f2 ∙ f1
19 20
28° arc
(a)
FIGURE 2.16  Historical representation of transverse dispersivity in hydrogeology texts, including (a) Danel46, (b) Bear47, and (c) Freeze
and Cherry48. Plume characterization and observations have provided new insights into transport dynamics, diminishing the significance of
transverse dispersion on plume transport.
Remediation Engineering
understanding of the heterogeneities that contribute to plume
development. Compared to the transport behavior represented
in Figure 2.16, several examples of groundwater plumes are
presented in Figure 2.17 that reflect the limited contribution
of transverse dispersion to plume evolution. While transverse
dispersivity plays an insignificant role in plume evolution,
other mechanical dispersion mechanisms associated with
aquifer use (for agricultural or drinking water purposes) or
shifts in flow direction caused by temporal changes or geo-
logic heterogeneities still contribute to dispersion influences
in plume development.
2.5.2.1  Solute-Based Transport
Contaminant migration and fate and transport beyond the
point of release are highly dependent on the velocity and
flow of aqueous environments in which it resides. The prop-
erties of water are highly unique relative to other fluids. The
dipolar arrangement of electron orbitals between O and H
atoms yields both strong negative (at the oxygen atom) and
positive (at both hydrogen atoms) charge densities and gives
water the strongest dielectric coefficient of any fluid.22 The
polarity and potential to form hydrogen bonds result in water
being an excellent solvent for both salts and polar molecules
that can dissociate and/or remain stable in solution. The
combination of a contaminant’s retardation and solubility
behavior with the natural advective groundwater velocity
(or  seepage velocity) ultimately controls the distance dis-
solved-phase plumes migrate and their potential influence
on sensitive receptors.
Solute transport in groundwater plumes is often described
in terms of relative mass flux (J) and mass discharge (Md). Mass
flux is a measurement of an instantaneous rate of contaminant
transport for a given location or geologic interval within a
plume. Mass flux is expressed in units of mass per time per
area, with area defined in two dimensions perpendicular to
θ = 34°
Direction of
average flow
Source
of tracer
(continuous
injection)
(b)
(c)
Contaminant Characteristics 59

Borden aquifer studies – Rivett, Feenstra and Cherry TCE concentration

(µg/L)

TCM 322 Days 10,000

–45 –10

27.5

Pan Section at 95 4m
27.5
5,000

1,000

500 –40–40

100 20 40 20

50
–40 –40 –40
5
Source area
40 40

20
20

–30 –45 –25

40 40

10 10 PCE concentrations

5–100 μg/L
–35 –35 –32.5 –17.5

20 40 40 20
100 100–1000 μg/L
100

1
8
0 100 200 >1000 μg/L
15
–19 –15 –18
15 –26 –25 –27
meters

FIGURE 2.17  Several observed groundwater plumes reflecting the highly focused nature of contaminant transport and lack of transverse
dispersivity influence on overall plume development. Compared to Figure 2.16, actual groundwater plume transport is narrow and focused.

the flow of the plume. Mass discharge is related to mass flux,
but represents a sum of all mass flux measurements for a given
solute within a defined plume.49
Mass flux is defined by the following relationship:
J = KiC (2.33)
where
J is the mass flux of a given contaminant (g/day/m2)
K is the hydraulic conductivity (m/day)
i is the groundwater gradient (m/day)
C is the solute concentration (g/m3)
As mass flux estimates are linked to the relative permeability
of an aquifer, values of J can be highly variable across the ver-
tical through which a contaminant plume travels. Mass trans-
port through the more permeable and advective flow paths
travels faster and contributes most strongly to overall plume
size, while contaminant mass entrained in lower-permeability
strata migrates lower and has a lower associated mass flux.
As shown in Figure 2.18, the same contaminant concentration
results in significantly variable values of J depending on the
relative permeabilities of an aquifer. In Figure 2.18, a theoreti-
cal monitoring well containing 1 mg/L of a given contaminant
is installed in a formation with equal average values of K (3 ×
10 –3 cm/s). While the average K values are equivalent, the aqui-
fer shown in Figure 2.18b exhibits 3 orders of magnitude differ-
ence in K values associated with permeable and impermeable
soil strata. The resulting value of J in the most permeable zone
shown in Figure 2.18b is 4 orders of magnitude higher than the
surrounding soil type and three times higher than that deter-
mined from Figure 2.18a. This example demonstrates that the
most permeable soil strata will ultimately contribute most to
overall plume transport. As the more mobile fraction is often
the most accessible for remediation techniques, understanding
the relative differences in stratigraphy and its relationship to
contaminant transport is a key component to identify appro-
priate remedial strategies for focused treatment of the most
mobile contaminant mass, while still accounting for the less
mobile mass that may later contribute to the primary transport
pathways as remediation progresses.
Mass flux determinations are often made by characterizing
the relative differences in contaminant concentration and soil
stratigraphy across multiple transects of a plume. The accuracy
of flux estimates is correlated to the overall volume of field
information, and these determinations have benefited consider-
ably from real-time investigation techniques that can be used to
collect high-density data sets for use in mapping contaminant
concentrations to the relative soil permeabilities. The combina-
tion of multiple transects spaced along the length of the plume
can therefore allow the identification of dominant flow path-
ways and assess changes in mass flux along a plume’s length.
These estimates can be related to other monitoring well data
or completed over time to also identify a plume’s behavior and
whether it’s stable, expanding, or shrinking. A plume’s mass
discharge at any given time is the integrated sum of the mass
flux estimates, as defined by the following equation (ITRC):
ò
M d = J dA (2.34)
A
where
J is the variable contaminant flux observed within plume
(g/day/m2)
A is the area of the plane associated with individual values
of J (m2)
Coupled with an appropriate monitoring network, an under-
standing of a given plume’s mass flux and mass discharge
supports the development of a complete conceptual site
model and is an effective tool to guide remedial decision-
making. These measurements are not associated with existing
60
(a)
(b)
FIGURE 2.18  Conceptual representation of hydraulic conductivity and flux differences in two theoretical soil matrices. Both (a) and (b)
exhibit the same average value of K, but flow conditions and associated contaminant flux in (b) behave significantly different than defined
by the average K measurement.
contaminant regulatory standards, but can inform risk-based
decision-making based on contaminant distribution and its
relative transport along a plume flow path.
2.5.3 Volatilization and Transport in the
Unsaturated Zone
While transport in the vadose zone can include the migration
of gaseous, aqueous, and separate-phase materials (as discussed
in Section 2.2.1), unsaturated zone transport is discussed here
with respect to the partitioning and migration of gaseous vola-
tile contaminants within the vadose zone. Volatile subsurface
contaminants partitioning from either NAPL or groundwater
will migrate upward toward land surface and can result in vapor
intrusion risk via migration through voids in building founda-
tions or walls. For constituents with increased vapor pressures,
the degree of volatilization is governed by equilibrium partition-
ing relationships (see Equation 2.5) with surrounding or adjacent
soil gas. Once volatilized, contaminants migrate via diffusive
processes from areas with high to low concentrations (e.g., from
groundwater upward toward the ground surface) and via advec-
tion (via applied or natural pressure gradients) (Figure 2.19).
The variability in contaminant concentration, relative
depth to land surface, soil moisture content, soil permeabil-
ity and heterogeneity, the presence/absence of confining lay-
ers, and a contaminant’s degree of biodegradation all affect
the extent of which it will migrate away from the source.
Assessment of vapor intrusion was initially supported by
the development and application of the Johnson and Ettinger
Remediation Engineering
K J
(cm/s) g/day/m2
3 × 10–3 cm/s 2.5 × 10–2
1 × 10–5 cm/s 8.6 × 10–6
1 × 10–2 cm/s 8.6 × 10–2
1 × 10–5 cm/s 8.6 × 10–6
model,50,51 which served as an empirical tool to generate
an attenuation factor (α) to estimate the potential impact of
source concentrations beneath a building on concentrations
within indoor air. Expanded modeling assessments have been
developed to incorporate 3D simulations that better capture
the nature and complexity of dynamic subsurface conditions
that affect vapor transport52–55 for both aerobically degradable
and recalcitrant contaminants.
Within the subsurface, initial vapor transport from an exist-
ing source is generally upward toward the land surface (i.e., from
groundwater or near groundwater NAPL upward into soil gas).
Once present within vadose zone soil gas, diffusion processes
result in a radial distribution of soil vapors from the area of high-
est concentration. The volume of impacted soil gas is therefore
linked to the spatial distribution of NAPL or dissolved-phase
impacts from which it originates. At increased depth, diffusion
mechanisms generally represent the dominant mode of vapor
transport, with increased  diffusion observed in soil-gas envi-
ronments with increased porosity and low moisture content.43,56
Gaseous concentrations decline with increased transport dis-
tance due to multiple attenuation mechanisms (discussed in the
following text) depending on the overall soil permeability.
As soil vapors near the surface (generally within 1–2 m),56
advective pressure differences play a more considerable role
on the transport of soil gas. These mechanisms are attrib-
uted to the pressure influence exerted on the subsurface by
building activities (e.g., changes in ambient building tempera-
ture, operation of heating and air conditioning units) that can
result in both negative and positive pressure conditions that
Contaminant Characteristics 61

Vertical cross-section view

–2

0.1
Depth bgs (m)

4
1E–
0.3

1E–3

0.01
–4 0.5

0.7
–6
0.9
Water table Vapor source
–8

Plan view at 2 m bgs

70

60

50

0.1
40 0.2
y (m)

30
0.0

20
1E
1E

1
–3
–4

10

0
0 10 20 30 40 50 60 70 80 90 100
x (m)
Building footprint Vapor migration
Vapor source zone footprint

FIGURE 2.19  Conceptual representation of vadose zone soil gas transport and developed concentration gradients from a localized source
of contamination. (From United States Environmental Protection Agency, Conceptual models for the vapor intrusion pathway, Office of
Solid Waste and Emergency Response, Washington, DC, February 2012.)

can induce or impede vapor intrusion, respectively.56 Due to
these processes, characterization of building operations is a
critical component of any soil gas assessment. As an example,
buildings that operate under constant temperature control and
maintain positive pressures are far less susceptible to vapor
intrusion risk than buildings with old or degraded founda-
tions that are more prone to larger fluctuations in tempera-
ture variation. While many vapor intrusion evaluations are
conducted assuming steady-state conditions, these advective
transport mechanisms help illustrate the transient nature of
soil gas migration under variable field conditions. As a result,
while available models have improved the ability to character-
ize and evaluate potential vapor intrusion risk, these quanti-
fication methods are meant to be supported by field sampling
programs to accurately calibrate the modeled outcome.
2.6  TRANSFORMATION PROCESSES
The mechanisms described in the proceeding sections all
serve to control a contaminant’s fate and transport based on
physicochemical behavior and direct interaction with the hydro-
geologic environment through which they migrate. In con-
junction with these processes, contaminant interactions with
subsurface materials (e.g., oxidation, reduction, precipitation,
solubilization), direct utilization by microbial communities (e.g.,
aerobic and anaerobic biodegradation), and chemical decompo-
sition (e.g., hydrolysis) all serve to directly transform contami-
nants from their original composition to alternative chemical
states. Nearly all in situ remediation engineering technologies
employ at least one form of direct transformation process and
utilize chemical reagents or nutrient substrates to directly react
with or foster the development of subsurface conditions to facili-
tate contaminant destruction, mineralization, or immobilization.
2.6.1 Abiotic Transformation
Abiotic transformation processes are driven by a contami-
nant’s physicochemical properties and its interaction with the
specific geochemical and mineral composition of the environ-
ment in which it’s entrained.
62
2.6.1.1  Oxidation and Reduction Reactions
In redox reactions, an overall net change in oxidation level
occurs during reaction between the target contaminant and
the chemical species with which they interact. The major-
ity of these reactions involve the direct transfer of electrons
from one species to the other, with participating species being
either oxidized or reduced depending on whether they receive
a net loss or gain in electrons. A chemical species that trans-
fers electrons to another is referred to as an electron donor (or
reductant), and the species that receives electrons is referred
to as an electron acceptor. Through this process, the electron
donor is oxidized and the electron acceptor is reduced. The
terms oxidation and reduction are therefore used to refer to
whether a contaminant is oxidized or reduced, respectively.
In oxidation reactions, oxidation can be associated either
via the introduction of oxygen into a molecule, via the removal
of hydrogen, or via conversion of a molecule to a higher oxi-
dation state, as shown in the following examples:
For an organic compound:
R-CH2-H → R-CH2-OH → R-CHO (2.35)
For a metal species (iron):
Fe2+ (l) + 3H2O → Fe(OH)3 (s) + 3H+ + e− (2.36)
In the equation for the organic compound earlier, the first step
in the reaction sequence is the incorporation of oxygen via a
substitution reaction (to form an alcohol), which is then fol-
lowed by dehydrogenation that oxidizes the carbon atom to
a higher formal oxidation state (forming a carbonyl group).
As shown in the example metal species, ferrous iron (Fe[II])
is oxidized by receiving oxygen and increasing in overall
valence state to ferric iron (Fe[III]).
Reduction reactions occur when there is a transfer of elec-
trons from an electron donor (i.e., reductant) to an electron
acceptor (i.e., oxidant). Typical examples of abiotic reduction
reactions are as follows:
For an organic compound:
R-Cl + Fe0 + H+ → R-H + Fe2+ + Cl− (2.37)
For a metal species (iron):
CrO4− (l) + 3Fe2+ → Cr(OH)3 (s) + 3Fe(OH)2 + 4H+ (2.38)
In abiotic redox reactions, equilibrium processes between
chemical elements and the specific geochemical conditions
exhibit the strongest control over whether individual reactions
will occur. This tendency can be characterized as the redox
potential. Accordingly, redox reactions that do not result in
direct contaminant destruction and only a change in oxidation
state (e.g., metals) are fundamentally reversible depending
on the specific geochemical equilibria. Naturally occurring
chemical elements that are most commonly impacted by abi-
otic reducing reactions are inorganic elements (e.g., Fe and
Mn) and inorganic metallic ions (e.g., Cr6+ and As5+).
Just as the concentration (activity) of free protons (hydro-
gen ions, H+) can be utilized to assess the acid–base status of
Remediation Engineering
the subsurface environment, the activity of the free electron
(e−) can be utilized to assess the redox potential. The redox
potential is often defined in terms of the negative logarithm of
the free electron activity:
pE = log(e−) (2.39)
Large values of pE indicate low values of electron activity
and indicate the existence of an electron-poor (i.e., oxidized)
environment. Small values of pE indicate high electron
activity and thus correspond to electron-rich (reduced)
environments.
2.6.1.2  Precipitation and Solubilization
Inorganic compounds can occur in many species depending
on the specific geochemical equilibrium (e.g., pH, pE, pres-
ence of other solid or aqueous compounds). As changes in
the environmental conditions occur, the speciation of both
solid- and aqueous-phase compounds may also change as a
new geochemical equilibrium is established.
In groundwater, six categories have been suggested in
which an element or compound may exist57: (1) free ions (Na+,
Fe2+), (2) insoluble precipitates (Cr(OH)3, PbS), (3) metal/
ligand complexes (Cu-humate), (4) adsorbed species (arsenic
adsorbed to ferric hydroxide surfaces), (5) species held on by
ion exchange (Ca2+ on clay surfaces), and (6) species that dif-
fer in oxidation states (Fe(II) vs. Fe(III), Cr(III) vs. Cr(VI)).
As these phases include soluble, complexed, and bound states,
understanding the nature of the element or compound is
important for remediation engineers as this greatly impacts
the fate, transport, reactivity, and toxicity of species in the
natural environment.
While an understanding of a contaminant’s behavior is
integral to assessing overall environmental risk, it is also
critical to the consideration and application of engineered
in  situ treatment technologies. In  situ technologies can be
used to facilitate the direct precipitation and immobilization
of inorganic metal contaminants, but altered geochemical
equilibrium will also affect the speciation of redox sensitive
metals present within the native soil minerals. As a result,
understanding the behavior of both target contaminants and
nontarget species is a key component for achieving complete
environmental restoration. Manipulation of subsurface envi-
ronments and their effect on both precipitation and solubili-
zation reactions for remediation of certain contaminants are
discussed in Chapters 6 and 7.
2.6.1.3 Hydrolysis
Hydrolysis is a chemical transformation that occurs when an
organic molecule (RX) undergoes a substitution reaction with
water to cleave the covalent bond with X (the leaving group)
in the original molecule. The net reaction may or may not
entail the formation of anionic or carbocation intermediates,
but ultimately results in the hydration of the original molecule
and displacement of X by OH−:
RX + H2O → ROH + H+ + X− (2.40)
Contaminant Characteristics
In this reaction, certain functional groups (X) are potentially
susceptible to hydrolysis58: amides, carbonates, epoxides, ali-
phatic and aromatic esters, alkyl and aryl halides, nitriles,
ureas, and organophosphorous esters. Organic functional
groups that are relatively or completely inert to hydrolysis
are alcohols, phenols, glycols, ethers, aldehydes, ketones,
biphenyls, and pesticides.58 In the case of pesticides, while
hydrolysis serves as a transformation process (opposed to
destruction), the resulting species can be considerably less
toxic than the original compound.59
When an organic compound undergoes hydrolysis, a
nucleophile (an electron-rich nucleus, in this instance water)
attacks an electrophile (electron-deficient electron seeker such
as a carbon or phosphorous atom) to displace a less electro-
negative leaving group (e.g., chloride). It should be noted that
while the abiotic hydrolysis mechanism may play a larger role
in the degradation of certain classes of chlorinated compounds
(e.g., 1,1,1-TCA and 1,2-dichloropropane), rates of hydrolysis
for many chlorinated ethenes are negligible.
In many instances, abiotic hydrolysis can occur when
biodegradation cannot (or at considerably higher rates) and
can result in the formation of byproducts with increased sus-
ceptibility to biodegradation. As a result, hydrolysis can be a
significant process affecting the fate and transport of select
contaminants and can increase the likelihood for eventual
contaminant biodegradation and mineralization. The rate of
abiotic hydrolysis is strongly dependent on environmental fac-
tors such as pH, temperature, the presence of humic materials,
or natural metals within the subsurface. In biologically medi-
ated hydrolysis, the microbial community and enzyme activ-
ity act as controls. Both biotic and abiotic hydrolytic reactions
are not mutually exclusive and may jointly contribute to the
breakdown of a contaminant.
The effect of pH can be attributed either to specific acid–
base catalysis effects or to a change in speciation of the com-
pound. In addition to nucleophilic attack by H2O, hydrolytic
reactions are sensitive to specific acid and base catalysis
(i.e., catalysis by hydrogen ion H+ and hydroxide ion OH−,
respectively). Accordingly, hydrolysis kinetics must take into
account the potential for H2O to dissociate. Even at pH 7.0
(where the concentration of H+ and OH− is only 10 –7 M), spe-
cific acid and specific base catalysis occurs because hydrogen
ions provide an alternative mechanism for hydrolysis that is
energetically more favorable.
Temperature effects on the rate of hydrolysis can be
pronounced. Compared to acid-catalyzed, base-catalyzed,
and natural hydrolysis with water (all generally first-order
reactions), temperature-dependent hydrolysis rates exhibit
second-order reactions. For a 10°C change in temperature,
the hydrolysis rate constant could change by a factor of 2.5
(with increasing temperature corresponding to increasing
rate constants).18 Based on the relationship between the rate
of hydrolysis and temperature, it is intuitive that the extent
of degradation attributed to hydrolysis will be encountered
depending on site location and climate. The benefits of these
mechanisms are utilized in engineered in situ thermal reme-
diation systems in which the heat applied to the subsurface
63
promotes contaminant removal via hydrolysis as well as vola-
tilization and capture (Chapter 8).
The presence of metal ions such as calcium, copper, mag-
nesium, iron, cobalt, and nickel has been observed to cata-
lyze the hydrolysis of certain compounds when the metal ions
are present at high concentrations. It has also been suggested
that in some circumstances, metal ions associated with soil
medium (i.e., clay minerals) serve to catalyze hydrolysis as
well as increased concentrations of OH—when elevated dis-
solved metals concentrations are observed. In most natural
systems, however, typical concentrations of dissolved metals
exhibit negligible impact (relative to acid- or base-catalyzed
and temperature effects) on the rate of hydrolysis.
2.6.2  Biological Transformation
The combination of numerous environmental contaminants,
microbial biodiversity, and continued evolution of microor-
ganisms to utilize compounds within their environment has
resulted in a vast spectrum of available biodegradation path-
ways and mediating microbial species. While the mecha-
nisms discussed in the proceeding sections all serve to control
the fate and transport of contaminants in the natural envi-
ronment, biologically mediated transformation can be highly
advantageous in expediting contaminant attenuation relative
to otherwise slow physicochemical or abiotic processes.
Microbially mediated reactions affect the fate and trans-
port of almost all organic compounds and most inorganic
compounds in both natural and engineered environments.
Direct biodegradation of organic contaminants often entails
the utilization of contaminants as food substrates (electron
donors or acceptors) for energy (ATP) or biomass growth.
Biodegradation can also be facilitated by indirect cometa-
bolic processes that require direct contaminant interaction
with enzymes or cellular processes that are unrelated to the
contaminant’s presence. As a rule, direct biodegradation
requires the combination of the appropriate microorganisms
at sufficient concentration with sufficient substrate availabil-
ity for use in sustaining cellular activities. In remediation
engineering, biological transformation mechanisms are uti-
lized to facilitate natural contaminant transformation in the
absence of direct manipulation (natural attenuation) or are
enhanced via the delivery of supplemental substrates to over-
come substrate deficiencies to promote microbial proliferation
and activity.
The terms biotransformation, biodegradation, and bio-
catalysis are often used to explain the same process. While
they have similar meanings, they should be used in differ-
ent contexts. Biotransformation is more of a technical defi-
nition and should be used to describe a metabolic process.
The term biocatalysis is used similarly to biotransformation,
with the additional connotation of metabolism for the purpose
of making a useful compound. The term biodegradation, by
contrast, is most typically used when the objective is taking a
compound away: a microbial process by which a potentially
toxic contaminant is transformed into a nontoxic one or few.
Bioremediation is a more recently coined term that refers to
64 Remediation Engineering

the application of biodegradation reactions for the practical Couple E0΄(V)

cleanup of chemical contamination.60 CO2/glucose (–0.43) 24 e– –0.50
In general, numerous bacteria are involved in the metab- 2H+/H2(–0.42) 2 e–
olism of certain classes of compounds, such as aliphatic –0.40
CO2/methanol (–0.38) 6 e–
hydrocarbons, aromatic hydrocarbons, chlorinated aliphatic
NAD+/NADH (–0.32) 2 e– –0.30
hydrocarbons, or heterocyclic ring compounds. The presence
CO2/acetate (–0.28) 8 e–
or absence of oxygen often dictates the type of biodegradative –0.20
S0/H2S (–0.28) 2 e–
pathway and the types and number of bacteria involved in bio-
degradation. General terminology used to describe biodegra- SO42–/H2S (–0.22) 8 e– –0.10
dation include either aerobic or anaerobic mechanisms, which Pyruvate/lactate (–0.19) 2 e–
0.0
are generally applied based on the nature of transformation
occurring in the presence or absence of oxygen. As many +0.10
organisms are facultative and groundwater systems can con-
sist of variable electron acceptor (e.g., oxygen, nitrate, iron, Fumarate/succinate (+0.03) 2 e– +0.20
sulfate) concentrations over short distances, it is encouraged Mn3+/Mn2+ (+0.2) 1 e–, (pH 7)
+0.30
that descriptions of these processes be drawn around micro- NO3–/NO2– (+0.42) 2 e–
bial oxidative versus microbial reductive reactions. +0.40

2.6.2.1  Microbial Oxidation +0.50

Within microbial oxidizing zones, contaminants (e.g., BTEX,
ketones) act as reductants while electron acceptors (O2, NO3−,
SO42−) function as oxidants. At neutral pH, thermodynam-
ics mainly determines the order in which microorganisms use
electron acceptors, as microorganisms tend to perform redox
reactions close to thermodynamic equilibrium. Electron accep-
tors are utilized in the order of decreasing free energy (Figure
2.20) and overall substrate availability. Where elevated metal
oxide minerals exist within the native soil matrix, reductive
dissolution mechanisms can become important contributors to
oxidation processes. Zones of oxygen utilization, iron reduction,
sulfate reduction, and methanogenesis often overlap depending
on the volume of electron acceptor present in the subsurface. As
an example, methanogenic groundwater conditions often coin-
cide with petroleum LNAPL and sorbed soil mass within the
immediate vicinity of a UST release, while groundwater condi-
tions are frequently iron or sulfate reducing further downgradi-
ent where only dissolved petroleum species are observed.
Engineered biological oxidation applications entail the
focused delivery of substrates to supplement the depleted
natural supply of electron acceptors. Traditional aerobic treat-
ment methods have relied on various means of oxygen deliv-
ery to initiate the transformation of chemical contaminants
using oxygen as the electron acceptor. Since O2 in the subsur-
face is not very reactive with most contaminants, microorgan-
isms must invest metabolic energy to convert this oxygen into
a more effective oxidant via mediating enzymes with metals
(e.g., oxygenases) and coenzymes like NAD(P)H. Engineered
oxygen delivery treatment applications have been used to
address contaminants present within both vadose zone and
saturated soils via multiple means. While the Gibbs free
energy results in oxygen being the most energetically favor-
able electron acceptor, oxygen’s limited solubility and persis-
tence in the subsurface mandate engineering programs that
can both distribute oxygen within the treatment zone and sus-
tain it over time. Vadose zone applications include air sparging
and forced vadose zone venting, which serve to increase and
sustain oxygen in soil gas to promote biological degradation
+0.60
NO3–/½ N2 (+0.74) 5 e– +0.70
Fe3+/Fe2+ (+0.76) 1 e–, (pH 2)
+0.80
½O2–/H2O (+0.82) 2 e–
+0.90
FIGURE 2.20  The electron tower for commonly encountered
redox couples within soil and groundwater systems. Couples are
arranged from the strongest reductants on top to the strongest oxi-
dants at the bottom. The magnitude of reduction potential between
electron donor and electron acceptor is correlated with amount
of energy released. (From Madigan, M.T. et al., BrockBiology of
Microorganisms, Prentice Hall, Upper Saddle River, NJ, 2003.)
on soil surfaces. Within saturated soils, oxygen’s limited
aqueous solubility and its consumption by a variety of aero-
bic microorganisms that may or may not contribute treatment
benefit often require active air or oxygen sparging, sustained
injection of oxygenated water, or the delivery of aqueous or
solid-phase peroxide materials that react and release oxygen
over time. These applications have been applied widely with
success for the remediation of petroleum-derived or aromatic
hydrocarbons, as discussed in Chapter 6.
While oxygen-mediated oxidation methods have histori-
cally been most widely applied, engineered anaerobic oxi-
dation applications have gained traction as viable means to
deliver elevated concentrations of nonoxygen electron accep-
tors into the subsurface. While nitrate and sulfate are less
energetically favorable than oxygen, the solubility of each
of these anions allows for elevated dosing in aqueous-based
injection applications.
2.6.2.2  Microbial Reduction
In the inverse of microbial oxidation, contaminants in micro-
bial reducing zones (e.g., carbon tetrachloride, TCE, PCE,
TCA, methylene chloride) act as electron acceptors (oxidants)
while other electron donors (e.g., degradable organic matter,
Contaminant Characteristics
a. Oxygenolytic C C OH C O
dechlorination
1 O2 Cl
2 H
b. Hydrolytic
dechlorination C OH
(H2O)
C Cl + CI–
c. Reductive
dechlorination C H
2e–, 2H+
d. Elimination C CH3
FIGURE 2.21  Four fundamental dechlorination mechanisms
capable of cleaving the carbon–chlorine bond. (Adapted and modi-
fied from Wackett, L.P. and Hershberger, C.P., Biocatalysis and
Biodegradation, ASM Press, Washington, DC, 2001.)
applied organic carbon substrates) function as the electron
donor (reductants). The widespread use and release of haloge-
nated organic chemicals over the course of the twentieth cen-
tury have resulted in widespread deployment of engineered
reductive dechlorination treatment programs. For chlorinated
solvents, microorganisms have evolved different strategies to
remove the chlorine substituent and utilize these chlorinated
compounds for their own benefit. Commonly observed meta-
bolic mechanisms for dechlorination are (1) oxygenolytic
dechlorination, where under aerobic conditions the chlorine is
replaced by a hydroxyl group derived from oxygen; (2) hydro-
lytic dechlorination, where the chlorine is replaced by the
hydroxyl group derived from water; (3) reductive dechlorina-
tion, where (under mostly anaerobic conditions) the chlorine
is replaced by hydrogen; and (4) elimination (Figure  2.21).
Of these, reductive dechlorination is the most dominant and
prevalent microbial reaction responsible for the complete
transformation of chlorinated organics.
Reductive dechlorination is a biologically mediated reac-
tion that entails transferring electrons to the chlorinated
contaminant of interest from the electron donors. The more
oxidized the chlorinated compound is, the more susceptible it
is to reduction. The reduction of chlorinated solvent molecules
that are used as electron acceptors cleaves individual chlorine
atoms and replaces them with hydrogen, leading to sequential
dechlorination patterns from compounds with more chlorine
atoms (e.g., PCE, TCE) to lesser chlorinated species (e.g., cis-
1,2-dichloroethene, vinyl chloride). These microbially medi-
ated reactions and their remedial design considerations are
discussed in detail in Chapter 6.
2.6.2.3  Cometabolic Biodegradation
Microorganisms express genes to mediate a variety of cel-
lular activities, including the production of enzymes neces-
sary to perform degradation reactions. While many enzymes
are specific to their substrates, certain enzymes produced
for a specific microbial function are less discriminate and
can affect other molecules or substrates that are unrelated
to the enzyme’s original intent. Cometabolic transformation
processes are fortuitous in that they occur following contact
65
Methane oxidation
H H O
MMO H
H C H H C O H C O H C O H CO2
H H
2H, O2 2H 2H
TCE epoxidation (cometabolic oxidation)
Cl Cl MMO Cl O Cl
C C C C ? CO2, Cl–, H2O
Cl Cl Cl H
2H, O2
(a)
H3C O C CH3
CH3
Methyl-tert-butyl ether
(b)
FIGURE 2.22  MMO-facilitated oxidation processes for methane
and TCE. Note: “?” represents unknown intermediates.
between a contaminant and a mediating enzyme and result
in no overall benefit to the microorganism from which the
enzyme was excreted. While cometabolic degradation has
been identified for a number of different contaminants, it
is often not the dominant process when metabolic degrada-
tion is viable based on available growth substrates. Several
of the chlorinated aliphatic hydrocarbons can be microbially
transformed through cometabolism, as was first demonstrated
for TCE in 1985.62 A summary of this process is provided in
Figure 2.22, where methane monooxygenase (MMO) initiates
the oxidation of methane by forming methanol. This process
also requires molecular oxygen and a supply of reducing power
noted as 2H. MMO also fortuitously oxidizes TCE, convert-
ing it into TCE epoxide, an unstable compound that degrades
biochemically into many compounds that can be mineralized
by many microorganisms. Cometabolic degradation has also
been documented for the emerging contaminant 1,4-dioxane,
again in the presence of monooxygenase enzymes produced
by known methane, propane, and toluene degraders.
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1. Graedel, T.E., Hawkins, D.T., and Claxton, L.D. (1986).
Atmospheric Chemical Compounds: Sources Occurrence and
Bioassay. Academic Press, New York.
2. Goldstein, A.H. and Galbally, I.E. (2007). Known and
unexplored organic constituents in the Earth’s atmosphere.
Environmental Science and Technology 41(5): 1514–1521.
3. National Research Council. (2012). Alternatives for Managing
the Nation’s Complex Contaminated Groundwater Sites. The
National Academies Press, Washington, DC.
4. Doherty, R.E. (2000). A history of the production and use of car-
bon tetrachloride, tetrachloroethylene, trichloroethylene, and
1,1,1-trichloroethane in the United States: Part 1—Historical
background; carbon tetrachloride and tetrachloroethylene.
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future in light of the past. Annals of the New York Academy of
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tion of PCBs: A review. Biotechnology 10(3): 241–251.
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I.T., de Voogt, P., Jensen, A.A., Kannan, K., Mabury, S.A.,
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2016.
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24. Welkom, J.H. and Montgomery, L.M. (1990). Ground Water
Chemicals Desk Reference. Lewis Publishers, Boca Raton, FL.
25. Luthy, R.G., Aiken, G.A., Brusseau, M.L., Cunningham,
S.D., Gschwend, P.M., Pignatello, J.J., Reinhard, M., Traina,
S.J., Weber Jr., W.J., and Westall, J.C. (1997). Sequestration
of hydrophobic organic contaminants by geosorbents.
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26. Chen, W., Kan, A.T., Newell, C.J., Moore, E., and Tomson,
M.B. (2002). More realistic soil cleanup standards with dual-
equilibrium desorption. Ground Water 40(2): 153–164.
27. Suthersan, S.S. and Payne, F.C. (2005). In Situ Remediation
Engineering. CRC Press, Boca Raton, FL.
28. Kueper, B.H. and Davies, K.L. (2009). Assessment and delin-
eation of DNAPL source zones at hazardous waste sites.
Ground Water Issue. United States Environmental Protection
Agency, Washington, DC.
29. Brost, E.J. and DeVaull, G.E. (June 2000). Non-aqueous phase
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Soil screening guidance: Technical background docu-
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action applied at petroleum release sites. American Society
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32. ASTM PS 104-98. 1998. Standard provisional guide for risk-
based corrective action. American Society for Testing and
Materials, West Conshohocken, PA.
33. Johnson, P.C., Hertz, M.B., and Byers, D.L. (1990). Estimates
for hydrocarbon vapor emissions resulting from service sta-
tion remediations and buried gasoline-contaminated soils.
Petroleum Contaminated Soils 3: 295–326.
34. Mott, H.V. (1995). A model for determination of the phase
distribution of petroleum hydrocarbon release sites. Ground
Water Monitoring and Remediation 15(3): 157–167.
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Program, Princeton University, Princeton, NJ.
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for hydrocarbon vapor emissions resulting from service sta-
tion remediations and buried gasoline-contaminated soils.
Petroleum Contaminated Soils. Kostecki, P.T. and Calabrese,
E.J. (eds.), Vol. 3, Lewis Publishers, MI, pp. 295–326.
37. Pfannkuch, H.O. (1983). Hydrocarbon spills, their retention in
the subsurface and propagation into shallow aquifers. Water
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38. Lin, C., Pinder, G.F., and Wood, E.F. (1982). Water Resources
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Trichloroethene residuals in the capillary fringe as affected
by air-entry pressure. Journal of Environmental Quality 18:
72–77.
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889–895.
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Contaminant Characteristics
42. Zytner, R.G., Biswas, N., and Bewtra, J.K. (1993). Retention
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evaluation. United States Environmental Protection Agency
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Groundwater restoration: Large-scale benefits of small-scale pro-
cesses. Groundwater Monitoring and Remediation 33(3): 31–37.
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­trichloroethylene in soil. Applied Environmental Microbiology
49: 242–243.
 3 Principles of Integrated Design
3.1 INTRODUCTION
While there are as many different perspectives on design as
there are references that touch on it, from an engineer’s per-
spective, design represents the development of a plan that will
support the implementation of a concept. The word “design”
can be used to refer to either the plan or the act of creating the
plan. In either case, design is required for complex systems to
ensure that the final form successfully supports the functions
and objectives originally envisioned and that all other critical
parameters (safety, sustainability, etc.) are also fulfilled.
By definition, the field of engineering is intertwined with
design. This vocation is devoted to solving challenges faced
by our society; it harnesses the sciences and through their
creative application in the design process has the potential
to deliver innovations that can impact cultural and indus-
trial development at a broad scale. While this is certainly
a very high-level perspective, at a more practical level, we
can simply say that design, and more precisely the methods
used in the design process, will affect the results achieved
for the focus of the design. As a consequence, entire careers
have been devoted to the subject of engineering design, trade
journals focused on it, and schools chartered to hone its phi-
losophy. As much as the engineers in training are focused
on mastering the sciences, they are often equally focused on
how to merely think, in part to make them better designers.
The design process is a common thread for all engineer-
ing disciplines and is typically represented as a circular and
iterative set of process elements. There are literally hundreds
of graphical interpretations of the engineering design pro-
cess, each with its own focus and with varying levels of detail.
Figure 3.1 is an adaptation that we can apply to problems
encountered in the field of environmental remediation.
It is important to note that we have specifically chosen to
refer to these as process elements rather than steps, because
while there is an aspect of chronology to them, they do not
have to (and often don’t) happen in perfect sequence. While
the process depicted by Figure 3.1 is fairly easy to grasp, put-
ting it into practice is complicated. This complexity can be
appreciated through a closer look at what is represented by
each of the elements in the process. In the sections that follow,
we will first describe each element in this design process and
then consider what it means for the process to be “integrated.”
Finally, we will explore some common stumbling blocks that
can affect the outcome of the design process, specifically as it
relates to environmental remediation.
3.2  REMEDIATION DESIGN PROCESS
As previously depicted by Figure 3.1, the conventional approach
to remediation design can be broken into six process elements.
In many cases, these process elements are implicitly realized
by design teams, but the ability to explicitly realize them can
support an improved outcome. Highlights for each process ele-
ment are provided here, some of which will be touched on in
greater depth later in this chapter. As we explore each of these,
something that will become apparent are the multiple levels
of design that are layered into the process—the activities that
are germane to several of the process elements require their
own design.
3.2.1 Element 1: Define
In order to adequately respond to a particular design chal-
lenge, it must be sufficiently understood. This primarily
relates to the articulation of both requirements and con-
straints. Requirements represent necessary functional and
nonfunctional characteristics of the system being designed
(what it must do and features it must have) and as such deter-
mine the technical success of the design. These are some-
times documented in a performance specification, and for
a remediation design might include things like flow capac-
ity, limits of treatment that can be achieved, and sustained
system operation (often referred to as uptime)—some of
which is predicated on the understanding of the site condi-
tions and development of an accurate conceptual site model.
By comparison, constraints represent restrictions that the
system must conform to or be designed around for ease of
implementation or satisfaction of stakeholders and as such
determines the practical success of the design. For a reme-
diation design, this might include overall cost, size/footprint
limitations, and degree of visibility or disruption to other
site operations.
In some cases, requirements placed on a design can be
vague. An example might be that a groundwater treatment
system must meet drinking water criteria. This warrants
clarification to ensure there is a sufficient amount of detail to
inform the design: For what compounds will this be relevant
at the site in question? What will be the basis of demonstra-
tion? Often, it is not possible to satisfy all requirements and
constraints. Once they are adequately understood, it is pos-
sible to map them out in a matrix to identify and even rank
conflicts between the two in terms of importance so they can
be prioritized for resolution.
An added component of this design process element (some-
times shown as a separate, stand-alone element) is to fully
research the problem to understand the spectrum of available
solutions, related risks, and opportunities for improvement.
This will ensure that the design team is aware of the current
state of relevant technology and isn’t retracing ground already
covered by others.
69
70
Define
Brainstorm
Plan
Refine
Test
Deploy
FIGURE 3.1  Design process.
3.2.2 Element 2: Brainstorm
In the famous words of Dr. Linus Pauling, “the best way to
have a good idea is to have a lot of ideas.” Before moving into
design, it is natural to brainstorm possible solutions. This is a
process that is scalable depending on the nature of the design
challenge; it can be focused and quick for simple design chal-
lenges, or relatively broad and more time consuming for large
complicated challenges. In either case, brainstorming delivers
important building blocks that can be used in the basis for a
final design solution.
There are many philosophies on methods for brainstorm-
ing, but there are two things they all seem to agree on. The
first is that brainstorming requires the input of a team. For
complicated design challenges, this involves making sure the
right disciplines are represented and including a variety of
experience levels and backgrounds to encourage new perspec-
tives and thinking that diverges from the norm. The second is
that the process should encourage creativity and avoid imme-
diate dismissal of ideas. Even something that might at face
value be seen as out of bounds could stimulate a discussion
that yields a viable solution.
An example that is often used to illustrate the importance
of these two facets of effective brainstorming is the story
behind how Pacific Power and Light developed its approach
to safely remove ice buildup on power lines.1 The traditional
practice was to send linemen out to climb the poles and physi-
cally shake the lines. This was a dangerous practice that the
company wanted to find an alternative to, so they set up sev-
eral brainstorming sessions to that end. In one of the sessions,
a lineman made a comment during a coffee break that he
had been chased by a bear one time when coming down off
a pole. The group joked that they should train the bears to
climb the poles for them. The conversation turned to how they
might motivate the bears to climb the poles, and a member of
the group offered the idea of placing honey pots on top of the
poles—perhaps using the helicopters reserved for the corpo-
rate executives. At that point, a secretary recounted her expe-
rience with helicopter downwash as a field nurse in Vietnam
and wondered whether the downwash would be powerful
enough to knock the ice off the lines. The group instantly
realized they had identified a solution, and it had come from
the most unlikely of sources.
Remediation Engineering
Not every brainstorming dialogue leads to this type of
breakthrough, but even when it doesn’t, it does help increase
the level of engagement within the team, strengthen the team
dynamic, and increase the potential for a successful session.1
3.2.3 Element 3: Plan
In this element of the process, the available information is
synthesized into a plan for implementation.2,3 In practice, this
is often divided into three phases: (1) the conceptual or 30%
design, (2) the embodiment or 60% design, and (3) the detailed
or 90% design (referred to as such because it is typically not
deemed 100% until approved by the governing agency). The
rationale behind this sequence is that it provides opportunity
for iterative reevaluation of the design in the ­central loop
depicted in Figure 3.1.
As with brainstorming, there are significant texts devoted
to explaining the goals and methods embodied in each of
these planning phases. The following are highlights:
Conceptual design: In his text on conceptual design,
Michael French said that “this is the phase where
engineering science, practical knowledge, production
methods, and commercial aspects need to be brought
together, and where the most important decisions are
taken.”4 Also, “it is the design phase that makes the
greatest demands on the designer and where there is
the most scope for improvement as fundamental errors
at the conceptual stage can be the most serious and
elusive.”
The synthesis involved in developing a conceptual design
schematic describing the whole proposed system that
satisfies the requirements and constraints of the proj-
ect can truly be one of the most challenging aspects of
the design process. Most engineers are equipped for
analysis (ironically, the etymological root of which
is “anal”). Analysis involves the reduction of a com-
plex system into its component parts for examination,
but this ignores the interactions of those parts.5 This
is where synthesis comes in—helping to create new
system concepts and breakthrough solutions by decon-
structing known concepts or processes and selectively
reassembling key elements to form something new.5
The ability to synthesize in support of design requires
the intuition that can only be developed through prac-
tice and has been viewed by some as an art as much as
it is based in science.6
There is never one right answer for a given problem, so at
the conceptual design phase, there may be a compara-
tive evaluation of several alternatives to help select
something that seems to best fit the mix of require-
ments and constraints for the project. After this deci-
sion is made, it becomes increasingly difficult to make
significant departures. This relates to both human
nature and the inertia developed as a design pro-
ceeds, which underscores the observations made by
Mr. French.
Principles of Integrated Design
Embodiment design: This planning phase is also some-
times referred to as the layout design or configuration
design.7 In this phase, the scheme chosen in the con-
ceptual design phase is refined into something that can
actually be implemented. This involves establishing a
more definitive selection of key equipment and materi-
als, layout of mechanical and electrical systems, devel-
opment of a preliminary operational program, and an
initial set of specifications to support construction/
implementation. It also typically involves producing
a draft set of engineering drawings to convey these
details. These drawings are accompanied by calcula-
tions and other information necessary to document the
basis for the design and its conformance to relevant
codes of regulation.
In addition to the previous text, this planning phase is
where safety and reliability are more carefully consid-
ered to ensure adequate management of physical risks.
These need to be considered through all of the planning
phases, but the embodiment design is where the details
begin to take form. Reliability is focused on the likeli-
hood that in a given environment a system will oper-
ate as intended over the intended time frame. A failure
reflects a situation when the system stops functioning
properly. Safety is focused on avoiding injury and/or
damage to property. The two are largely intertwined
and should be considered concurrently.
The conventional method for accomplishing this is
referred to as Failure Mode and Effect Analysis
(FMEA).8 FMEA is a systematic approach to reliabil-
ity analysis that involves the study of the failure modes
in every subcomponent of the system. While anticipat-
ing that every failure mode is not possible, the design
team should formulate as extensive a list of potential
failure modes as possible so they can be ranked and
addressed as appropriate in the design. This is an
extensive topic with a significant body of literature and
practice behind it, so we will delve into it further later
in this chapter.
Detailed design: This is the final phase of planning and
involves comprehensive completion of design cal-
culations, dimensioning and tolerancing, material
specification, and other details required to facilitate
implementation. Prior to beginning this phase of the
planning process, the design should be roughly com-
plete and testing performed to verify performance. At
this phase, the remaining uncertainties should be few.
One of the critical elements of this planning phase is
the preparation of the final design documents. These are
meant to be used directly by those that will be respon-
sible for the construction and operation of the system,
so should include both. Whenever possible, the direct
involvement of the contractors and technicians that
will be responsible for operation can help improve the
final design and save a lot of time during deployment
(Element 6 of the design process).
71
Each of the planning phases mentioned earlier can rely
on/benefit from information yielded by Element 4 of
the design process loop (discussed next). The number
of planning phases can vary from one to all three for
any given design project, depending on the complex-
ity of the system being designed.
3.2.4 Element 4: Test
This element of the process is devoted to guiding design
refinement through the collection of critical proof of concept
and other physical information required to validate various
elements of a design. This can range from a thought experi-
ment to real experiments either in the laboratory or in the field,
to further characterization of the site conditions, all of which
require careful planning and design in their own right. Most
of these activities are categorized as “predesign,” as they lie
between the initial concept and completion of the final design.
Some form of predesign testing is nearly always needed, and
it can come in many different flavors. We will discuss this
element in greater depth later in this chapter.
3.2.5 Element 5: Refine
This element of the design process represents the bridge
between the conceptual phase of the design process and the
detailed design phase. Information from predesign testing is
incorporated into the next iteration of the design to further
refine it. This process is not limited to the number of design
phases (i.e., 30%, 60%, 90%) and should be repeated until
uncertainties regarding performance, reliability, or safety
have been reduced to an acceptable level.
3.2.6 Element 6: Deploy
This element of the design process includes the activities
necessary to deploy the system to the field and achieve full
operational capability. This typically involves four steps:
(1) construction (with quality management), (2) operational
testing and evaluation (typically referred to as system shake-
down), (3) field modification based on the shakedown results
(although the need for field modification can be encoun-
tered after the system has entered into long-term operation,
monitoring, and maintenance), and (4) long-term operation,
monitoring, and maintenance. There are typically detailed
reports (recurrent in the case of long-term operation, moni-
toring, and maintenance) generated for each of these steps.
This process ensures that the system that has been designed
remains reliable and usable and conveys the related details
to stakeholders.
Over the years, studies conducted on designers of vary-
ing degrees of experience and education have connected a
number of characteristics to better outcomes.3 These include
the ability to understand the requirements and constraints
connected to a problem, the ability to allow creative brain-
storming without fixating, getting stuck, or allowing too
many variants, the ability to work in teams, and the ability to
72
effectively communicate. All of this provides valuable insight
into a process that is at the core of remediation engineering.
But it doesn’t capture an important evolution that has occurred
over the past 15 years. We will explore this next.
3.3  INTEGRATED DESIGN: AN OVERVIEW
In the conventional paradigm, designers tend to divide prob-
lems into their individual pieces. This is most commonly
reflected in the segregation of each area of expertise during the
design process, with the various designers meeting occasion-
ally to ensure that their solutions don’t clash, but for the most
part staying out of each other’s way. By comparison, an inte-
grated design process involves the team working together as a
collective to understand and develop all aspects of the design.
The design can then emerge organically, with the full benefit of
each expert’s input. While successful outcomes can certainly
be realized for simple systems using the conventional approach,
the integrated approach can lead to enhanced outcomes by
identifying and leveraging connections between the parts.
The Rocky Mountain Institute, an independent nonprofit
Colorado-based think tank, spends much of their time on the
subject of integrated design, calling it “integrative” design
as a reflection of an adaptive versus fixed practice.9 In one
of their technical briefs, they make the point that optimizing
individual parts of a system with little thought to their interac-
tions yields inferior results,10 and their cofounder wrote in one
of his books:
Designing a window without the building, a light without the
room, or a motor without the machine it drives works as badly
as designing a pelican without the fish.
Optimizing components in isolation tends to pessimize the
whole system—and hence the bottom line. You can actually
make a system less efficient while making each of its parts
more efficient, simply by not properly linking up those com-
ponents. If they’re not designed to work with one another,
they’ll tend to work against one another.11
Where this becomes glaringly apparent is when the sys-
tem or solution being designed is only one part of a much
larger puzzle. Take for example the need to restore an entire
watershed. A watershed is an area of land that drains to
the same river, lake, or coastal estuary. Given the scale of
most watersheds (tens to thousands of square miles) and
multiple media involved (surface water, groundwater, soil,
sediment, etc.), the ability to protect and/or restore them is
highly complicated and costly. Designing management or
restoration solutions in the context of a watershed involves
developing a technical understanding of the overall water
balance, contaminated media (and other human influences),
natural resources, and their interactions and overlaying this
conceptual site model with relevant political, regulatory, and
business considerations to support reasonable solutions to
restore, sustain, or enhance watershed functions. Complex
hydrologic and geochemical conditions can also be a bar-
rier to achieving stakeholder alignment on a reasonable
Remediation Engineering
remediation concept. The complexity prevents clear visual-
ization of the issues creating uncertainty and in turn slowing
down the decision-making.
The watershed example is extremely relevant because the
industries with the largest environmental footprint (resource
extraction, food production, etc.) all have significant water-
and watershed-related implications. This is one of the next
frontiers for environmental remediation, creating oppor-
tunities for practitioners to develop sustainable strategies
at remediation sites once thought to be intractable due to
scale. In their reflections on lessons learned over 20  years
in the efforts to restore the 1500 square mile Coeur d’Alene
River basin due to impacts from the Bunker Hill Mining
and Metallurgical Complex Superfund Site, the National
Research Council, among their many conclusions, pointed
to the lack of a basin-wide understanding of contaminant
fate and transport and connections between areas being tar-
geted for remediation and unremediated areas (i.e., potential
for recontamination).12 The best outcome for a site like this
often involves a strategy to minimize the level of effort and
risk associated with long-term stewardship (vs. identifying a
“final” remedy). The goal would be to avoid invasive, detri-
mental, and unnecessary remediation and support reasonable
solutions that can protect the environment with a low level
of long-term stewardship and can lead to systems that are
self-sustaining beyond the time frame of human intervention.
This in turn will garner broader support from stakeholders
for implementation.
In summary, there are three key characteristics of an inte-
grated design effort that are relevant to environmental reme-
diation, as follows:
1.
Holistic or whole-system viewpoint: As we’ve already
touched on, holistic thinking is the underpinning
of integrated design and can lead to dramatically
improved effectiveness. It relies on the creation of an
easy-to-understand macroscale conceptual model—
something that can be interactive and is often based
on the smart simplification of large data sets using
electronic tools that were not available 10 years ago.
This supports better contextual visualization of the
system, identifying the system elements that have
the greatest influence on the desired outcomes along
with their connection to other elements of the sys-
tem. The ability to help stakeholders visualize the
whole system can be a powerful tool in negotiating
a reasonable response, thereby helping to neutral-
ize the scale factor for very large sites. It allows the
team to prioritize areas of focus and develop more
detailed submodels as needed to further refine the
understanding of the risks, limitations, and benefits
in developing solutions.
Integrated development: The opportunity for integra-
2.
tion in design planning is present on two fronts: syn-
ergy between different components of a large-scale
or complex rehabilitation effort and collaboration
Principles of Integrated Design
between multiple disciplines to create a team that
acts as a unit. The former creates the potential to
leverage the benefits of work in one area to modify
(minimize) the level of effort in another area or real-
ize a cumulative effect, the net of which will end up
achieving the desired results. The latter creates the
potential to optimize the approach as a result of the
entire team being part of the design development. In
some cases, this can/should include the client along
with the technical team, to allow for clarification and
potential real-time adjustment of project require-
ments and constraints.
3.
Incremental implementation: This essentially rep-
resents adaptive management. At the small scale,
it boils down to the timely adjustment of a remedy
configuration or operation (or both) to ensure opti-
mal performance. At the large scale, it involves
approaching a remedy in increments to facili-
tate meaningful progress guided by observation,
a concept pointed to by the NRC in their recom-
mendations related to lessons learned on the Coeur
d’Alene River basin.12 For many large sites, there
are certain remedial measures that provide value
regardless of whatever the full characterization
may ultimately reveal. These measures can often
be agreed to and possibly expedited and imple-
mented in phases, while data collection are geared
toward understanding the cumulative effect toward
site rehabilitation. These data feed back into the
decision-making process and can both accelerate
the remedy and lead to more creative and optimized
solutions. In either case (small or large scale), the
design of the data collection and the responsiveness
of the decision-making process are key to success,
and something we will touch on further later in this
chapter when we discuss performance monitoring.
For a remediation practitioner, it is worth considering how
an integrated approach to remedy planning and design might
lead to more coordinated strategies for both small and large
sites. As the industry has matured and is turning to address
the types of problems once thought to be unsolvable, this phi-
losophy is overtaking conventional design. This is particularly
useful where the project may involve the need to incorporate
other service lines outside of remediation, such as support for
infrastructure installation, protection, or relocation. While
most clients procuring remediation services certainly do not
spend a lot of time thinking about design philosophy, they
will gravitate toward the practitioner that can deliver at this
level of performance.
3.4  KEY FACTORS IN REMEDIATION DESIGN
Now that we have covered the philosophy of remediation
design and the benefits of taking an integrated approach,
there are a number of key factors that can affect the success of
73
remediation design efforts that are worth touching on. These
include
1. Health and safety (H&S)
2. Predesign efforts
3. Biogeochemical considerations
4. Environmental considerations
Each of these four topics can be mapped back to the elements
of the engineering design process. While there are numerous
other subelements of the design process that we could spend
time on, most are covered in the many books on engineering
design or are subject to the policies of the particular organiza-
tion doing the work. What makes these worthy of separating
out is that from a practical perspective, they can (and often do)
impact the feasibility, implementability, and cost of a remedy.
3.4.1 Health and Safety in Design
Simply put, if something can’t be done safely, it shouldn’t
be done at all. H&S must be the first priority throughout the
entire design process. This includes integrating H&S into the
initial proposal decision process, the project planning pro-
cess, project execution, and project closeout.
Demonstration of an effective safety program is typically a
threshold criterion for doing business in the remediation mar-
ketplace. As a result, most companies that offer remediation
services have adopted behavior-based safety programs that
focus on the elimination of behaviors that can result in acci-
dents. While we don’t need to explore this very deeply for our
purposes, one important distinction is that this goes far beyond
the creation of a project-specific H&S plan (HASP). Such plans
are designed to collect and document important project specific
safety program information such as roles and responsibilities,
emergency procedures, and identification of safety critical tasks
and communicate the controls to be implemented for each. In
design, we have the opportunity to identify the hazards up front
and then consider how the design might be adapted in order to
eliminate them altogether or minimize them through substitu-
tion or isolation. This happens before the HASP is finalized.
With this in mind, there are three topics related to the sup-
port of safe designs that we will focus on for this discussion:
hazard identification and critical failure analysis, the hierar-
chy of hazard controls, and response planning. The following
sections offer more insight into each of these.
3.4.1.1 Hazard Identification and
Critical Failure Analysis
As it applies to remediation design, safety (the avoidance of
personal injury and/or damage to property) can involve things
like process-related risks (risk of injury based on the tasks to
be completed), ergonomics (the risk of injury based on the
placement of equipment), the adequacy of material and equip-
ment specifications (risk of injury or equipment damage due to
chemical or physical incompatibilities), or the implications of
site factors that may complicate operation. This is by no means
an exhaustive list, but clearly represents a mix between hazards
related to process/task and hazards related to system reliability.
74
The identification of such hazards is a critical part of the
design and typically involves questions such as the following13:
What can go wrong? What are the consequences? How could
it arise? What are other contributing factors? How likely is it
that the hazard will occur? While anticipating that every haz-
ard is not possible or practical, the design team should think of
as many of the main hazards as possible so they can be ranked
and addressed as appropriate in the design. One systematic
approach that can help accomplish this for both process-/task-
related hazards and system reliability–related hazards is a
FMEA. FMEA involves the study of potential failure modes
in every subcomponent of a system.8 This type of analysis is a
topic with a significant body of literature and practice behind
it. Those practices vary slightly between industries and orga-
nizations, but there are two common elements14:
1.
Creating a block diagram of the system and opera-
tion process: This will highlight the major compo-
nents or process steps as blocks, with lines to indicate
how the components or steps are connected/related.
The goal is to show the logical relationships of the
major components and establish a structure around
which the FMEA can be developed.
Completing an analysis worksheet: This can be
2. that for a system, failure of one component can
done on a custom form or make use of commercially
available computer software. The goal is to docu-
ment the outcome of the review so that the recom-
mendations can be acted upon, and there is a record
of the actions to reduce risk and increase reliability.
A generic example worksheet is provided in Tables
3.1 through 3.4. As shown, the fields on a typical
worksheet include the following:
a. System element: This involves a description of
a specific mechanical component or operational
function/activity, its role, and any relevant quan-
tification or metrics that can be attached to either.
b. Failure mode: This involves identifying the
manner in which a system element could poten-
tially fail to meet the design intent. This includes
mechanical components and operational activi-
ties. For mechanical system components, it might
reflect things like material degradation and fail-
ure, overheating, line blockage or rupture, and
electrical short. For operational activities, it
might reflect things like loss of containment,
ignition of an explosive gas, subsidence of work
area, and obstruction to safe access.
c. Effects and severity: For each failure mode iden-
tified, the design team must attempt to quantify
the severity of the effects. This should be specific
regarding the level to which it affects either the
system, the operators, or the area surrounding the
system. The level of system in operability typi-
cally breaks down to total failure, partial failure,
intermittent failure, overfunction, or unintended
function. Other effects could include equipment
damage, personal injury, or unintended release
Remediation Engineering
of chemicals or nuisance odors to the environ-
ment. The severity of the effect is one of the
three variables that are assigned with a numeric
rating as part of the analysis to support priori-
tization and/or justification for design modifica-
tions. The common industry standard is to use
1 to represent no effect and 10 to indicate very
severe effects that come with no warning. Tables
3.1 through 3.4 provide a sample ranking chart
for failure mode and safety issue severity.
d.
Causes and probability of occurrence: For each
failure mode identified, the design team must
also consider the cause. These should be iden-
tified very specifically and in technical terms.
Examples of potential causes of mechanical
component failure might include the incompat-
ibility of piping materials with the chemicals
they are in contact with, excessive pressure
generation due to line sizing, introduction of
debris, and geochemical reactions. For opera-
tional activities, examples might include inad-
equate head clearance due to poor positioning
of equipment, and containment capacity. Note
be the cause of failure in another component.
Probability of occurrence is the second of three
variables that are assigned with a numeric rat-
ing as part of the analysis to support prioritiza-
tion and/or justification for design modifications.
The common industry standard is to use 1 to
represent not likely and 10 to indicate inevitable.
Tables 3.1 through 3.4 provide a sample ranking
chart for probability of occurrence.
e.
Current controls and likelihood of detection:
These are factors in the current design that would
either prevent the cause of the failure mode from
occurring or detect that the failure is likely and
provide advance warning so it can be managed.
Detection is the third of three variables that are
assigned with a numeric rating as part of the
analysis to support prioritization and/or justifi-
cation for design modifications. The common
industry standard is to use 1 to represent almost
certain to detect and 10 to indicate no chance of
detection. Tables 3.1 through 3.4 provide a sam-
ple ranking chart for detection.
Risk priority number (RPN): This is the prod-
f.
uct of the rankings for severity, occurrence, and
detection. These values can range from a low end
of 1 to a high end of 1000. While these values
are relative only with no significance in absolute
terms, in general, the higher the risk priority num-
ber, the more serious the risk. It is important to
recognize that the RPN provides a relative means
of ranking failure modes. There is no threshold
value for RPNs above which it is mandatory to
take action or below which action is excused.
 Principles of Integrated Design
TABLE 3.1
Example Failure Mode and Effects Analysis Worksheet
Completion
Date:
Project
Name:
Review
Team:
Probability Likelihood Risk
Severity of of Priority
System of Effect Causes of Occurrence Current Detection Number Recommended
No. Element Role Failure Mode Failure Effect (1–10) Failure (1–10) Controls (1–10) (1–1000) Actions Follow Through
Name of the Description of Identification Quantification of Numerical Identification of Numerical Elements Numerical Product of Documentation Documentation
system what the of the the potential ranking root cause for ranking to of the ranking to severity, of actions of follow
element system manner of outcomes of of failure. For describe current describe occurrence, recommended through, to
being element failure for failure—degree severity, mechanical the design the and by the design ensure effective
evaluated being mechanical of impaired 1 being components likelihood that likelihood detection team to implementation
(can be a evaluated components system no effect, this might of a failure. would of ratings; address/control of
function or accomplishes (material operability 10 being include 1 being either detecting provides a a system recommended
activity vs. in the system degradation, (total failure, most chemical least 10 prevent the cause relative component actions; should
a specific operation overheating, partial failure, severe incompatibility, being the cause of a means of that could assign an
mechanical blockage, intermittent with no excessive greatest. of the failure ranking potentially fail, individual to be
component) electrical failure, warning. pressure due to See table. failure mode. failure or a particular responsible and
short, etc.) overfunction, See line size, mode or See table modes operational a target date for
as well as unintended table. introduction of detect activity that completion,
failure for a function) and debris and that the could create an with final
function/ equipment geochemical failure is unsafe confirmation of
activity (loss damage, reaction. For a likely and condition completion
of personal injury, function/ provide
containment, releases to the activity, this advance
ignition of environment, might include warning
an explosive regulatory ergonomics and so it can
gas, noncompliance, containment be
subsidence etc. capacity. managed
of work area,
obstruction
to safe
access, etc.)

75
76 Remediation Engineering

TABLE 3.2
Severity Effect: Evaluation Ranking Criteria
Rank Severity Severity Effect
10 Hazardous without warning Destructive, life-threatening failure mode that can occur without warning
9 Hazardous with warning Destructive, life-threatening failure mode that can occur with warning
8 Very high Extreme effect, system damaged, inoperable, and a safety problem; may cause severe injury
7 High Major effect, system inoperable with equipment damage; may cause injury
6 Moderate Significant effect, compromises system operation, and possibly regulatory compliance with minor damage
5 Low Moderate effect, compromises system operation, and possibly regulatory compliance with no damage
4 Very low Some effect, system operable with significant degradation of performance
3 Minor Slight effect, system operable with noticeable degradation of performance
2 Very minor Very slight effect, system operable with minimal degradation of performance
1 None No effect

TABLE 3.3
Probability of Failure Occurrence: Evaluation Ranking Criteria
Rank Probability Description
10 >1 in 2 Very high–failure almost inevitable
9 1 in 3
8 1 in 8 High–repeated failures likely
7 1 in 20
6 1 in 80 Moderate–occasional failures likely
5 1 in 400
4 1 in 2,000
3 1 in 15,000 Low–relatively few failures likely
2 1 in 150,000
1 1 in 1,500,000 Remote–failure unlikely

TABLE 3.4
Likelihood of Failure Detection: Evaluation Ranking Criteria
Rank Detection Likelihood
10 Absolute uncertainty Design control cannot detect potential cause/mechanism and subsequent failure mode.
9 Very remote Very remote chance the design control will detect potential cause/mechanism and subsequent failure mode.
8 Remote Remote chance the design control will detect potential cause/mechanism and subsequent failure mode.
7 Very low Very low chance the design control will detect potential cause/mechanism and subsequent failure mode.
6 Low Low chance the design control will detect potential cause/mechanism and subsequent failure mode.
5 Moderate Moderate chance the design control will detect potential cause/mechanism and subsequent failure mode.
4 Moderately high Moderately high chance the design control will detect potential cause/mechanism and subsequent failure mode.
3 High High chance the design control will detect potential cause/mechanism and subsequent failure mode.
2 Very high Very high chance the design control will detect potential cause/mechanism and subsequent failure mode.
1 Almost certain Design control will almost certainly detect a potential cause/mechanism and subsequent failure mode.

g.
Recommended action: This documents the
action(s) recommended by the design team to
address/control a system component that could
potentially fail or a particular operational activ-
ity that could create an unsafe condition. These
actions could include selection of different
components or materials, modified equipment
layout, limiting operating range for a piece of
equipment, providing monitoring mechanisms,
performing preventative maintenance, and inclu-
sion of backup systems or redundancy. Each rec-
ommendation would fall somewhere into the
hierarchy of controls, which is discussed in the
next section.
Principles of Integrated Design
h.
Follow through: This clearly assigns responsi-
bility and sets a schedule for the recommended
action to be completed.
This process creates a living document that should be
revisited and updated periodically throughout the system
lifecycle and whenever there is a substantive change to
the system. These updates can and often do identify new
failure modes. The value in this process is lower risk of
personal injury and damage to property, strengthened per-
ception of reliability in the marketplace. It is also often
required to comply with safety and quality standards such
as those published by the International Organization for
Standardization (ISO). The analysis also can be a valuable
tool for training new employees in the steps required to
perform their jobs safely.
3.4.1.2  Hierarchy of Hazard Controls
Once a hazard has been identified, a control measure must
be put in place. Building from the discussion in the previous
section, this in effect would reduce the RPN by changing the
severity of the failure, its frequency, or its detection—or some
combination thereof. All hazard controls fall into a three-
tiered hierarchy, as follows15:
1.
Engineering controls: Engineering controls are the
most reliable and effective controls because they
directly eliminate or minimize hazard. This is
accomplished by such means as providing sufficient
ventilation, substituting a less hazardous substance
for a process, physically isolating the hazard, or
incorporating process safety controls that are clearly
documented and understood.
2.
Work practices and administrative controls: Safe
work practices include general workplace rules
and other operation-specific policies that may
apply. It is important to conduct a review to make
sure that all such applicable policies are identified
and incorporated into the deployment element of
the design. This might include subsurface utility
clearance requirements for confined space entry.
Administrative controls overlap with safe work
practices, but can be limited to control or manipula-
tion of the work schedule or work habits to further
limit exposure. Job rotation is a type of administra-
tive control. Training is also considered an adminis-
trative control.
3.
Personal protective equipment (PPE): When expo-
sure to hazards cannot be engineered completely out
of a design, and when safe work practices and other
forms of administrative controls cannot provide suf-
ficient additional protection, a third method of con-
trol is the use of protective clothing or equipment.
This is collectively called personal protective equip-
ment (PPE). The correct PPE to be used are deter-
mined by the residual hazards after application of
other controls.
77
The hierarchy mentioned previously is listed in order of pref-
erence based on reliability, with PPE the last resort. In prac-
tice, a combination of controls is often used, but whatever the
combination that is arrived at, the opportunity for incorporat-
ing controls comes in the design. This should be monitored,
updated as needed, and positively reinforced through a larger
H&S program.
To illustrate the application of this hierarchy in design, we
can consider a project that involved the need to mix large vol-
umes of concentrated sulfuric acid with a volume of soil to
support the evaluation of an experimental treatment process.
This was to be done in situ and if possible in an open area.
Proper handling and storage of the acid and monitoring of air
quality around the area of application were all areas of focus
for a safe design minimizing the exposure potential for field
employees. The following are the controls that were incorpo-
rated into the design at each level of the hierarchy:
• Engineering controls
• Vapor control: To eliminate risk of generating
sulfur dioxide fumes, fully hydrated 50% sulfu-
ric acid was used in place of concentrated (96%)
sulfuric acid.
• Method of storage: In order to minimize han-
dling, the acid was delivered in a chemical
tanker truck, and the chemical tanker was stored
onsite until all of the acid was utilized.
• Secondary containment: To minimize the risks
of an associated release. A secondary contain-
ment representing 120% of the largest delivery
volume of acid (compared to the 110% required
by OSHA). The secondary containment con-
sisted of flexible sides that could be lowered
or flattened to allow for access by the storage
tanker.
• Piping and valving: All piping and valves were
chemically compatible with 50% sulfuric acid.
The piping was set up to allow the acid to grav-
ity drain from the tanker to the treatment cell,
preventing the line from pressurizing. The flow
was managed using a pneumatically actuated
valve and controls located outside of the exclu-
sion zone, with remote flow measurement. Acid
was discharged from the tanker in a top-load
configuration, allowing the flow to be shut down
even in the event of a failure of the pneumatic
valve, with siphon breaks to allow the line to
drain down, and a clean water tie in to flush the
line after each use.
• Neutralization capacity: Sufficient granular
limestone was kept on hand for neutralization
capacity in the event of a small/incidental acid
release.
• Administrative controls
• Staff involvement and training: All staff that
were to be involved in the actual acid handling
process during field implementation were part
78
of the design and construction team and were
intimately familiar with the procedure that was
established.
• Documentation of procedures: Regardless of the
staff involvement and training, the acid-loading
procedure was carefully documented with haz-
ards and hazard controls identified in a job safety
analysis. This analysis was used and updated in
the field in real time.
• Staffing rotation: To avoid overexertion, staff
were rotated out of the exclusion zone every
45 min. Further, all staff were removed from the
exclusion zone during acid addition.
• Site management: The site was set up with outer
fencing to demarcate the limits of the support
zone and inner fencing to demarcate the exclusion
zone. Access to the exclusion zone was gained
through the contamination reduction zone. Two
separate chemical management areas were set up,
one for the acid and one for all other chemicals to
be used in the treatment. A wind sock was used
to keep the support team upwind of the treatment
area during acid addition and mixing.
• Environmental management: To ensure the
safety of staff in the support zone and site per-
sonnel in the larger area surrounding the treat-
ment location, air sampling was conducted to
monitor for sulfur dioxide, excessive levels of
carbon dioxide, particulates, and a variety of
other parameters. The mixing area was sub-
jected to continuous misting to suppress particu-
lates. In addition, the temperature and pH of the
treatment cell were carefully monitored to pre-
vent steam generation through the heat of neu-
tralization, or excessive pH swings.
• PPE
• Regardless of all the engineering and adminis-
trative controls, the staff that were to be posi-
tioned in the exclusion zone during the mixing
(a)
FIGURE 3.2  Hazard controls at an in situ remediation site. (a) Work practice and administrative controls in the form of site management
(exclusion zone, highly visible safety barrier around the work area, and visible wind direction indication), coupled with level B personal
protective equipment to protect against potential fumes related to sulfuric acid. (b) Engineering controls in the form of storage method,
secondary containment, and remote valve actuation for acid addition to the treatment cell.
Remediation Engineering
conducted between each acid addition were
specified to wear chemical resistant PPE (inner
and outer gloves, chemical protective boots,
splash apron) and Level B supplied air with a
cascade system and escape bottle.
Figure 3.2 presents photographs depicting some of the con-
trols mentioned earlier. The combination of controls that were
employed allowed the addition and mixing of over 6000 gal
of 50% sulfuric acid with the targeted volume of soil to be
completed over a period of approximately 6  days, with no
incidents. The knowledge gained through this process would
support refining of the individual controls to find the optimum
balance of efficiency and risk management.
3.4.1.3  Response Planning
One final aspect of H&S planning during design relates to
the preparation of response plans. It is not enough to sim-
ply develop the controls designed to prevent an incident. If
there is a failure, the team needs to be ready to respond. This
requires planning that follows the four pillars of emergency
response, as follows:
1.
Prevention and mitigation: Identifies and reduces the
impacts and risks of hazards before an emergency or
disaster occurs
2.
Preparedness: Increases the ability to respond
quickly and effectively to emergencies and to recover
more quickly from their long-term effects and
involves actions taken prior to an event to ensure the
capability and capacity to respond
3.
Response: Outlines actions to be taken during or
immediately after an emergency situation for the
purpose of managing the consequences
4.
Recovery: Outlines actions taken after an emergency
is controlled, to reestablish preemergency conditions
The intent of the first pillar is accomplished through the
process of completing the hazard identification and critical
(b)
Principles of Integrated Design
failure analysis and following through with the incorporation
of controls to support hazard prevention or mitigation, which
leaves the remaining three pillars unaddressed. The need to
do so will be limited to certain situations where there is a
residual hazard that has not been completely eliminated and
has a significant severity ranking. For these, the design team
needs to consider an appropriate emergency response plan
that will cover preparedness, response, and recovery.
For most projects, this will result in a very limited num-
ber of response plans. It is critical that the staff involved in
the operation of the system being designed receive training
to orient them with the details of the response plan so they
can execute without hesitation if the need arises. Here, we
can build on the example from the previous section, where
over 6000 gal of 50% sulfuric acid were added to and mixed
with a targeted volume of soil in situ. In that case, the controls
put in place significantly mitigated the risk of a catastrophic
failure of the acid storage tank by modifying the probabil-
ity and improving the ability to detect and stop the release.
Regardless, the relative severity of that type of failure would
be high, so a spill response plan was developed in conjunction
with the local fire department. While it was never needed in
execution, it was critical to have it.
3.4.2 Predesign Efforts
Predesign is synonymous with the testing element (Element
4) of the overall design process. While the title implies that
this phase of analysis occurs before the design begins, it often
(necessarily) happens simultaneously and possibly in several
iterations. The term predesign is more of a reflection of the
fact that these activities lie between formulation of the initial
design concept and completion of the final detailed design.
The types of predesign activities common to environmental
remediation typically involve either experimentation (the act of
conducting a controlled test to determine/demonstrate how well
something works) or characterization (collecting physical and
chemical information that more fully describes the features of
the subject). Experimentation can be further broken down into
thought experiments and real experiments, either in the labora-
tory or in the field. By comparison, characterization typically
involves the collection of additional site data to clarify gaps in
the understanding of the area targeted for remediation to better
inform the design. There is some overlap between these catego-
ries, but we will use these designations for our purposes.
3.4.2.1  Concepts and Definitions
Before we begin drilling into the details, we need to focus on
a few concepts and definitions. The first is that to be effec-
tive, predesign activities beyond thought experiments funda-
mentally require proper design in their own right. There are
usually three steps in the predesign process: data collection
design, data collection, and data analysis. As with the larger
design process, these steps are not independent and may
require some iterative refinement.
As a practitioner, it is important to recognize that collect-
ing data is costly. Funding and time are major constraints,
79
so the benefits of the information to be gained have to be
weighed against the cost of collection, both financially and in
time spent. There are three important questions that can help
support the decision to propose/pursue data collection:
1.
What purpose will the data serve? It might seem
important to simply focus on identifying the ques-
tions the data will answer—but that alone cannot
convey a clear need because not all questions need
to be answered. Articulating how the data will be
used and how that in turn will benefit the overall out-
come of the design effort provides a better basis. For
example, we could propose detailed vertical aquifer
sampling along the planned orientation of a perme-
able reactive barrier in order to better understand the
contaminant concentration profile and stratigraphy
that the barrier will be installed in. This may not pro-
vide sufficient reason to proceed. However, it makes
a much stronger case if it is pointed out that these
data are critical to ensuring the final design that sup-
ports complete treatment and that they also create
the opportunity for optimization and lower overall
remedy costs.
2.
What is the cost of the data collection? The answer
to this question should look at financial cost, time
required to complete the activity, and any risks that
may be relevant over the time frame of the data collec-
tion. Financial costs should reflect planning, gaining
required approvals, collecting the data, and analyz-
ing the data collected. The question of time can be
answered with a simple schedule, and the question
of risks could pertain to hazards in execution, com-
pliance deadlines that may be missed, complications
with stakeholders, or many other possibilities.
3.
Does the potential benefit justify the cost? There is
no specific formula for determining a cutoff point in
this regard. The benefits in how the data will be used
will speak for themselves. Costs can be compared
to the anticipated cost for the overall remedy being
designed. The evaluation of time and potential risks
is necessarily more subjective.
This loosely fits with the EPA’s seven step data quality objec-
tives process.16 In this process, the investigator must consider
the following: What is the problem and related question that
needs resolving? What data can answer the question and from
where? How will the decision be made based on the data?
What is an acceptable range of uncertainty? The final step is
to articulate how the data will be collected.
Care must be taken to not get bogged down in this pro-
cess. The goal is to prioritize the critical technical issues in
the interests of making progress and avoiding getting bogged
down in unraveling all the complexities at a site. If we look
back on the example of vertical aquifer sampling along the
planned orientation of a permeable reactive barrier, there
could be a wide range in the level of sampling depending on
the number of locations and the number of discrete intervals
80
targeted at each location. A scope must be developed that
provides a good balance between the cost of the effort and
the data yielded. At the scale of such a remedy, planning for
vertical profiling on 5 ft centers is likely to be unnecessary.
However, every 50 ft or greater may be both more reasonable
and adequate for the purpose, depending on the site charac-
teristics. Once the data collection effort is justified and the
objectives clear, the data collection program can be finalized
to ensure that the questions of interest can be answered accu-
rately within any constraints.
Another key concept in predesign is the distinction of
what represents proof of concept testing and what does not.
Proof of concept testing is used to demonstrate the technical
validity/feasibility of something. This is most often accom-
plished in a laboratory at the bench scale, but can extend to
pilot testing when the technology is new and unproven, such
that field-scale implementability can be demonstrated under
the operating conditions and environment in which the rem-
edy is intended to function.
3.4.2.2  Thought Experiments
A thought experiment is a mental exercise used to investi-
gate the nature of physical things,17 a mental test using the
scientific method and first principles to validate a theory,
principle, or hypothesis. In remediation, thought experi-
ments can be used to test theories about the physical environ-
ment. This can help eliminate misinformation and improve
stakeholder clarity. Thought experiments can also be used
to screen technology applications to avoid completing costly
real experiments where there is a high potential for failure.
In this case, the goal isn’t to simply save the cost of a failed
lab or field experiment.
There are a number of interesting thought experiments
involving the physical environment in the recent publication
Remediation Hydraulics.18 One of these involves an exploration
of the validity of random walk as an explanation for disper-
sion, that is, the random movement of a groundwater “particle”
around soil grains as it flows forcing the particle to move far-
ther and farther from the centerline on which it started. Another
involves the exploration of the notion that fluid injection into
an aquifer can displace existing groundwater laterally, as the
injected fluid takes up the space that the groundwater once
occupied. These thought experiments, respectively, revealed
that statistically speaking random walk could not result in wide
dispersion patterns as groundwater moves through a porous
media, and that the injection of a fluid into an aquifer has a very
limited chance of displacing the existing groundwater laterally,
more than likely the pressure required to do so would result in
failure or fracturing of the formation media first. Instead, the
existing groundwater is predominantly displaced vertically.
Where thought experiments are used to screen technol-
ogy applications, the process will follow the following set of
questions:
1.
What are the mechanisms to be applied and the
desired result? This orients the thought experiment
on what to focus on and the benchmark for success.
Remediation Engineering
2.
Can the proposed mechanism work? This is a thresh-
old question focused on technical viability outside of
a field setting. If first principles tell us the mecha-
nisms won’t work, there is no need to pursue further.
This may be easy or hard to answer depending on the
nature of the technology involved. Where possible,
calculations can be completed to provide insight into
whether the mechanisms being invoked can meet the
benchmark for success from a physical–chemical
perspective.
3.
Is the method deployable? This is a refining question.
There are many cases in which a proposed method
works in the lab, but can’t be supported in an aquifer.
4.
Is the method cost effective? Another refining ques-
tion. Questions of cost effectiveness are always rela-
tive and will be subjective depending on the various
drivers for the project.
This type of technology evaluation won’t necessarily be
definitive, but can help identify key questions to be asked
along the way. It can also (of course) incorporate any data
that might be available. A good example of a thought experi-
ment related to the screening of an innovative technology
involves the encrustation of NAPL. This type of technology
would be designed to form a skin or solid crust at the NAPL
surface/water interface, with the express goal of slowing
down diffusive transfer of contaminant mass from the NAPL
to groundwater to in turn reduce the dissolved contaminant
mass flux leaving the area of NAPL in groundwater (essen-
tially reducing dissolved mass flux without significantly
reducing source mass). Some additional goals would be to
accelerate weathering of the NAPL (destruction of the more
soluble components) and slow its mobility in the subsurface
where that is an issue.
This type of mechanism was first postulated by Richard
Luthy of Carnegie Mellon in 1993.19 In later years, a study
was completed at the University of Waterloo exploring the use
of the chemical oxidant potassium permanganate to form a
crust of manganese dioxide minerals around an NAPL body
to achieve the desired effects. The initial study was a labora-
tory study, followed by a field study using a small emplaced
source of coal tar in the Borden aquifer.20–22 Around the time
that these studies were going on, a group of researchers at the
University of Florida developed a streamtube model to link
NAPL source architecture to dissolved contaminant mass flux
emanating from the source.23 On a parallel path, a commer-
cial extensions of this NAPL encrustation approach was being
developed, focusing on the use of permanganate-based chem-
ical oxidants for NAPL source zone control and weathering.
This creates an opportunity for a thought experiment.
The fundamental question is whether reducing contaminant
diffusion from an NAPL source at the NAPL/water inter-
face through encrustation would materially reduce dissolved
mass flux from the source zone. The key parameters to the
University of Florida streamtube model were the degree
of NAPL saturation, the tubetime (residence time of the
water next to the NAPL surface as a reflection of the NAPL
Principles of Integrated Design 81

architecture), and the mass transfer coefficient. As depicted
by Figure 3.3, the model showed that a four to six order of
magnitude decrease in mass transfer would be needed to yield
a meaningful decrease in average mass flux, and that regard-
less of the mass transfer, equilibrium at the NAPL/water inter-
face is still achieved in minutes. In order for a crust around
an NAPL body to achieve this, it would have to decrease the
hydraulic conductivity around the NAPL body by the same
amount (multiple orders of magnitude).
This calls into question the technical viability of the mech-
anism. However, we need to keep in mind that the results of
this thought experiment may not be definitive, so we should
explore the next question in the process related to deploy-
ment. For this we can draw some support from the short- and
long-term observations published on the Borden aquifer field
study.21,22 This raises a few more questions:
• Oxidant-target compatibility: Permanganate is a
selective oxidant that works well for some petro-
leum hydrocarbons and very poorly for others. As a
consequence, successful weathering of the coal tar
could enhance solubility of those components not
affected by the oxidant by changing the NAPL com-
position, increasing their dissolved concentrations.
This effect was observed in the laboratory portion of
the published creosote experiments for compounds
such as biphenyl, dibenzofuran, and fluoranthene.21
• Secondary water quality effects: This relates to the
types of long-term consequential impacts to water
quality that could arise from the technology appli-
cation. The solubility enhancement of compounds
not susceptible to oxidation by permanganate would
have a limited impact if the diffusion-limiting mech-
anism works. Even the by-products from incomplete
oxidation leaving behind high concentrations of par-
tially oxidized organic compounds would tend to be
transient, as these would be highly susceptible to bio-
degradation. By comparison, something that could
be  a longer-term concern would be the stability of
the manganese deposited in the subsurface as part of

é é kC (T - ti ) ù ù
n ê exp ê s ú ú
r
C (T ) = f cC s å ê1 -
ê
ë N û
é kC (T - ti ) ù
ú
ú
i =1 ê exp[k Siti ] + exp ê s ú - 1 ú
êë ë rN û úû
Time (days) C(T ) (mg/L) k (1/h) Tubetime (days) NAPLSAT Model of mass flux response to change in NAPL
100.0000 0.3599 0.0010 100.0000 0.0010 arhitecture and mass transfer from Fure et al.23
100.0000 3.5607 0.0100 100.0000 0.0010
100.0000 32.0342 0.1000 100.0000 0.0010
• Ŝn is the average NAPL saturation along flow
100.0000 136.4250 1.0000 100.0000 0.0010
trajectory
100.0000 150.0000 10.0000 100.0000 0.0010
100.0000 150.0000 50.0000 100.0000 0.0010 • k is the mass transfer rate coefficient
100.0000 150.0000 100.0000 100.0000 0.0010 • T, ti is the total time and reactive travel time
Time (days) C(T ) (mg/L) k (1/h) Tubetime (days) NAPLSAT
• C(T) is the flux averaged concentration
100.0000 1.7982 0.0010 100.0000 0.0050
100.0000 17.0421 0.0100 100.0000 0.0050
100.0000 105.0925 0.1000 100.0000 0.0050 Modify k, Ŝn, T, ti
100.0000 149.9991 1.0000 100.0000 0.0050
100.0000 150.0000 10.0000 100.0000 0.0050 • NAPL saturation and tubetime (architecture);
100.0000 150.0000 50.0000 100.0000 0.0050 mass transfer coefficient are key parameters
100.0000 150.0000 100.0000 100.0000 0.0050
• Typical baseline k values on the order of 10(1/h)
Time (days) C(T ) (mg/L) k (1/h) Tubetime (days) NAPLSAT
100.0000 0.3599 0.0010 100.0000 0.0100 • Four to six order of magnitude decrease in k
100.0000 3.5607 0.0100 100.0000 0.0100 needed to drive meaningful decrease in average
100.0000 32.0342 0.1000 100.0000 0.0100 mass flux
100.0000 136.4250 1.0000 100.0000 0.0100 • Equilibrium still achieved in minutes (not shown)
100.0000 150.0000 10.0000 100.0000 0.0100
100.0000 150.0000 50.0000 100.0000 0.0100
100.0000 150.0000 100.0000 100.0000 0.0100
Time (days) C(T ) (mg/L) k (1/h) Tubetime (days) NAPLSAT
100.0000 1.7982 0.0010 100.0000 0.0500
100.0000 17.0421 0.0100 100.0000 0.0500
100.0000 105.0925 0.1000 100.0000 0.0500
100.0000 149.9991 1.0000 100.0000 0.0500
100.0000 150.0000 10.0000 100.0000 0.0500
100.0000 150.0000 50.0000 100.0000 0.0500
100.0000 150.0000 100.0000 100.0000 0.0500

FIGURE 3.3  Model of source control via encrustation.

82
the treatment. Manganese is susceptible to reductive
dissolution in anaerobic environments. Given that
the prevailing environment around a coal tar source
is typically strongly anaerobic (to the point of metha-
nogenesis), it would be important to understand the
long-term fate and risk associated with manganese.
• Uniformity of coverage: This relates to the ability to
achieve uniform coverage of the NAPL surfaces. In
addition to logistical challenges, the mode of delivery
would tend to be self-limiting. As the oxidant reacts
at the NAPL surface, there would be significant gen-
eration of gas (carbon dioxide) and precipitation of
manganese oxide solids. Delivery of the treatment
solutions using high-pressure direct push methods
would exacerbate the lack of uniform coverage by
causing formation failure (fracturing), which affects
the delivery pattern and degree of vertical and lateral
distribution.
In conclusion, the investigators found that the treatment pro-
duced no long-term effect on the dissolved plumes emanating
from the coal tar source. When considering all of the issues
mentioned above, there would certainly be reason to ques-
tion the level of success that could be achieved with such a
technology.
3.4.2.3  Real Experiments
Most thought experiments don’t require a design per se but are
rather a free-form type of problem solving where the experi-
menter explores different angles to see what insights they
can provide. Compared to thought experiments, and because
they involve the collection of physical data, real experiments
require a rigorous design prior to their execution.24,25
Real experiments help confirm what outcome will occur
when a particular factor or set of factors are manipulated. The
purpose for doing this can include the following:
• Confirming viability of a process: Determining what
combination of factors will yield a successful result
based on the goals of the experiment.
• Confirming the significant factors: Sometimes an
experiment can point to significant success factors
that were previously unknown or unanticipated.
• Optimizing inputs: Determining the optimal level of
various inputs that will still yield a successful result
based on the goals of the test. This often involves
breaking down the factor levels used in an initial
experiment to smaller increments.
• Selecting between alternatives: Supporting selection
between various process alternatives representing a
range of quality and cost, based on how they affect
outcomes.
• Reducing variability: Identifying ways to improve
the reproducibility of an outcome.
The scope and scale of an experiment can vary significantly
depending on the focus, but repeatable procedure and logical
Remediation Engineering
analysis of the results are common threads regardless of focus.
In the circles of academia and certain sciences, an experiment
usually tests a hypothesis (an educated guess about the possible
relationship between two or more variables). In remediation,
experiments more frequently aim to answer a question or dem-
onstrate a process, without expectation about what the experi-
ment will reveal. This is often referred to as treatability testing.
Clearly defining the details of an experiment supports the
desired outcome and ensures the validity of the results. This
is critical for remediation designers given that the experi-
mental data are often used to drive decisions in a larger-scale
design. In addition, the overall data collection and analysis
plan must consider how the experimental factors, both con-
trolled and uncontrolled, fit together in a way that will meet
the specific objectives of the experiment and satisfy the prac-
tical constraints of time and money. The goal should be for
the experiment to utilize the available resources in a manner
that maximizes the information gained relative to the question
being investigated.
There are significant texts available on experimental
design. For our purposes, we will review a few key definitions:
• Focus and goals: This is critical for ensuring that
stakeholders have clear and appropriate expecta-
tions in terms of the question that is the focus of the
experiment and on what will constitute a successful
experiment.
• Factors: These are the variables relevant to the
experiment. Dependent variables are those that are
manipulated by the experimenter. Independent vari-
ables are those that change in response to manip-
ulation of the dependent variables. There are also
factors that represent noise in the experiment. These
are factors that are present and can induce variation
in the outcome, but cannot be effectively controlled.
• Framework: There are numerous frameworks that
can be applied to experimental design, but facto-
rial experimental frameworks are probably the most
common and widely accepted for remediation appli-
cations. A full factorial experiment is an experi-
ment whose design consists of two or more factors,
each with discrete possible values or levels, with the
experiment testing all possible combinations of these
factors and their levels. Full factorial experiments
can be costly to pursue, so fractional factorials are
often used in their place. Figure 3.4 illustrates the
concept of a fractional factorial experimental design.
This involves selecting only a fraction of the possible
combinations required for the full factorial for test-
ing based on their relevance.
• Control: Experimental control is a test setup that is
not exposed to a chemical or treatment being inves-
tigated so that it can be compared with test setups
that are exposed to the chemical or treatment. This
supports the validity of the results by confirming the
portion of the observed outcome that can be directly
attributed to the action of the chemicals or treatment
Principles of Integrated Design
Test Amendments
# Notes
Nutrients Molasses EVO Methanol Nitrate Heat
Test 1
Test 2
Test 3
Test 4
Test 5
Test 6
Test 7
Test 8
Test 9
Test 10
Test 11
Test 12
FIGURE 3.4  Example fractional factorial experimental design and controls.
versus other factors present in the control. Figure 3.4
illustrates the concept of a control.
• Replication: To improve the statistical significance
of an experimental result, replication (repetition) is
required. Replication can help determine the repro-
ducibility or variability of the results and therefore
the confidence level that can be assigned to the effec-
tiveness of the treatment. Replication is of course
costly, so it is often limited to situations where a
positive outcome is anticipated.
• Methods: The methods employed to execute the
experiment must be carefully considered in their
ability to yield the desired information without the
introduction of noise factors that could confound
the results. Experimental methods are typically
described in great detail and include the equip-
ment, materials, setup, procedures, and analyses.
Examples of different setups typically relied on for
remediation designs include batch or microcosm
testing and column testing. Batch or microcosm test-
ing typically involves individual containers that are
relatively static in their exchange with the outside
environment and are often configured so they are
completely closed. By comparison, column experi-
ments typically involve the passing of water and/or
reagents through a column of media.
• Analysis and interpretation: The manner in which
the data collected from the experiment is analyzed
and conclusions drawn. Examples include the
following:
• Simple correlations that look at the change in
one factor as another is modified. Correlation of
factors does not automatically indicate that one
is the cause of the other. The variations in two
factors may be highly correlated without one
causing the other; they may both be caused by
a third factor.
83
Tests to evaluate the ability of different organic carbon substrates, an electron
acceptor, and a small increase in temperature (10°C relative to the other tests)
to support biodegradation of the target contaminants.
Tests to evaluate the potential positive effect of nutrients to support biode-
gradation of the target contaminants when applied alone, or in combination
with organic carbon substrates, compared to the tests without nutrients.
Control set - two controls with soil and water only with no amendments to
rule out effects resulting in losses in the tests that are unrelated to the
amendments. One is sterile and one natural, to distinguish between biological
and nonbiological mechanisms. The third control is a heated natural control
to evaluate the effects of higher temperature on natural biological mechanisms.
• Time to reach a certain level of contaminant
reduction. The level would be a preselected
reference point that has relevance to the proj-
ect, and the units of time would be relevant to
the rate of change expected with the specific
process.
• Regression analysis to identify and describe
trends and associated kinetics. This provides a
level of predictability that can be useful in the
design when appropriately applied. Most often,
this involves linear (zero order) and exponen-
tial (first order) trends. These types of trends,
respectively, imply a constant reaction rate
that is concentration versus a reaction rate that
declines as concentrations decline. Trend analy-
sis can also involve Monod kinetics, where the
rate variation is based on microbial growth and/
or inhibition.
• Statistical tests to evaluate variance or confi-
dence levels exhibited in the data set. For labora-
tory experiments, it is important to view results
such as rates of degradation as approximations
of what might actually be achievable in the field,
with field testing required for further validation
of a full-scale design. This is related to the fact
that laboratory-scale treatments can overesti-
mate or, in some cases, underestimate perfor-
mance of a full-scale system based upon degree
of contact or other factors.
These definitions are most relevant to experiments completed
in a laboratory setting, but experiments can also be com-
pleted in a field setting. Because factorial experimentation
is most economically handled in the lab, field testing is typi-
cally limited to one or possibly two factor combinations that
have in a sense been prequalified. A key difference between
field tests and most laboratory tests is that field tests allow
84
for adaptive operation, where key factors can be adjusted
in real time to see how they impact outcomes/performance.
This requires that the key factors be clearly identified ahead
of time, a monitoring program set up to track them, appro-
priate bandwidths for their adjustment be defined up front,
and some rationale established for the adjustments that might
be made based on the data generated. Focusing on key fac-
tors is critical to prevent this from becoming too onerous; it
cannot be overly comprehensive. If something is observed
that can only be explained by some factor outside of those
deemed most important for regular operation, then the suite
of monitoring can be temporarily expanded to accommodate
troubleshooting.
Field experiments can range from pilot tests to simple field
tests. While these are often used interchangeably, they are
different. The term pilot implies a level of process demon-
stration, whereas a simple field test is usually geared toward
determining a site-specific engineering parameter for the
purposes of design. This generally makes pilot tests much
longer in duration than simple field tests—most pilot tests
last months to more than a year depending on the technol-
ogy being tested, while most field tests last days to weeks.
An example of a pilot test would be a demonstration that a
bioremediation technology is deployable to the field and can
be supported in the site-specific environment. An example
of a simple field test would be the determination of the site-
specific relationship between applied vacuum, soil vapor
recovery rates, and radial distance to which the recovery rate
will drive meaningful pore volume exchange. In either case, it
is critical that the right goals be established to temper expec-
tations. For example, the goals for a pilot test to demonstrate
the application of in situ bioremediation for groundwater res-
toration (using an approach that requires reagent injection)
might be as follows:
1. Collect site-specific data from hydraulic injection/tracer
testing to support engineering design of the full-scale
injection program. This would focus on injectability
factors and hydraulic factors. Injectability relates
to sustainable injection capacity at rates that won’t
result in system damage due to overpressurization
(determines time needed for a complete injection).
Hydraulic factors involve injection volume–delivery
radius relationships (which determine well spac-
ing), and groundwater flow rate and direction (which
determines the spacing of multiple injection lines).
2. Demonstrate creation of a geochemical environment
conducive to degradation of the targeted compound(s).
This would require clarification of what that opti-
mal environment is, the parameters that can con-
firm it, and the frequency with which they should be
monitored.
3. Demonstrate evidence of enhanced contaminant deg-
radation. This is important because within the time
frame of a pilot, target contaminant concentrations
(in some situations) may not drop significantly or
may even increase slightly. Alternatively, increases
Remediation Engineering
in degradation products associated with the targets
could provide sufficient evidence of enhanced con-
taminant degradation.
We will now examine an example of a real laboratory
treatability experiment connected with an active indus-
trial facility with operations dating to the World War II
era (1940s). The operations required the aboveground stor-
age of 1,2-dichloroethane (1,2-DCA). Historic releases
resulted in the presence of 1,2-DCA at concentrations up to
4900 mg/L in shallow groundwater beneath the site. This
represents nearly 60% of saturation, indicating the pres-
ence of NAPL.
The project team was interested in evaluating the poten-
tial for harnessing and/or enhancing natural biodegradation
as a means to drive groundwater restoration. Consequently,
a laboratory treatability test was planned with the objective
of evaluating the following using microcosms of site soil and
groundwater:
1. The rate and nature of 1,2-DCA degradation without
the addition of remedial amendments
2. The rate and nature of 1,2-DCA degradation with
the addition of remedial amendments, as compared
to unamended controls, one set of which would have
been sterilized to eliminate microbial activity as a
factor
3. The relationship between 1,2-DCA concentration
and degradation rates
These objectives were pursued in two phases. The first
phase examined the ability of various amended systems to
degrade an initial 1,2-DCA dose of 30 mg/L. The second
phase examined the effect of increasing 1,2-DCA concen-
tration on the rate of degradation in those microcosms com-
pletely degrading the 1,2-DCA that was initially present.
The sequence of concentration increases was 100, 200, 300,
500, and 1000 mg/L.
The study employed site soil and groundwater combined
in sealed vessels (microcosms) to which various reme-
dial amendments were added in an attempt to stimulate
increased 1,2-DCA degradation. A summary of the treat-
ments incorporated into the study and how they related to
a factorial setup can be found in Figure 3.4. Three elec-
tron donors—molasses, emulsified vegetable oil (EVO), and
methanol—an electron acceptor (nitrate), and supplemen-
tal nutrients in the form of diammonium phosphate (DAP)
were added to the microcosms alone and in combination
to determine which could stimulate the degradation of 1,2-
DCA. The experiment also included unamended and abi-
otic (autoclaved) controls. The abiotic controls were used
to monitor nonbiological losses from the microcosms due
to abiotic reactions or other losses. Additional unamended
treatments were prepared and incubated at a higher tem-
perature (25°C) to evaluate the effect of temperature on the
degradation of 1,2-DCA. These microcosm experiments
provided a screening tool that was useful for quantitative
Principles of Integrated Design
comparison between treatments. The material and meth-
ods used in the experiment, and the observed outcome are
described below.
Materials and Methods
Sample collection and processing: Three 4 ft long cores
in acetate sleeves were collected from the aquifer
zone targeted for remediation. The sleeves were
sealed using wax and plastic liner caps immediately
upon retrieval, then packed in coolers with ice, and
sent by overnight courier to the treatability labora-
tory. Upon arrival, they were placed in an anaero-
bic glove box, passed through ¼ in. sieves to remove
large particles, and then transferred to glass jars.
Preliminary soil analysis: Initially, sieved soil from dif-
ferent cores and/or depths (designated subsamples)
was kept separate so that the contribution of each of
the soil subsamples to the final aqueous concentra-
tions of 1,2-DCA concentrations in experimental
microcosms could be estimated. In order to predict
the contribution of the site soil to dissolved 1,2-DCA
in the experimental microcosms, preliminary mock
microcosms containing 40 g of site soil and 72 mL
of distilled, deionized water were constructed in
duplicate in sterile 120 mL serum bottles for each
soil subsample. The amounts of soil and groundwa-
ter in each mock microcosm were less than those of
the normal experimental microcosms, but the ratio of
soil to water was identical. The bottles were shaken
and allowed to remain static overnight, and then the
aqueous phase was analyzed for volatile organic
compounds to determine the concentration of DCA
that was dissolved/desorbed from the soil. After the
soil subsample mock microcosms were analyzed, the
final blend of subsamples to be used in the experi-
mental microcosms was determined. All soils for use
in the microcosms were thoroughly homogenized
prior to use in order to obtain as uniform as possible
a distribution of microorganisms as well as 1,2-DCA.
Preliminary water analysis: Fifteen liters of ground-
water were obtained from an area coincident with
where the cores were collected. The groundwater
was collected in 1 L glass containers, filled to the
top to eliminate headspace, capped, securely packed
in coolers with ice, and shipped by overnight courier
to the treatability laboratory. Once at the laboratory,
the groundwater was stored at 4°C and analyzed to
determine pH and 1,2-DCA concentrations.
Microcosm preparation: In an anaerobic glove box,
the microcosms were created using sterile 250 mil-
liliter (mL) screw-cap bottles and filled with 100 g
of homogenized site soil and 180 mL of nonster-
ile site groundwater. The bottles were sealed with
Telfon-coated Mininert™ screw caps. The threads
under the screw caps were wrapped with polytet-
rafluoroethylene tape. The abiotic controls were
autoclaved for 3 consecutive days in an attempt to
85
kill nearly all bacteria, including spore-forming
organisms. Microcosm treatments and controls
were set up in triplicate. 1,2-DCA was added to the
microcosms to achieve the targeted concentration
using a gas-tight syringe. The bottles were incu-
bated lying on their sides in the dark to prevent any
headspace in the bottle from coming into contact
with the screw cap thus limiting the potential for
significant oxygen diffusion into the microcosms.
The incubation temperature was controlled to a
value approximating the average groundwater tem-
perature of the site (12°C), except for the elevated
temperature systems.
Amendments: The amount of electron donor added to
each bottle was calculated based upon an estimate of
the stoichiometric demand of the primary contami-
nant and the background demand imposed by the
competitive electron-accepting processes of nitrate
reduction and sulfate reduction. A safety factor of
10× was used to account for competitive processes
that could not be easily quantified (e.g., iron reduc-
tion and methanogenesis). The organic carbon con-
centration in each of the amended treatments was
monitored and adaptively managed to maintain suf-
ficient concentrations to stimulate microbial activity.
This was more frequent for soluble donors and less
for EVO. Nutrients were added only at the beginning
of the study.
During the study, the concentration of DCA and its related
degradation products were monitored over time using gas
chromatography. Total organic carbon (TOC), nitrate and
nitrite (where applicable), and pH were monitored regularly,
with adjustments made to TOC and pH when needed to main-
tain consistent conditions. Sampling occurred every several
weeks initially, then increased in frequency after the first sev-
eral months once the microbes began to acclimate. The study
was conducted for nearly 1 year. 1,2-DCA degradation trends
observed during the study are presented in Figure 3.5. The
key experimental findings were as follows:
• All carbon substrates were capable of supporting
rapid and complete DCA degradation.
• Degradation rates of 1,2-DCA at concentrations
between 30 and 1000 mg/L appeared to be zero
order, indicating a lack of toxicity.
• Degradation of 1,2-DCA in the absence of any added
amendments is also possible.
• The addition of nutrients was not an important factor
in stimulating degradation.
These findings satisfied the objectives of the experiment and
provided sufficient information for the team to proceed to the
design of a pilot demonstration. It also revealed a factor that
was previously unknown—the fact that natural degradation
could be stimulated with the addition of some heat.
 86
Phase 1—DCA degradation (~30 mg/L 1,2-DCA)
350

300

250 Respike 100 ppm — unamended control at 25°C

Unamended at 12°C 1000
Molasses
DCA (μM)

1,2-DCA

DCA and ethene (μM)

200 800
EVO Ethene
150 Methanol
600
Molasses + nutrients
100 EVO + nutrients
400
Methanol + nutrients
50 Unamended at 25°C 200

0 0
0 50 100 150 200 250 300 0 10 20 30 40 50 60 70
Time (days) Time (days)

Respike 300 ppm—EVO Respike 500 ppm—EVO Respike 1000 ppm—EVO

3500 5000 10,000
1,2-DCA
DCA and ethene (μM)

3000

DCA and ethene (μM)

DCA and ethene (μM)

4000 8,000 Ethene

2500
3000 6,000
2000
1500 2000 4,000
1000 1,2-DCA
1,2-DCA 1000 2,000
500 Ethene
Ethene
0 0 0
0 10 20 30 40 50 60 70 0 10 20 30 40 50 60 70 0 20 40 60 80 100
Time (days) Time (days) Time (days)

Remediation Engineering
FIGURE 3.5  Degradation trends from 1,2-DCA bioremediation bench test.
Principles of Integrated Design
3.4.2.4  Predesign Characterization
Characterization is a broad topic that can have a wide variety
of focal points ranging from strategy, to methods, to physi-
cal targets. As early as 1991, the USEPA acknowledged the
need to consider possible remediation methods early in the
site characterization process to allow for the collection of
data that would support remedy selection and design, in an
effort to reduce the time it would take to initiate cleanup
efforts.26 Over the years, the very linear characterization pro-
cess relying on coarse techniques has given way to methods
like the triad approach, which combines systematic planning,
dynamic work strategies, and advancements in real-time
data collection with the goal of reducing the uncertainty of
decision-making while providing spatial coverage for an area
without sacrificing sample representativeness or driving up
total sampling program scope and cost.
In the context of remedy design, predesign characterization
needs are generally focused on better understanding contami-
nant mass distribution, stratigraphy, and other relevant physi-
cal or chemical parameters within an already delineated area
of interest. This is where techniques that can provide rapid
results at high resolution (and with 3D visualization capabil-
ity) can pay off by helping to make the right remediation tech-
nology selection and focus it, where it can provide the most
value in working toward the goals for the site.
An example of where this type of predesign approach
supported a change in final remedy is the former Spellman
Engineering Company site in Orlando, Florida, a long defunct
aerospace company that over its history of operation had
releases of trichloroethene (TCE), a common chlorinated sol-
vent used for part cleaning. Over the years, these releases con-
taminated about 40 acres of groundwater underlying the site
and the adjacent properties. The final remedy selected for the
site involved the use of surfactant-enhanced chemical oxida-
tion for the source zone, defined as the area where TCE con-
centrations in groundwater exceeded 100,000  µg/L. Within
this area, surfactant/cosolvent flushing was to be used initially
to remove the bulk of the contaminant mass, with subsequent
treatment using chemical oxidation to destroy any remaining
contaminant mass.
To ensure an appropriate and successful remedy design, a
predesign investigation was implemented in the source area
to improve the understanding of contaminant mass distribu-
tion and its overlay with the local stratigraphy. The inves-
tigation made use of a membrane interface probe (MIP) in
concert with cone penetrometer testing equipment. Because
the MIP soundings provide only qualitative, screening-level
data, physical samples were collected at one foot intervals
and analyzed in real time on-site. The data were used to cre-
ate a 3D model to support visualization of the contaminant
mass and hydraulic conductivity profile of the source area.
The predesign investigation revealed new information that
ultimately led to a change in the remedial strategy for the
source area. The main finding was that the majority of the con-
taminant mass in the source area was located within the fine-
grained soils, and not in the permeable materials. As a result,
87
the planned approach of using surfactant/cosolvent flushing
was determined to be a poor match given that the technol-
ogy relies on the ability to achieve contact with the mass
through circulation of the extraction fluid. Without the ability
to eliminate any NAPL using this approach, the chemical oxi-
dation polish would not be effective either. Consequently, it
was determined that in situ thermal remediation via electrical
resistance heating would be employed to complete the source
zone remediation.
3.4.3  Biogeochemical Considerations
Biogeochemistry is a term that combines the effects of micro-
biological stimulation, aqueous chemistry, and geochemistry.
These are all topics that most remediation practitioners would
prefer to avoid, but can have disastrous consequences for
remediation systems if not properly anticipated. Our under-
standing of these topics allows us to manipulate and manage
various reactions to support remediation, as well as control
their effects on the success or failure of a remedy design.
There are a number of ways that biogeochemical effects on
a remedy can be manifested, most commonly the following:
Fouling of wells and equipment: This relates to the
1.
buildup of organic or mineral solids to an extent that
impedes proper and/or safe system function.
Porosity reduction in the formation: This relates to
2.
reductions in aquifer permeability as a consequence
of porosity reductions, which can have a significant
impact on the operational cost of injection or extrac-
tion based remedies.
Secondary water quality impacts (SWQIs): This
3.
relates to changes in general water quality result-
ing from the biogeochemistry of an in situ remedia-
tion process that can potentially delay restoration of
groundwater to a beneficial use.
Material compatibility: This relates to both the
4.
structural integrity of various materials used in a
remedial system due to an incompatibility between
the materials and the chemicals being handled, and
the potential for interference with equipment being
relied upon for system control (floats, sensors, etc.).
In most cases, each of these ways can be anticipated. Careful
consideration during remedy design can help identify poten-
tially significant geochemical effects up front, creating the
opportunity to effectively address them via a combination of
engineering, monitoring, and active management in the form
of operational adjustment and/or maintenance. Designing
with this in mind will ensure better overall system perfor-
mance and avoid surprises during the implementation. The
following sections explore each of the categories mentioned
earlier of biogeochemical effects in greater detail.
3.4.3.1  Fouling of Wells and Equipment
The manipulation of groundwater and the delivery of reagents
to the subsurface can create conditions that lead to fouling.
88
This is a condition that through deposition of solid material
on surfaces limits proper system function through the block-
age of piping, wells, pumps, and other system components.
In addition to slowing or halting effective treatment, if left
unchecked, fouling can permanently damage system infra-
structure and in some cases represent a safety concern. There
are four basic types of fouling that can be encountered in
remediation systems:
1.
Microbially induced fouling: This is where microbes
generate a sufficient mass of biofilm to begin
restricting the flow in a system (pipe flow or porous
media).27 Biofilm consists of bacteria and the extra-
cellular polymeric substance (EPS) that they pro-
duce. The EPS helps microbes with attachment to
surfaces, agglomeration, protection from environ-
mental stressors, and even nutrient capture.28 EPS
composition is widely variable, but generally consists
of compounds such as polysaccharides, proteins,
nucleic acids, glycoproteins, and phospholipids.
When encountered, the type of microbes involved
in biofouling may be partially diagnosed based on
visual observation and odors, but is often bolstered
by laboratory analysis.
Because of the complexity of biofilms, there are a
number of techniques that are often brought to bear
to sort out their composition. This can include (but is
not limited to) any of the following:
a. Simple transmitted light microscopy as a quick
look at the biofilm and deposits.
b. High-level indication of microbial community
composition using biological activity reaction
tests, which can identify iron-reducing bacteria,
sulfate-reducing bacteria (SRB), heterotrophic
aerobic bacteria, algae, etc.
c. More detailed analysis of the taxonomic com-
position and relative abundance of each mem-
ber through phospholipid fatty acid profiling
or DNA-related analysis. DNA-related methods
can include tests such as denaturing gradient gel
electrophoresis, terminal restriction fragment
length polymorphism, and fluorescent in  situ
hybridization.
d. Evaluation of deposits in the EPS through x-ray
diffraction and electron microscopy techniques.
The analytical program used to investigate biofoul-
ing sources and composition will depend on the
degree of knowledge about the factors behind the
fouling and the physical manifestation of the fouling.
The following is a list of common culprits in biofoul-
ing cases and some of the physical conditions that
they are typically associated with27:
a. Sulfate-reducing bacteria: These bacteria, typi-
cally referred to as SRBs, thrive in anaerobic
environments and generate sulfide through the
reduction of sulfate. The sulfide is character-
ized by a rotten egg odor, and when it combines
Remediation Engineering
with inorganics (such as iron), it forms solid
sulfide particulates that impart a black color to
the biofilm. SRBs often proliferate in protected
locations, beneath other biofilms or within tuber-
cules of corrosion products.
b. Iron- and manganese-oxidizing bacteria: These
bacteria can derive energy from the oxidation of
divalent iron and manganese and carbon from
carbon dioxide dissolved in the water. This pro-
cess generates varying amounts of iron and man-
ganese oxide and hydroxide precipitates, which
impart reddish to orange to brown color to the
biomass. There are many different types of these
bacteria, most commonly ribbon and tube-form-
ing species, and they can sometimes be associ-
ated with sulfate-reducing bacteria.29
c. Aerobic bacteria: The readily available energy
gained from aerobic respiration supports rapid
growth of a wide variety of heterotrophic aerobic
bacteria and related biomass generation in the
presence of readily degradable organic carbon-
containing compounds. These bacteria use the
organic carbon as a source of energy and carbon
for cellular growth and can have various appear-
ances and odors. For example, certain species of
Pseudomonas bacteria are known hydrocarbon
degraders and can generate a fish-like odor when
flourishing.
d. Algae: These simple plantlike organisms can
generate their own energy via photosynthesis
and create a strong vegetable-like odor when
they flourish. The presence of algae is typi-
cally reflective of a light source to support their
growth or leakage from a surficial source where
algae have proliferated.
e. Fungi: These are typically filamentous organ-
isms once classified as plants, but which lack the
ability to generate energy via sunlight. They are
mostly aerobic and play a significant role in the
degradation of complex organic material. Fungi
can form filamentous mats and can proliferate in
environments that would be inhibitory to most
bacteria.
The passing of nutrients over surfaces that micro-
organisms can adhere to creates the opportunity
for their colonization and proliferation, particularly
when competition is low. Whether or not biofouling
develops will depend on a variety of factors, includ-
ing the availability of an energy source (organic car-
bon or other), the availability of nutrients (carbon,
nitrogen, phosphorous), the availability of electron
acceptors for respiration (oxygen and its alternatives),
residence time where the surfaces are in contact with
a continual influx of all three (energy source, nutri-
ents, and electron acceptors), temperature, and pH.
Mineral scaling: The abiotic formation of mineral
2.
precipitates can occur when something changes or
Principles of Integrated Design
manipulates the water chemistry. For something to
form scale, it has to be able to form rapidly enough
and sufficient quantities to build up. Calcium car-
bonate is a mineral that is often implicated in
scale formation, but there are many other forms of
scale  that can be produced. Regardless of the type
of scale, prediction of whether something can rea-
sonably be expected to precipitate comes from its
solubility product. In contact with water, a mineral
will dissolve to yield its component ions in solution
at a specific ratio, and the solubility product or Ksp
describes that equilibrium. The general formula for
the solubility product of a solid with two component
ions can be expressed as follows30:
K sp = {M y +}x {A x -}y (3.1)
In this formula, the brackets denote the activity of
the ion. This is expressed in units of molar concen-
tration (moles per liter) and reflects only the reactive
portion. Activity is an issue as the concentration of
ions in solution increases. Electrostatic interactions
between the ions increase with ionic strength, limit-
ing individual ion activities to something less than
their measured concentration. In practice, aqueous
solutions with ionic strength lower than seawater are
generally considered to have an activity coefficient
of one.31
Whether a particular solid could reasonably be
expected to precipitate will depend on how its pub-
lished solubility product compares to the actual con-
centrations of its component ions (more specifically,
the product of the reactive dissolved molar concen-
trations, referred to as the ion activity product). This
comparison yields the saturation ratio, as follows
(again, for a solid with two component ions):
{M y +}x {A x -}y (3.2)
Saturation ratio =
K sp
Saturation ratios calculated in this manner can be
interpreted as follows:
a. ≤1 indicates undersaturation: This is a condi-
tion that would tend to dissolve the targeted solid
(if any is present) until equilibrium is reached.
b. =1 indicates equilibrium: This is a condition where
the targeted solid won’t dissolve or precipitate.
c. ≥1 indicates oversaturation: This is a condition
in which the targeted solid would tend to precipi-
tate until equilibrium is reached.
Table 3.5 summarizes some of the more common
forms of mineral scale and their associated solu-
bility products under standard temperature and
pressure and at neutral pH. While saturation ratios
provide a simple (and somewhat conservative)
89
TABLE 3.5
Point of Zero Charge for Common Metal Oxide Minerals
Mineral Formula PZC (pH)
Amorphous iron oxyhydroxide Fe(OH)3 8.5
Iron oxyhydroxide (goethite, lepidocrocite) FeO(OH) 7.8
Iron oxide (hematite) Fe2O3 6.7
Aluminum oxyhydroxide (boehmite) AlO(OH) 8.2
Aluminum hydroxide (gibbsite) Al(OH)3 5.0
Magnesium Oxide (periclase) MgO 12.4
Source: Kirk, G.: The Biogeochemistry of Submerged Soils, John Wiley &
Sons, West Sussex, U.K., 2004. Copyright Wiley-VCH Verlag
GmbH & Co. KGaA. Reproduced with permission.
means of screening for scale formation potential,
there are a number of assumptions inherent to these
calculations that are not always correct:
a.
Total analytical values equal free ion concentra-
tions: Some ions can form complexes, which are sol-
uble associations that render the complexed fraction
unreactive. Examples of ions that tend to form these
associations are carbonate and sulfate (can associate
with various metals like iron). Care should be taken
to fully evaluate the potential for this type of interac-
tion to reduce free ion concentrations, particularly in
highly concentrated solutions.
b.
Carbonate concentrations can be estimated with rea-
sonable accuracy: This is typically completed based
on analysis of alkalinity, which if not corrected can
be biased high by noncarbonate sources.
pH is a constant: This parameter can vary depend-
c.
ing on a number of factors that may be manipulated
by the process for which scaling is being examined.
For example, changes in temperature can result in
changes in pH, if carbon dioxide is driven off.
d.
Kinetics are not a factor: When a solid is supersat-
urated, precipitates implicated in scaling can form
directly on surfaces or in the bulk fluid.32 In either
case, there are a variety of factors that can affect the
rate at which this occurs, including the availability
of nucleation sites for crystallization, temperature,
pressure, and pH.
Considering the correctness of these assump-
tions will lead to more accurate estimates of scal-
ing potential. Many engineers choose to make use
of geochemical modeling tools to ensure that the
complex considerations are accurately accounted for.
Mitigating techniques for scaling can be
grouped into three general categories: (1) adjust
feed water chemistry, (2) optimize operating
parameters and system design, and (3) antiscalant
addition. Selection among these methods/tech-
niques depends on the nature of the feed water,
membrane compatibility with acid or scale inhibi-
tor, and cost.
90
Rust
2Fe2+ + ½O2 + 4OH–
Fe2O3 + 2H2O Water
OH–
Fe2+
O2
Cathode
Iron e– O2 + 2H2O + 4e–
Anode
Fe0 Fe2+ + 2e–
FIGURE 3.6  Oxidation of iron metal in water.
3.
Corrosion: Corrosion is the deterioration of a
material due to interactions with its environment.33
The corrosion of metals generally involves the
transfer of electrons from the metal to a receptor,
oxidizing the metal and reducing the receptor. This
creates an electrical circuit, where the anode is the
point on the metal surface where the electrons are
generated and the metal is oxidized/corroded, and
the cathode is represented by whatever the elec-
trons flow to.
Figure 3.6 shows a depiction of corrosion at the
surface of a piece of metal. The metal is oxidized
and water (or another receptor) is reduced. As oxi-
dation proceeds in the anode region, an oxide film
begins to form on the metal surface. This film can
slow the rate of corrosion because oxidants have to
diffuse through it, so the uniformity and tenacity
(durability) of the film will determine the level of
protection. In addition, atomic hydrogen can absorb
onto the metal surface in the cathode region. The
hydrogen polarizes the cathode and blocks sites
where electron acceptors can be reduced. This in
turn slows the rate of corrosion because the oxida-
tion half of the reaction cannot proceed any faster
than the reduction half.
Corrosion is driven by a balancing of anodic
and cathodic reactions, both of which can be accel-
erated by various processes. If not controlled,
corrosion will cause structural damage and/or
debilitation of the well screens, piping, and equip-
ment, especially at connections and welded points.
The following are some common factors that can
cause or contribute to the corrosion of iron and
iron-based alloys:
a. Oxygen: Oxygen can drive corrosion in a number
of ways. The first relates to oxygen’s status as an
oxidizing agent. Oxygen can serve as an electron
acceptor in the cathodic regions of the corrosion
cell, as follows:
O2 + 2H 2O + 4e - ® 4OH - (3.3)
Remediation Engineering
The hydroxide created in this reaction is then free
to combine with the ferrous iron liberated at the
anode through another reaction involving oxygen,
as follows:
2Fe 2+ + 1/2O2 + 4OH - ® Fe 2O3 + 2H 2O (3.4)
4OH–
In addition, oxygen can react directly with the
metal through the following pathways:
2Fe 0 + O2 ® 2FeO( s ) (3.5)
4Fe 0 + 3O2 ® 2Fe 2O3( s ) (3.6)
While  these pathways are relevant, the solids cre-
ated by these reactions can accumulate to cover
the metal surface. This creates a barrier that over
time will typically slow the rate of corrosion.
Another way by which oxygen can accelerate cor-
rosion involves its reaction with atomic hydrogen,
as follows:
O2 + 4H + + 4e - ® 2H 2O (3.7)
This reaction removes the polarizing layer of
atomic hydrogen on the cathodic regions of the
metal surface, increasing the rate of corrosion.
b.
Chloride: Chloride itself is not an oxidizing
agent but can enhance corrosion in a number
of ways. Typically, the primary concern is that
it can promote pitting and crevice corrosion in
stainless steel, which represents localized attack
at locations where free access to the surrounding
environment is restricted. This type of corrosion
can proceed very rapidly to a failure by the fol-
lowing mechanisms:
i. Pit initiation: Corrosion starts in places where
the passive film on stainless steel is compro-
mised or weak. This can be due to scratches
or damage to the surface or areas along grain
boundaries where the film is weak or com-
promised under tensile stress. It can also start
in crevices where the film has been compro-
mised such as along threads or connections.
ii. Pit growth: The electrons yielded by cor-
rosion inside the surface defect flow to
cathodic regions peripheral to the pit, where
they react. This creates a positive charge
imbalance in the pit, which attracts chloride.
The chloride supports hydration of the fer-
rous iron liberated by the corrosion, which in
turn increases the acidity in the pit according
to the following reaction:
FeCl 2 + 2H 2O ® Fe(OH)2 + 2HCl (3.8)
Principles of Integrated Design
As the pH within the pit drops below 4, iron
oxyhydroxides are soluble, and atomic hydrogen
forms hydrogen gas. This inhibits the formation
of oxidation deposits and results in depolarization,
both of which accelerate the rate of corrosion.
c.
Hydrogen sulfide: In environmental applications,
hydrogen sulfide–based corrosion is typically
microbially induced, involving the action of
sulfate-reducing bacteria. Microbially induced/
influenced corrosion (MIC) is a complex process
that has been the subject of much research over
the years. There are a number of mechanisms by
which the activity of SRBs can drive MIC:
i. Acceleration of anodic reactions. In the
presence of reactive sulfide, ferrous iron is
removed from solution in the form of iron sul-
fide solids, such as by the following reactions:
Fe 2+ + HS- ® FeS( s ) + H + (3.9)
2+
Fe + H 2S ® FeS( s ) + H 2 (3.10)
This can drive the anodic reaction, but also
results in the formation of solid by-products
in the form of iron sulfides. While there are
a variety of sulfide precipitates that can form
depending on iron and sulfide concentrations,
the dominant precipitate is Mackinawite.
Sulfide films are inherently unstable and,
rather than suppressing corrosion through
surface passivation, can act to stimulate local-
ized corrosion where the film is damaged.
ii.
Acceleration of cathodic reactions: There
are a number of ways that MIC accelerates
cathodic reactions. The first is microbial
metabolism of molecular hydrogen. SRBs
can use molecular hydrogen for energy,
removing it from the metal surface, which
results in cathodic depolarization. The sec-
ond is chemical reduction of hydrogen sul-
fide created by SRBs. Hydrogen sulfide can
serve as an electron acceptor at the cathode,
via the following pathway:
2H 2S + 2e - ® 2HS- + H 2 (3.11)
The third involves the reduction of elemental
sulfur. Often, SRBs are found in layered bio-
films where the outer layer comprises aerobic
bacteria, with SRBs located at the interior
and anoxic regions of the biofilm. This can
result in sulfide oxidation and the creation
of elemental sulfur at the anoxic/oxic inter-
face. Elemental sulfur can serve as an elec-
tron acceptor to drive cathodic reactions via
91
the pathway shown in the following text. Iron
sulfide is highly conductive and can promote
solid-state acceleration of corrosion by pass-
ing electrons to elemental sulfur.
S0 + H 2O + 2e - ® HS- + OH - (3.12)
d.
Carbon dioxide: Carbon dioxide (CO2) itself is
not an oxidizing agent, but it can increase the
rate of steel corrosion in aqueous solutions pri-
marily by enhancing cathodic reactions that lead
to hydrogen evolution. This relates to the rate at
which H + ions are made available at the iron sur-
face, particularly at pH > 4, which is common for
most carbon dioxide saturated systems. In water,
carbon dioxide forms carbonic acid:
CO2 + H 2O ® H 2CO3 (3.13)
The carbonic acid can then yield additional
hydrogen ions through dissociation:
H 2CO3 ® H + + HCO3- (3.14)
HCO3- ® H + + CO32- (3.15)
The hydrogen ions subsequently serve as an elec-
tron acceptor in the cathodic region of the metal
surface, yielding hydrogen gas as follows:
2H + + 2e - ® H 2 (3.16)
In addition, there is some debate as to whether
carbonic acid and bicarbonate may also serve
as electron acceptors themselves and undergo
direct reduction depending on the pH and carbon
dioxide partial pressure, as follows34:
H 2CO3 + 2e - ® H 2 + 2HCO3- (3.17)
2HCO3- + 2e - ® H 2 + 2CO32- (3.18)
This set of reactions versus the reduction of
hydrogen would be most likely to occur at high
partial pressures of carbon dioxide and higher
pH. In a carbon dioxide saturated system, it is
also possible for iron carbonate solids (FeCO3)
to form, which as with other corrosion products
can form scale in the area of the corrosion.
e.
Acids: Acids accelerate corrosion by affecting
the pH of the system. At a pH below approxi-
mately 4, iron oxyhydroxide solids produced by
the corrosion reactions become soluble. This
prevents passivation of the metal surface through
the accumulation of a protective oxide coating,
92
leaving the metal surface in direct contact with
the water, which encourages anodic corrosion
reactions. In addition, hydrogen ions combine
more readily to form hydrogen gas at a pH below
approximately 4, supporting depolarization and
driving cathodic corrosion reactions.
f. Water velocity: When water velocity is extremely
high, it can remove protective layers of corrosion
products, exposing unprotected metal to propa-
gate corrosion. Water velocities of 30–40 ft/s are
usually considered to enhance corrosion through
these mechanisms.
4.
Particulate fouling: Particulate fouling is gener-
ally caused by the movement of fine grained aqui-
fer material into the filter pack causing a decrease in
permeability and through the screen where the par-
ticulate buildup can decrease the amount of avail-
able screen and can cause excessive wear of pump
impellers. Particulate fouling is caused primarily by
poor well design, inadequate well development, and
improper well operation.
3.4.3.2  Porosity Reductions in the Aquifer
The solid matrix of an aquifer acts as a physical regulator for
remediation. Aquifers have a finite capacity to assimilate liq-
uids, gasses, and solids introduced by a remedy, either directly
or indirectly, without compromising the ability for a remedy
to perform. This is critically important for remedies that inter-
cept contaminant flux (like a permeable reactive barrier) and
remedies that rely on the injection and subsurface distribution
of water and/or reactive reagents. For these, temporal changes
in aquifer permeability can dramatically reduce remedy
effectiveness and cost.
In the literature, there is evidence through empirical
relationships like the Kozeny–Carman equation that small
reductions in porosity can result in much larger reductions in
permeability.35,36 While this is dependent on the mechanism of
the reduction, real data support this with one literature study
reporting an order of magnitude decrease in permeability
after only a 10% decrease in porosity.37 This is based on data
for saturated flow. Relative permeability will vary depending
on the nature of the intrusion into the absolute porosity (from
the edges vs. in the core). Research on relative permeability in
oil/water systems show that oil intrusion into a water-wetted
system results in much lower relative permeability for the
water than water intrusion into an oil-wetted system because
in the latter, the water occupies the center of the pore space
instead of the oil.38
Some of the key biogeochemical factors that must be con-
sidered at the design stage to minimize this risk include the
resorting of fines, gas formation, and mineral precipitation.
These are each discussed in the following text.
3.4.3.2.1  Gas Formation and Accumulation
The formation and accumulation of gases in a treatment zone
will decrease permeability through the entrapment of gases
within the aquifer matrix, leaving the occupied pore space
Remediation Engineering
devoid of water. The relevance of this to in  situ anaerobic
bioremediation is only beginning to gain attention in the lit-
erature,39 while it has been a focal point for zerovalent iron
reactive barriers for some time.35,37 Regardless of the treat-
ment technique, the extent of gas accumulation within the
pore space is a balance between the rate of gas generation
and the rate of dissipation. Consequently, lower permeability
aquifers with significant interbedding (less conducive to gas
dissipation) will be more susceptible to extended periods of
permeability loss by gas generation than aquifers with high
permeability and little interbedding.
For remedies relying on the stimulation of anaerobic activ-
ity, the metabolism of organic carbon substrates ultimately
yields dissolved gases. Most soluble carbon substrates are
readily metabolized, and gas generation can occur in real
time during an injection once the microbial ecology is estab-
lished around the injection points. This is more prevalent
during large-volume, long-duration injections. Figure 3.7
shows this effect in the field where a soluble carbon substrate
(alcohol) was injected as pulsed inputs within a continuously
run large-scale recirculation system. After an initial acclima-
tion period, elevation head began increasing in the injection
well and would only recover during periods without substrate
injection. These transient effects could not be improved by
mechanical or chemical well rehabilitation, and there were no
stratigraphic interferences. The likely factor attributing to the
declining injection performance was increased aquifer resis-
tance resulting from gas formation. This was addressed by
increasing the intervals between the pulsed substrate injec-
tions to allow time for gas dissipation and recovery of the
water level between injection events.
Another source of gas generation includes abiotic reac-
tions related to reactive solids or an injection solution itself.
For example, the introduction of acidic solutions to an aquifer
with high alkalinity and carbonate minerals in the soil matrix
can generate carbon dioxide. Similarly, the acid titration of
an alkaline water source to prevent carbonate scaling can
0
Injection well depth to water
(feet below land surface)
5
10
15
20 Water level
Substrate injection events
25
0 5 10 15 20 25
Time (days)
Soil grain Gas accumulation: blocks
largest portion of the pore
space
FIGURE 3.7  Gas-induced injection network hydraulic response.
Principles of Integrated Design
also generate carbon dioxide. Another example would be the
addition of bicarbonate to raise or maintain pH in a microbial
reactive zone, which would also generate significant amounts
of carbon dioxide. These reactions relate to the equilibrium
between the three forms of carbonate (carbonate, bicarbonate,
and carbonic acid).
Off-gassing can also occur during a shift in ionic strength
resulting from the addition of injected fluid. This is directly
related to the “salting-out” effect whereby gas solubilities
decline with increasing ionic strength (i.e., as more water
molecules are engaged in dissolving the salt, there are fewer
available to dissolve the gas).
3.4.3.2.2  Dispersion of Fines
When freshwater is injected into a brackish aquifer, it can result
in the dispersion of clay particles, allowing them to accumu-
late and block the pore throats, thereby dramatically reducing
permeability. This is driven predominantly by sodium ions
and their disruption of the charge balance between the nega-
tively charged surfaces of clay particles, something that is a
factor in soil dispersion due to surface releases of brine. The
initial brine release does not disperse the clays—the density
of cations in the brine solution more than sufficiently counters
the surface charge of the clays. However, sodium will take
a larger role given that it’s predominance over other cations
with higher charge density (in seawater, sodium is present at
concentrations 25 times greater than calcium). When the first
rain event hits, the brine is diluted and the sodium can no
longer maintain the charge balance, so the clay particles repel
each other and are dispersed. Swelling of the clay particles as
a result of enhanced hydration is also a possibility where we
have salinity contrasts and would exacerbate the effects of the
particle dispersion.
The effects of freshwater injection into saline aquifers have
been studied in the petroleum industry for many years,40 with
related research more recently emerging in the areas of reme-
diation and aquifer storage and recovery.41,42 In remediation-
related column studies, researchers saw dramatic and rapid
10.00
Natural concentration (mg/L)
Specific injection capacity
1.00
(gal/min/psi)
0.10
0.01
0 2,000
FIGURE 3.8  Injection capacity changes observed during injection of freshwater and engineered saline solutions into naturally saline
groundwater.
93
reductions in permeability across their test columns.43,44 Up to
90% reduction in permeability was observed within only a few
pore volumes. The Kozeny–Carman equation approximates
“average” effects of porosity reduction, so in this research,
it underestimated permeability reductions from the clay
agglomeration, which would occur at the center of  the pore
throats maximizing the effects. This is similar to the effects
one would expect with gas accumulation. One important thing
that has been observed is some recovery of permeability when
saline water is reintroduced, up to approximately 65% of the
original porosity. This means that a portion of the effects
could be permanent.
Figure 3.8 depicts trends in specific injection capacity
(injection rate in gallons per minute as a function of injec-
tion pressure in pounds per square inch) for a freshwater
injection solution compared to a saline injection solution at
a site with a naturally saline groundwater. The site where
these injections were completed is located very close to the
ocean, so the cation profile of the groundwater is dominated
by sodium. As part of a pilot test, an injection was completed
using potable water, but injection capacity rapidly dropped
by over 2 orders of magnitude reaching a point where further
injection was impractical and injection volumes less than one
third of what was targeted. Following this initial injection,
it was recognized that particle dispersion and possibly some
clay swelling were likely factors in the dramatic reductions
in injection capacity. In response, a recipe was developed to
provide the injection solution with sufficient cation charge
density to prevent particle dispersion. The use of this injec-
tion solution resulted in not only a partial recovery of injec-
tion capacity but also sustained injection capacity so that the
next injection event easily achieved volumes that exceeded
what was targeted.
3.4.3.2.3  Biomass Accumulation
Just as it is a factor in equipment fouling, biomass accumu-
lation in an aquifer can block pore space and dramatically
reduce permeability. This is most relevant to large-volume,
Groundwater ionic profile
–
Ion Na
+
K+ Mg2+ Ca2+ Cl SO42+ HCO3 Br–
12,000 684 953 444 28,000 2,900 308 90
Freshwater-specific injection capacity
Saline-specific injection capacity
4,000 6,000 8,000 10,000 12,000 14,000 16,000 18,000
Cumulative volume injected (gal)
94 Remediation Engineering

Land surface
0 100

15 Depth to 90
water Rehabilitation

Cumulative injection volume (104 gal)

30 80
event
45 70

(feet below land surface)

Flow rate (gpm)

Depth to water
60 60
(a)
75 Cumulative 50
injection
90 volume 40

105 30

120 20
Flow rate
135 10

150 0
0 7 14 21 28 35 42
(c) Time (days)

(b)

FIGURE 3.9  Biofouled injection well screen (a) before and (b) after rehabilitation and (c) fouling-induced injection well hydraulic response.

long-duration injection programs and is amplified in continu-

ously fed recirculation systems.
Uncontrolled microbial growth is driven mostly by the
availability of organic carbon, dissolved oxygen, nutrients,
and reduced iron or manganese, which can be utilized by
slime producing iron and manganese-oxidizing bacteria. The
presence of these compounds allow mixed microbial consor-
tia to proliferate opportunistically, with growth occurring on
surfaces of pumps, mixing equipment, conveyance piping,
injection well casing and screen, and the granular material
surrounding the injection well (filter pack and native aquifer
soil).45,46
The buildup of organisms (ultimately resulting in the for-
mation of biofilms) will result in resistance to fluid flow and
in some cases can compromise well integrity by accelerating
the corrosion of certain materials. Figure 3.9 shows photo-
graphs of biofilm on an injection well screen and the same FIGURE 3.10  Calcium carbonate scale buildup in a water treat-
screen section after rehabilitation. The hydraulic monitoring ment system pipe.
data associated with this system (Figure 3.9) show the grad-
ual increases in water level in response to biomass growth precipitation. This can be extended to an aquifer setting; there-
and clogging of the screen and filter pack. For this large- fore, engineered precipitation within a reactive zone must be
scale injection system, water levels eventually reached the designed to spread the precipitates over an adequate aquifer
high-water cutoff inside the casing, resulting in rapid system volume in order to minimize hydraulic effects. Research has
cycling. Sustained injection could only be reestablished after shown that the accumulation of precipitates in these types of
chemical rehabilitation of the injection wells. scenarios can have a less dramatic effect on permeability than
gas (or biomass) accumulation.37,47 This is presumably related
3.4.3.2.4  Mineral Precipitation to the fact that gas will accumulate in the largest portion of
The abiotic precipitation of various minerals can also impact the soil pores (where the bulk fluid movement occurs), while
all aspects of the treatment system, compromising injection precipitates will form as a coating on the surfaces of the soil
performance. Figure 3.10 shows the effects of scale formation particles, slowly building outward toward the center of the
that can occur inside conveyance piping related to mineral soil pores.
Principles of Integrated Design
This construct, however, does not hold when there is rapid
bulk precipitation. An example of this involves the intentional
neutralization of highly acid or alkaline groundwater. These
types of conditions are characterized by elevated dissolved
solids from chemical weathering of the native aquifer miner-
als including elevated concentrations of dissolved metals such
as iron, aluminum, and calcium along with elevated concen-
trations of dissolved silica. While the composition of acidic
versus alkaline groundwater will be very different, the role
of silicon, aluminum, and iron are common threads given
that they are the second, third, and fourth most abundant ele-
ments in the earth’s crust, and their common mineral forms
are highly pH-sensitive. The introduction of bulk acidity or
alkalinity to a highly alkaline or acidic groundwater with the
intent of rapid neutralization will yield the undesirable result
of rapid re-precipitation of dissolved solids into a low-density
(high volume) amorphous mass, filling all of the available
pore space.
3.4.3.3  Secondary Water Quality Impacts
One unavoidable aspect of in  situ remediation is the sec-
ondary effect it can have on water quality, resulting from
the biogeochemistry of various process options and their
interaction with the aquifer matrix. These effects are
potentially persistent changes that can delay restoration of
groundwater to a beneficial use, representing impacts in
their own right related to parameters other than the con-
taminants targeted for treatment. As the experience base
with engineered in situ treatment techniques has increased,
so has the awareness of and attention to secondary water
quality impacts (SWQIs). To date, the level of attention
from one regulatory jurisdiction to another is inconsistent,
but SWQIs are gaining prominence in the United States
among both state and federal regulators. Evidence of this
can be seen in a brief review of how potential SWQIs are
addressed in key technology specific guidance documents.
Starting with in  situ chemical oxidation (ISCO), early
reviews by the environmental security technology certifica-
tion program (ESTCP) and the groundwater remediation
technology analysis center in 1999 had little if any mention
of secondary effects outside of what would be an immedi-
ate H&S concern.48,49 Guidance issued later by the interstate
technology and regulatory council (ITRC) and the strategic
environmental research and development program (SERDP)
between 2001 and 2005 highlighted potential detrimental
effects, expanding beyond gas and heat evolution to discuss
mobilization of metals, toxic intermediates, and other by-
products.50–52 The 2006 USEPA ISCO review contains an
entire section devoted to consideration of by-products and
geochemical effects.53 Guidance documents for enhanced
anaerobic bioremediation follow a similar trend, starting with
very little if any mention of secondary effects in the early
reviews by ITRC and ESTCP in 1998 and 2002.54,55 Guidance
issued later by the Air Force Center for Environmental
Excellence in 2004 and ITRC in 2008 contain entire sec-
tions devoted to consideration of by-products and geochemi-
cal effects.56–58 Existing in situ thermal treatment reviews and
95
guidance documents have relatively little focus on secondary
water quality effects except for temperature recovery and tar-
get contaminant rebound.58–60 However, the effects of ther-
mal systems on microbial communities, biological oxygen
demand, oxidation–reduction potential, chloride concentra-
tions, and long-term abiotic treatment have been studied.61,62
SWQIs are now acknowledged as a full-fledged emerging
issue, with a SERDP-funded research effort underway (proj-
ect ER-2129) titled Secondary Impacts of In Situ Remediation
on Groundwater Quality and Post-Treatment Management
Strategies. This project is projected to be complete in 2014
and has focused on furthering the understanding of in situ
remediation technology impacts on groundwater quality,
specifically for thermal remediation and subsequent micro-
biological treatment.
Outside the information found in historical technical
guidance documents, there is an existing but not compiled
body of knowledge (published and nonpublished) that pro-
vides more insight into quantitative evaluation of various
SWQIs. In general, SWQI can be classified in the following
five categories:
3.4.3.3.1  Reactant-Related By-Products
This category includes any intrinsic component of the reac-
tant being delivered to support remediation that could show
up as a by-product, such as trace metal impurities, cations,
anions, acidity, alkalinity, and heat. An example of this is
provided in our reviews of the impurities in permanganate
oxidants.63,64 Some of the by-products in this category have
drinking water standards or can contribute to other sec-
ondary effects (i.e.,  supporting the liberation of naturally
occurring metals) discussed in the next section. They can
also provide additional remediation benefit, that is, the sul-
fate produced when persulfate oxidizes organics can also
be an electron acceptor in the anaerobic oxidation of hydro-
carbons.65 Heat intended to cause physical removal mecha-
nisms can also accelerate hydrolysis of some chlorinated
solvents.66
Impacts in this category tend to be transient in nature, but
should be evaluated relative to the uses (current or planned) of
the resource being treated.
3.4.3.3.2  Cycling of Metals in the Aquifer Matrix
Metals in an aquifer can be mobilized and (re)precipitated
in response to specific geochemical changes. This is true for
both metals that are naturally occurring/geogenicin origin
and metals that are the result of human activity/anthropogenic
in origin.
This category of SWQI is highly relevant as redox-
sensitive metals such as arsenic, iron, and manganese are eas-
ily affected and have received a lot of attention in this regard.
There are also other metals that can be mobilized depending
on the native mineralogy and the geochemical conditions,
such as aluminum, barium, chromium, and vanadium, to
name a few.
There are three primary mechanisms that the release of
metals in an aquifer.67
96
3.4.3.3.2.1   Development of High- or Low-pH
Extremes  Fluctuations in groundwater pH will affect the
surface charge of naturally occurring metal oxide miner-
als (and organic matter) in an aquifer. This in turn affects
the electrostatic interactions by which these materials retain
surface bound/adsorbed metals. At low pH, the abundance
of hydrogen ions (H+ ) saturates sorption sites giving the sur-
faces a predominantly positive charge, attracting anions, and
repelling cations. As pH increases, there are fewer hydrogen
ions and the surfaces will exhibit a predominantly negative
charge, attracting cations, and repelling anions. Somewhere
between the two extremes, there is a pH where a point of
zero/neutral surface charge occurs. Table 3.6 lists the point
of zero charge (PZC) for several common metal oxide
minerals.
At extremely high or low pH, these interactions become
irrelevant because aquifer minerals lose their stability and can
actually be dissolved by the excess hydrogen or hydroxyl ions
in solution. This also affects the stability of naturally occur-
ring organic matter, which particularly at elevated pH can
become mobile in the form of colloidal particles complexed
with metal cations.
3.4.3.3.2.2  Increase in Ionic Strength or Specific
Dissolved Ion Concentration  As with pH, dissolved ion
concentrations affect both sorption interactions and intrin-
sic mineral solubility. The ions of metals sorbed to mineral
surfaces can be displaced by other specific ions competing
for sorption sites or through the formation of soluble com-
plexes. Preferential sorption can be based on differences
in electrostatic attraction, or differences in the strength
of electron sharing interactions. A good example of this
is phosphate displacement of arsenic from iron minerals.
Phosphate is a strong ligand (an ion that bonds with a metal
atom through electron sharing) that can preferentially dis-
place arsenic oxyanions from surface sites (a mechanism
that has been investigated to deliberately remove arsenic
from soil).68
As ionic strength continues to increase, it will eventu-
ally decrease the activity of all the ions in solution due to the
magnitude of the electrostatic interactions. This can actually
increase mineral dissolution as the aqueous system attempts
to balance out the constituent ions based on the solubility
TABLE 3.6
Common Forms of Mineral Scale and Their Associated Solubility Products
Scale Type Description
Hydroxyapatite Calcium phosphate
Struvite Magnesium ammonium phosphate
Calcite Calcium carbonate
Gypsum Calcium sulfate
a Solubility product at standard temperature and pressure, and assuming activity coefficients of 1 pKsp = −log(Ksp).
b Ball and Nordstrom.97
c Harrison et al.98
Remediation Engineering
product constant (Ksp) of the mineral (decreased activity,
denoted as γ, requires higher molarity):
K sp = {M y +}x {A x -}y = g M [ M y + ]x g A[ A x - ]y (3.19)
3.4.3.3.2.3  Stimulation of Oxidation or Reduction
Reactions  Certain elements are susceptible to changes in
valence state as a result of external processes that drive elec-
tron transfer, both chemical and biological. Figure 3.11 sum-
marizes stability characteristics for several redox-sensitive
metals, metalloids, and radionuclides, with their thermody-
namic ranking shown along with other key elements. As indi-
cated, some are stable only in oxidizing environments making
them susceptible to reductive dissolution, and just the oppo-
site for others. Some are soluble in any environment unless
they are sorbed to or incorporated with other minerals.
These reactions have the greatest effect on the amorphous
fractions with crystalline fractions generally more recalci-
trant.69 With respect to naturally occurring metals, these reac-
tions can also affect metals sorbed to or incorporated with
other minerals (or organic material) by virtue of their depen-
dence on the stability of the sorbing or incorporating material.
The following discussions examine these dynamics for both
oxidizing and anaerobic remedies.
Metals Mobilization in Oxidizing Systems
Chemical oxidation can have a significant effect on naturally
occurring metals, metalloids, and radionuclides via all three
mobilization triggers, making it relevant to a larger num-
ber of elements. In general, commercially available ISCO
approaches can be broken down into two types: (1) direct oxi-
dation (e.g., permanganate) and (2) advanced oxidation rely-
ing on the creation of radicals (e.g., catalyzed peroxide and
activated persulfate). The geochemical effects will vary by
oxidant system but can generally be expected to be greater for
those oxidants that have significant metals content and result
in significant increases in ionic strength and/or swings in pH.
In the case of permanganate, the oxidant itself comprises
sodium or potassium and manganese and is known to have
impurities that can contribute to its geochemical effects.63,64
The secondary effects of these impurities and inorganic compo-
nents of the oxidant will depend on the oxidant concentrations
Chemical Formula Solubility Product (pKsp)a
Ca 5 (PO 4 )3 OH 54.45b
NH4MgPO4 · 6H2O 13.15c
CaCO3 8.48b
CaSO4 · 2H2O 4.58b
Principles of Integrated Design 97

1.0 pe
Oxidation Oxidation pH = 7
Eh (V) Oxidized Reduced
state state 15
Primary pH = 7
0 O2 H2O –II
valence 0.8
Element statesa Stability V NO3– N2 0
Soluble in both
Arsenic (As) III, V valence states 0.6

Propagation of reduction reactions

IV MnO2 II 10

Propagation of oxidation reactions

(anionic) Mn2+
III relatively VI SeO42– HSeO3– IV
Chromium (Cr) III, VI insoluble, VI VI HCrO4– Cr(OH)3 III
soluble (anionic) 0.4
II soluble
5.0
Iron (Fe) II, III (cationic), III
IV HSeO3– Se 0
relatively insoluble 0.2
II soluble VI UO22+ UO2 IV
Manganese (Mn) II, III, IV (cationic), III and IV III Fe(OH)3 Fe2+ II
relatively insoluble V HAsO42– H3AsO3 III
0.0 0.0
0 insoluble,
Selenium (Se) 0, IV, VI IV and VI soluble
(anionic)
IV relatively –0.2 VI SO42– H2S –II
Uranium (U) IV, VI insoluble, VI IV HCO3– CH4 –IV
soluble (cationic) –5.0
a Relevant to natural systems –0.4

FIGURE 3.11  Stability characteristics for several redox-sensitive elements.

used and the site conditions. Sodium and potassium can be
attenuated through flushing and cation exchange on the soil
surfaces. Permanganate decomposition forms manganese
oxide solids that are stable under aerobic conditions but can
represent a long-term source of manganese in reducing envi-
ronments. The PZC for manganese oxide surfaces is relatively
low (ranges from pH 1.5 to 5), and they are known to have sorp-
tive capacity for many heavy metal cations, but under acidic
conditions can release certain surface-bound metal cations for
which they have lower affinity, such as nickel.64 Manganese
oxides are particularly effective at the oxidation of trivalent
chromium Cr(III) to hexavalent chromium Cr(VI) through a
series of reactions that start with Cr(III) sorbing onto the man-
ganese oxide surfaces.70 If not sufficiently buffered, this can
be exacerbated by excess acidity or alkalinity (increases the
solubility of Cr(III) hydroxides). Other elements that are more
soluble in their oxidized forms and can be similarly affected
include uranium, selenium, and vanadium.
Peroxide-based oxidant systems can also oxidize Cr(III)
to Cr(VI).71 As with permanganate, acidity generated by the
destruction of organic contaminants can liberate surface-
bound metal cations, an effect that is exacerbated by the rapid
oxidation of natural organic matter with which the metals
may have been associated.72
Persulfate is typically sold as a sodium salt and generates
acidity simply through its decomposition. In order to induce
effective oxidation via persulfate chemistry, an activator
must be present. This can include ferrous iron, alkalinity,
heat, or other options.73 Depending on the method selected,
the engineered application of an activator can have signifi-
cant geochemical effects that are either exacerbated or miti-
gated by the persulfate chemistry (through the generation of
acidity and the increase in ionic strength from the dosing).
Figure 3.12 presents data for several naturally occurring met-
als from a bench study conducted using sodium persulfate.
The study involved batch reactors constructed with soil and
groundwater set up into treatment trials with varying levels
of persulfate (none, 1%, and 5%). Each of these three trials
included treatments with ambient activation (no added activa-
tor), ferrous iron activation, and alkaline activation (sodium
hydroxide). Based on the data, the most significant impacts
were observed at the highest persulfate dosing and the spe-
cific metals affected determined by the final pH.
Based on the previous text, the development of pH extremes
appears to be a primary factor in the mobilization of natu-
rally occurring metals by chemical oxidation, followed by the
effects of direct oxidation (attack of organic matter to which
metal cations may be sorbed and redox-sensitive metals such
as chromium). In a field application, the most mobile metals
liberated by oxidation would be the products of oxidation such
as hexavalent chromium. For the most part, the mobility of
any other metals liberated should be limited by pH neutral-
ization and moderation of ionic strength. These will support
both precipitation and sorption to naturally occurring aquifer
materials. In some cases, the precipitation of certain metals
could further enhance the precipitation of others (fresh alumi-
num and iron hydroxides can interact with many other metals
through sorption and coprecipitation). All of the interac-
tions mentioned earlier can be evaluated as part of predesign
efforts, both in the laboratory and in the field.
Metals Mobilization in Anaerobic Systems
Of the three key triggers for metals mobilization, reduction
reactions are most relevant to engineered anaerobic biore-
mediation. While some acidity can be generated, the typi-
cal operating range of pH does not include extremes that
 98
Metals concentrations (μg/L) Cr concentrations as a function of pH
Treatment ID Arsenic Cadmium Chromium Manganese Nickel Zinc pH 300
Cr
250 Presulfate only and
0% S2O82– 5 <4 <11 69 <20 <50 8.8 persulfate +Fe
treatments:
0% S2O82–+ Fe 4 <4 <11 110 37 <50 7.1

Concentration (µg/L)
200 low pH
dissolution and
0% S2O82–+ NaOH 160 <4 33 18 35 <50 13.6 150
perhaps some
NaOH
treatments:
oxidation
2– high pH
1% S2O8 65 18 <11 480 290 510 4.3 dissolution and
100 mixed radical
1% S2O82–+ Fe 89 25 35 880 310 620 5.1 system oxidation

1% S2O8 2–+ NaOH 280 <4 160 <11 <20 <50 13.3 50
5% S2O82– 88 20 20 450 340 550 3.4
0
5% S2O82–+ Fe 130 27 60 1000 380 720 2.8 0 2 4 6 8 10 12 14 16
5% S2O82–+ NaOH 270 <4 270 <11 <20 <50 12.7 pH No persulfate

Al and Si concentrations as a function of pH Mn concentration (with Fe) as a function of pH As concentrations as function of pH

200,000 140,000 1200 350
Persulfate only As
180,000 and persulfate +Fe Al 40 Fe Persulfate only
120,000 300
treatments: Si Mn 1000 and persulfate
160,000 35
low pH dissolution Iron and persulfate +Fe
250

Concentration (µg/L)
140,000 100,000 treatments: exchangeable
30
Aluminum (µg/L)

800
Persulfate only As and Fe mineral

Manganese (µg/L)
120,000
Silica (µg/L)

25 80,000 200 dissolution

Iron (µg/L)

100,000
20 Alkaline activation 600
80,000 60,000 150
15 Iron only
60,000 400 100 NaOH
10 40,000 Background
40,000 NaOH treatments:
20,000 treatments: 5 200 50 point of zero
high pH dissolution 20,000 charge
0 0
0 2 4 6 8 10 12 14 16 0
0 0 0 2 4 6 8 10 12 14 16
0 2 4 6 8 10 12 14 16
pH No persulfate pH
pH No persulfate

FIGURE 3.12  Transient pH-dependent liberation of naturally occurring elements by chemical oxidation.

Remediation Engineering
Principles of Integrated Design
would have a significant effect on metals of environmental
relevance. Similarly, ionic strength will increase due to the
metabolism of injected organic carbon substrates. However,
these increases are typically moderate, and the amendments
don’t typically incorporate ions that offer strong competi-
tion for sorption sites (although nutrients like phosphate can,
something to be considered).
The reductive potential of organic substrates depends on the
number of electrons yielded during microbial respiration. For
example, alcohol (C2H6O) can yield six electrons per C atom,
while carbohydrates (CH2O) can yield four electrons per C
atom. At face value, this means that more or less of a specific
carbon substrate may be required to achieve a certain strength
of reduced conditions (mildly reducing vs. strongly reducing).
In reality, the degradability of a specific substrate balanced
against the available electron acceptors will determine the
dosing required to achieve a specific reductive poise. The size
and strength of the resulting reducing environment in conjunc-
tion with the native mineral characteristics will determine the
degree to which metals may be mobilized. This is true regard-
less of the source of organic carbon, something demonstrated
at sites impacted by releases of degradable petroleum hydrocar-
bons. Recent research does, however, indicate that high dosing
of fermentable substrates can facilitate more aggressive reduc-
tive dissolution of native minerals and mobilization of metals
by creating metabolites that act as electron shuttles or chelating
agents, affecting even crystalline mineral phases.74
Data from engineered anaerobic/reducing environments
created in normally aerobic aquifer settings have shown iron,
manganese, and arsenic to be of primary relevance. This is
likely attributable to the following:
• Both iron and manganese susceptible to reduc-
tion are soluble in their reduced valence states and
are abundant (Figure 3.13). Because they are also
ubiquitous, they are primary rungs in the ladder
of alternate electron acceptors used by microbes
for respiration in anaerobic environments. This
makes them significant in terms of the potential
for mobilization, with elevated dissolved iron and
manganese typical in engineered anaerobic reac-
tive zones.
• Arsenic is a metalloid that is soluble in all of its
valence states unless (typically) it is adsorbed to or
incorporated with other minerals (most often those
of iron). Although it is not abundant in the earth’s
crust as shown on Figure 3.13, arsenic is ubiquitous
in small amounts and can be liberated by direct
reduction, complexation with reactive sulfide, or
reductive dissolution of the iron minerals with which
it is typically associated.75
Available dissolved electron acceptors, hydrogeologic hetero-
geneities, and the complexities of solid phase–aqueous phase
interactions prevent rapid depletion of metals in the aquifer
matrix following creation of anaerobic groundwater environ-
ments. Instead, this process occurs very slowly over time, as
99
105
Crust concentration
Fe
104 Soil concentration
Concentration (mg/kg)
103
Mn Ba
102 Sr
V
Cr
Zn
Cu
101 Ni Li
Co Pb
Th
100 Cs U
Be Sn As
Mo
10–1 Sb
Cd Ag Se Hg
10–2
FIGURE 3.13  Relative abundance of selected elements. (From Bowen,
H.J.M., Environmental Chemistry of the Elements, Academic Press,
London, U.K., 1979; Schacklette, H.T. and Boerngen, J.G., Element
concentrations in soils and other surficial materials of the contermi-
nous United States, USGS Professional Paper 1270, USGS, Reston,
VA, 1984; Sposito, G., The Chemistry of Soils, Oxford University Press,
New York, 1984 by permission of Oxford University Press.)
indicated by the data in Figure 3.14. Some solubility control is
actually possible within the anaerobic zone due to the forma-
tion of iron and manganese carbonate minerals as well as iron
sulfides capable of incorporating some arsenic. Regardless,
the dissolved concentrations of these metals can be expected
to remain elevated while the anaerobic environment is main-
tained, even if that time frame is over years.
Fortunately, as indicated by the data in Figure 3.15, there
are natural processes that can control the mobility of metals
mobilized from the aquifer matrix. This is focused mainly at
the boundary of the anaerobic zone. In the absence of oxygen,
it is likely that sorption mechanisms dominate in importance
to at least initially impart this control. Ferrous iron is also
susceptible to sorption but can also oxidize via reaction with
certain soil minerals (such as manganese dioxides), creating
additional ferric iron minerals. Similarly, arsenic transport is
likely limited by partitioning to both naturally occurring and
freshly precipitated ferric iron minerals, and there is evidence
that it can also react with manganese dioxides in a similar
manner to ferrous iron. Divalent manganese is comparatively
more mobile than both arsenic and iron owing to the fact that
the reactions mentioned earlier will contribute to its solubility
at the edge of the anaerobic reactive zone, it is less susceptible
to sorption, and it requires more strongly aerobic conditions to
reoxidize and precipitate.76
One final but important concept is that the cycling of nat-
urally occurring metals can also enhance remediation, for
example, through the formation of reduced iron minerals such
as iron sulfide and magnetite that can react with target con-
taminants. There is a significant body of literature specifically
on the abiotic degradation of chlorinated solvents through
contact with such reactive minerals (i.e., numerous works
by Lee and Batchelor and Butler and Hayes), but the same
minerals are also reactive toward redox-sensitive elements
such as hexavalent chromium.77 As it relates to chlorinated
100 Remediation Engineering

40,000 800
Depletion of redox-sensitive
35,000 700 elements via reductive

Iron (mg/L) and arsenic (μg/L)

dissolution is very slow due to
30,000 600
Competing electron
Manganese (μg/L) acceptors
25,000 500
Hydrogeologic
20,000 400
heterogeneities
15,000 300 Solid phase–aqueous phase
interactions
10,000 200
Natural solubility control in
5,000 100 solid matrix
0 0
0 500 1000 1500 2000 2500
Manganese Time (days)
Iron Monitoring location approximately 40 days
Arsenic groundwater travel time downgradient of injection line

Soil data (Average) GW data (Average)

mg/kg mmol/kg mg/L mmol/L
Iron 4867 87.2 Iron 143 2.6
Manganese 90 1.6 Manganese 14 0.25
Arsenic 6.2 0.08 Arsenic 0.3 0.004

FIGURE 3.14  Dissolved metals data from a long-term engineered anaerobic in situ reactive zone.

Anaerobic reactive zone

Arsenic (μg/L) and iron (mg/L)

800 30
700 25

Manganese (mg/L)
600 Arsenic
500 Iron 20
400 Manganese 15
300 10
200
100 5
0 0
–100 0 100 200 300 400 500
Distance (ft)

Upgradient Location Downgradient

of injection
line
Conditions after 4.5 years of operation (1640 days)

FIGURE 3.15  Dissolved metals data through an engineered anaerobic in situ reactive zone.

solvents, this avenue of enhanced contaminant degradation Most of the dissolved metabolic by-products are a reflec-
has been coined biogeochemical reductive dechlorination tion of intense fermentation that indicates too rich a loading
or “BiRD” by the Air Force Center for Engineering and the of an organic substrate. These by-products are highly degrad-
Environment.78 able themselves so are typically transient in nature and do
not persist once organic carbon levels are moderated. The
3.4.3.3.3  Microbial Metabolic By-Products uncontrolled formation and evolution of microbially gener-
These are primarily associated with the fermentation of organic ated gases like methane can run the risk of creating signifi-
substrates (i.e., oils, carbohydrates, and proteins) and include cant porosity reduction challenges as discussed earlier in this
dissolved gases (methane, hydrogen sulfide), volatile fatty chapter and can even pose safety issues if not monitored and
acids, ketones (acetone, methyl ethyl ketone), alcohols, and aro- managed appropriately.
matic compounds (phenol). The mechanisms and quantitative
considerations associated with these are covered in wastewater 3.4.3.3.4  Nonmetal Inorganic Reaction By-Products
guidance and the general biogeochemistry literature, which are This includes reactions such as the conversion of naturally
not often familiar to many remediation practitioners but have occurring bromide to bromate by reaction with ozone80
been cited in some in situ remediation texts.56,79 or the conversion of nitrate to ammonia by reaction with
Principles of Integrated Design
zerovalent  iron.81 These by-products can be of significance
from a toxicity and persistence perspective but can also be
avoided or minimized in a careful design.
3.4.3.3.5 Degradation Intermediates of
Organic Contaminants
This includes transformation intermediates that are typically
monitored and targeted themselves for treatment such as would
be encountered with reductive dechlorination of chlorinated
solvents. Also included are intermediates that are not typically
monitored, such as partial oxidation products that can include
aldehydes, carboxylic acids, or other chlorinated compounds
that can form during chlorinated solvent oxidation.82
Some of these by-products can be anticipated and dis-
cretely monitored; in other cases, they cannot be discretely
monitored and only show up in bulk parameters. A good
example is using total petroleum hydrocarbon (TPH) analysis
to confirm the complete mineralization of petroleum-related
targets. This is particularly important as our ability to moni-
tor and quantify discrete compounds does not typically cover
the full spectrum of possible by-products, which for some
contaminant types can number in the thousands. This is
extremely relevant for emerging contaminants such as poly-
and perfluoroalkyl substances (PFAS), which include many
thousands of organic fluorine compounds that can transform
in the environment. This is driving the development of meth-
ods to quantify total organic fluorine (similar to TPH analysis
for petroleum hydrocarbons) to provide insight on the pres-
ence of a much more comprehensive range of PFAS.
3.4.3.3.6  Implications for Design
Consideration of the degree to which the categories of SWQI
mentioned earlier may be relevant to a particular remedial
strategy for groundwater is an important part of the design
process—they can have a major effect on the ultimate suc-
cess of a remedy relative to both its physical performance and
its completeness. The collateral impact of solid and chemical
interactions is gaining more attention in the scientific, regula-
tory, and consulting communities that form the backbone of the
environmental site restoration industry and will likely become
a more standard focus of associated monitoring programs.
3.4.3.4  Material Compatibility
The basic strength profiles of most materials (what pressures
and temperatures they can be exposed to without compromis-
ing their structural integrity) are well understood, but those can
change when compounded with other factors such as corrosion
(electrochemical attack), decomposition (chemical attack), and
solvation (dissolution). Consequently, where a remediation sys-
tem will either be recovering or delivering chemicals, the effect
of those chemicals and the physical setting (pressure, tempera-
ture, etc.) on the materials the system is constructed of must be
evaluated to ensure they are compatible.
With this in mind, the definition of “compatibility” for
this discussion involves the situation where the chemicals and
conditions that the system materials are exposed to will not
unacceptably impair the structural integrity of those materials
101
in their intended mode of deployment or affect contaminant
concentrations that are the target of monitoring through leach-
ing, sorbing, or other interactions.
The materials that most remediation systems are con-
structed from typically fall into the following two categories:
1. Plastics
a. Thermoplastics, which include compounds such
as polyvinyl chloride (PVC), polypropylene, and
acrylonitrile butadiene styrene (ABS)
b. Fluoropolymers, which include tetrafluoroethyl-
ene, fluorinated ethylene propylene, and polyvi-
nylidene fluoride
c. Fiberglass-reinforced materials, which include
fiberglass-reinforced epoxy and fiberglass-rein-
forced plastic
2. Metals
a. Most typically carbon steel, stainless steel, and
aluminum
The following sections contemplate high-level consider-
ations related to the compatibility of these materials for use
in environmental applications, but practitioners should always
­discuss/confirm material compatibility with the manufactur-
ers they are working with.
3.4.3.4.1 Plastics
Plastics are nonconductive and therefore generally immune
to corrosion/electrochemical attack. They are not, however,
immune to decomposition (polymer molecule destruction,
typically through oxidation, hydrolysis, photodegradation,
etc.) or solvation (polymer dissolution, which typically causes
transient swelling and weight gain).83,84 These types of inter-
actions can compromise the strength of the polymer resulting
in various modes of failure, including stress cracking.
Chemical compatibility of plastics used in environmen-
tal applications has been the subject of a variety of studies
over the years, including the special report series sponsored
by the U.S. Army Corps of Engineers in the mid-1990s.85–87
The first part of this study evaluated the behavior of a num-
ber of plastics in each of the subcategories identified earlier
when exposed to individual organic compounds, acidic condi-
tions, and alkaline conditions. Additional follow-up work was
done to evaluate the performance of PVC when exposed to
mixtures of chemicals. This work showed fluoropolymers to
be the most inert relative to the chemicals tested, with ABS
the most readily degraded. It also showed that despite how a
polymer performs in contact with a single organic chemical,
results can be much different when you combine them. As
it related to PVC, they concluded that softening of the PVC
does not appear to occur in any solutions where the sum of the
individual relative solubilities is less than 0.1 (where relative
solubility equals the concentration of a compound in solution
divided by its solubility).
Another piece of work was also published by the USEPA
around the same time88 as the work by the U.S. Army Corps of
Engineers, which tabulated a more comprehensive summary
of chemical compatibility and commented on interference
102
that various materials might have on the accuracy of water
quality measurement, given that polymers can both leach and
sorb certain compounds depending on their composition.84
This is something that is mainly relevant where monitoring
involves low contaminant concentrations, the monitoring of
which is increasingly accurate due to the continually improv-
ing resolution of commercial analytical capability. In general,
rigid plastics were found to be most inert, with more inter-
ference coming from flexible plastics (both sorption of target
contaminants and leaching of plasticizers).
3.4.3.4.2 Metals
By comparison to plastics, metals are very stable in presence of
most organic solvents. They are, however, susceptible to corro-
sion and other forms of electrochemical attack. Most compat-
ibility charts rate the performance of metals in terms of mils of
penetration per year (units of one thousandth of one inch per
year), reflecting the potential impact of these reactions.
An example is the fact that metals are highly incompatible
with acids and bases (or compounds that decompose to form
acids or bases). Under these conditions, the metals will react rap-
idly with the corresponding acid or base, generating a significant
amount of heat and decomposing to produce salts and hydrogen
gas. This rapidly erodes the metal, impacting not only its struc-
tural integrity but creating a potentially unsafe situation.
The natural corrosion of a metal is typically a slow process
that converts the metal from refined elemental form to a more
stable oxide or hydroxide. This type of reaction is typically
encouraged when any of the following conditions exist88:
• pH < 7
• DO > 2 ppm
• H2S > 1 ppm
• CO2 > 50 ppm
• Cl > 5000 ppm
Several of these parameters reflect extreme conditions relative
to most natural waters, with the first two simply indicating
that more acidic and highly oxygenated environments support
corrosion.
With respect to the impact that metallic components may
have on the accuracy of water quality measurement, they can
leach low concentrations of their component elements (e.g.,
iron, nickel, and chromium from stainless steel)89 and can also
adsorb elements of interest. Carbon steel casing can potentially
react with target contaminants to reduce them (in the case of
dissolved metals) or reductively destroy them (in the case of
certain organics)—the same interactions relevant to a zerova-
lent iron barrier. As indicated in the discussion related to plas-
tics, these interactions are mainly relevant where monitoring
involves low contaminant concentrations, the monitoring of
which is increasingly accurate due to the continually improv-
ing resolution of commercial analytical capability.
3.4.3.4.2.1  Implications for Design  It is important to
keep in mind that most of our knowledge in the area of chem-
ical compatibility of materials comes from manufacturer
information and other reports based on laboratory studies that
Remediation Engineering
don’t replicate field conditions (e.g., where a material might
be subjected to physical stresses such as aggressive scrubbing/
cleaning that are not examined in a laboratory setting).
As a result, designers need to consider what the ratings in
any given compatibility chart reflect (study conditions and
outcomes), and how outcomes might differ in a field appli-
cation from what was reported by a laboratory study. For
example, applications that involve elevated temperatures will
reduce the resistance of plastics to chemical attack by driving
reactions and can cause failure where it might not otherwise
be predicted by lower-temperature laboratory study results.
The same is true for combinations of chemicals. A best prac-
tice in this area is to get the most up-to-date information from
manufacturers and couple that with the practical experience
of those that have used a certain material in situations that
combine various factors.
3.4.4 Environmental Considerations
In any remediation design, there are peripheral environmental
factors that need to be considered and plans included to man-
age and mitigate the ones that are relevant, so that the proposed
remediation activities will not affect the environment or nearby
receptors. These factors include things such as the following:90
• Volatile emissions and odors: Volatile substances
can cause varying types and degrees of environ-
mental impact, such as explosive conditions, unac-
ceptable health risks (either acute or chronic), and
objectionable odors. All of these must be considered
in remedy design. The creation of odors can cause
worker and community concern due to perception,
regardless of actual health risk.
• Dust/particulate emissions: Dust and the chemi-
cals within it can have potential health and environ-
mental impacts if generated at unacceptable levels.
Meteorological conditions (e.g., wind) or human
activities (e.g., traffic, earthmoving) can generate
dust that can impact site workers and migrate off-site
to affect surrounding community members.
• Noise: Noise from earthmoving, compaction activi-
ties, pumps, blowers, machinery, sirens, and vehicles
can be a risk to worker hearing and a nuisance for
neighboring community members. Failure to ade-
quately address noise issues associated with reme-
diation activities may also have legal implications
depending on local rules and regulations.
• Vibration and subsidence: Vibration from con-
struction equipment operation and subsidence from
groundwater extraction can cause damage to nearby
structures (e.g., buildings, buried utilities, surface
paving) and/or cause a nuisance to those nearby.
• Traffic: In addition to being a source or dust, vola-
tile emissions, noise, and vibrations, traffic can pose
a serious safety risk to the communities that it is
routed through, increasing the risk of vehicular and
pedestrian accidents, as well as wear and damage to
road infrastructure.
Principles of Integrated Design 103

• Security: Necessary measures should be considered 6. Ertas, A. and J.C. Jones. 1996. The Engineering Design
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Mineral-Water Interface Geochemistry. M.F. Hochella and
A.F. White (eds.). p. 603. Mineralogical Society of America,
Washington, DC.
70. Guertin, J., J.A. Jacobs, and C.P. Avakian. 2005. Chromium
(VI) Handbook. CRC Press, Boca Raton, FL.
71. Rock, M.L., B.R. James, and G.R. Helz. 2001. Hydrogen per-
oxide effects on chromium oxidation state and solubility in
four diverse, chromium oxidation state and solubility in four
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and Technology. 35(20), 4054–4059.
72. Teel, A.L., R.E. Vaughan, and R.J. Watts. 2008. Cadmium
release from four sorbents during treatment of contaminated soils
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73. Block, P.A., R.A. Brown, and D. Robinson. 2004. Novel acti-
vation technologies for sodium persulfate in  situ chemical
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Conference on Remediation of Chlorinated and Recalcitrant
Compounds, Monterey, CA, May 2004. Paper 2A-05. Battelle
Press, Columbus, OH.
74. McLean, J.R., R.R. Dupont, and D.L. Sorenson. 2006. Iron
and arsenic release from aquifer solids in response to biostim-
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75. Smedley, P.L. and D.G. Kinniburgh. 2002. A review of the
source, behaviour, and distribution of arsenic in natural
waters. Applied Geochemistry. 17(5), 517–568.
76. Postma, D. and C.A.J. Appelo. 2000. Reduction of Mn-oxides
by ferrous iron in a flow system: Column experiment and reac-
tive transport modeling. Geochimica et Cosmochimica Acta.
64(7), 1237–1247.
77. Lee, W. and B. Batchelor. 2003. Reductive capacity of natural
reductants. Environmental Science and Technology. 37, 535–541.
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Field-scale demonstration of induced biogeochemical reduc-
tive dechlorination at Dover Air Force Base, Dover, Delaware.
Journal of Contaminant Hydrology. 88, 119–136.
79. Suthersan, S.S. and F.C. Payne. 2005. In  Situ Remediation
Engineering. CRC Press, Boca Raton, FL.
80. Ozekin, K. et  al. 1998. Molecular ozone and radical path-
ways of bromate formation during ozonation. Journal of
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81. Cheng, I.F., R. Muftikian, Q. Fernando, and N. Korte.
1997. Reduction of nitrate to ammonia by zero valent iron.
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K.S. Lowe. 2001. Principles and Practices of In Situ Chemical
Oxidation Using Permanganate. Battelle Press, Columbus, OH.
83. Scheirs, J. 2000. Compositional and Failure Analysis of
Polymers: A Practical Approach. John Wiley & Sons, Ltd.,
Chichester, U.K.
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Chemical Attack. Rapra Review Report Volume 11, Number
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ABS, FEP, FRE, FRP, PTFE, and PVC well casing to deg-
radation by chemicals. U.S. Army Corps of Engineers, Cold
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86. Ranney, T.A. and L.V. Parker. March 1995. Additional studies
on the softening of rigid PVC by aqueous solutions of organic
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87. Ranney, T.A. and L.V. Parker. October 1996. Further studies
on the softening of rigid PVC by aqueous solutions of organic
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Research and Engineering Laboratory, Hanover, NH.
88. McCaulou, Douglas R, David G. Jewett, and Scott G
Huling. July 1995. Nonaqueous Phase Liquids Compatibility
with Materials Used in Well Construction, Sampling, and
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and Emergency Response. Washington DC.
89. Parker, L.V., A.D. Hewitt, and T.F. Jenkins. 1990. Influence
of casing materials on trace-level chemicals in well water.
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Technology overview: Green and sustainable remediation:
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States Environmental Protection Agency, Office of Solid
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Elements. Academic Press, London, U.K.
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Chemical Engineering Transactions. 25, 309–314.
 4 Remediation Hydrogeology
4.1 INTRODUCTION
Remediation hydrogeology, the application of hydrogeology
to remediation engineering, is a relatively recent field, having
only emerged in the last few decades. As with any emerging
scientific field, major shifts in thinking have occurred over
the course of its young history. Early concepts in remediation
hydrogeology were based on ideas from more mature fields
of hydrogeologic study, like development of water resources
and aquifer storage. Challenges in the fields of groundwater
remediation and water supply both dealt with understanding
where and how groundwater flows in an aquifer. Landmark
environmental cases like the Love Canal and Woburn, MA,
sites increased the public awareness of contaminated site
cleanup, leading to increased application of remediation
hydrogeology. However, as the science entered the 1990s
and 2000s, it became clear that very few sites were clean-
ing up as quickly as had been predicted. Practitioners reex-
amined remediation hydrogeology and found out the reason:
small-scale variations in geology and permeability control
contaminant transport, but the fundamental groundwater
­ contaminant transport, new strategies for site characterization
flow concepts were developed from water supply engineer-
ing, which relies on large-scale averages rather than small-
scale variations (Figure 4.1). Remediation hydrogeology
began to take a new shape, based on mass flux, the impor-
tance of local-scale heterogeneities (variations) in geology as
expressed in contaminant storage and contaminant transport
zones, and the significance of diffusion rather than disper-
sion and transient rather than steady-state observations.
One of the key shifts in the field was from approaches
based on concentration (mass per unit volume) to those based
on mass flux (mass per unit area per time), as a flux perspec-
tive provides a measure of relative strength of individual
sources, which enables one to rank and prioritize remedies
accordingly. Mass flux is useful because it describes whether
a source is concentrated or diffuse; mass flux allows further
refinement in prioritization efforts and development of appro-
priate strategies to target and effectively mitigate it. Transport
behavior and the most effective cleanup options are differ-
ent along the length of a plume, because the plume matura-
tion process leads to different levels of contaminant mass in
transport zones and storage zones. Therefore, the flux-based
approach focuses remedies on the “mass that matters,” maxi-
mizing treatment efficiencies and minimizing total life-cycle
cost. It is important, then, to change our approach to site char-
acterization, focusing on tools and methods that enable the
identification of mass flux.
A new approach to site characterization is needed to
match our new understanding of remediation hydrogeology.
We call this new approach “Smart Characterization” Smart
Character­ ization methods integrate dynamic, real-time,
high-density soil and groundwater sampling with hydrostrati-
graphic interpretations and permeability mapping in three
dimensions. By correlating high-resolution concentration data
with hydrostratigraphy and permeability data, it is possible to
map and distinguish contaminant mass transport zones from
mass storage zones. This approach enables real-time classifi-
cation of the scales of variability that control mass transport
in the source and distal segments of groundwater plumes.
Finally, conceptual site models (CSMs) are built to rep-
resent the geologic, hydrogeologic, mass distribution, and
transport conditions at the site and serve as a framework for
making remediation decisions. The idea of a “living” CSM
is also experiencing a renaissance, with practitioners recog-
nizing the importance of continually testing and revising the
CSM based on updated information from investigations as
well as performance-based data from the site. Application of
3D visualization software for CSMs is transforming our abil-
ity to view and evaluate site data and resulting in more effec-
tive and efficient remedies.
With the shifts in thinking about groundwater flow and
and interactive, digital CSMs, it is truly an exciting time to be
a remediation hydrogeologist!
4.2 FUNDAMENTAL CONCEPTS
IN HYDROGEOLOGY
The primary goals of the remediation hydrogeologist are to
determine where groundwater is flowing and the behavior of
contaminants present in the groundwater. Therefore, the two
most important concepts relevant to the discussion of remedi-
ation hydrogeology are groundwater flow (Section 4.2.1) and
contaminant transport (Section 4.2.2).
4.2.1  Groundwater Flow
Before we can understand the fate and behavior of contami-
nants present in groundwater, we must first understand the
manner in which groundwater flows through the subsurface
and review a number of fundamental concepts of hydrogeol-
ogy, including aquifers, porosity, heterogeneity, and hydraulic
conductivity. The following text provides an introduction to
the major concepts of groundwater flow; the reader is encour-
aged to seek out one of the many textbooks on hydrogeology
for additional material.1,2
4.2.1.1  Aquifers and Their Characteristics
An aquifer is a geologic unit that has the ability to store,
transmit, and yield groundwater at rates sufficient for a speci-
fied need. For example, the well-known Ogallala aquifer, also
107
 108 Remediation Engineering

(e.g., permeability, porosity, geochemistry) can separate aquifer zones and represent important barri-
ers to flow; in these settings, an aquitard may be referred to
Observable aquifer characteristic

Representative elementary volume (REV) as a confining layer. As discussed in subsequent sections,

Average value
Classical Darcian hydrogeology
Remediation
hydraulics
Scale of observation
FIGURE 4.1  Representative volumes for water scale engineer-
ing and remediation hydrogeology. (From Payne, F.C. et al., Reme­
diation Hydraulics, CRC Press, Boca Raton, FL, 2008.)
known as the High Plains aquifer, is generally composed of
highly permeable coarse-grained sediment and is one of the
world’s largest aquifers, supplying about 30% of the ground-
water used for irrigation in the United States and drinking
water to about 80% of the more than two million people who
live within its boundaries.3,4 While this typical definition of
an aquifer is based on a large-scale water supply perspective,
thin transmissive zones can be significant for contaminant
transport, demonstrating the importance of scale in the dif-
ference between water supply hydrogeology and remediation
hydrogeology. An aquifer may consist of loose or uncon-
solidated sediment such as an alluvial aquifer or may be a
consolidated or fractured material such as sandstone or lime-
stone bedrock.
An aquitard is a layer or zone with relatively low perme-
ability and therefore cannot support a significant amount
groundwater flow or yield (Figure 4.2). Depending on
their continuity and geometry, low-permeability materials
aquitards and low-permeability material may allow signif-
icant contaminant storage through diffusion of mass and
act as a long-term secondary source continuing to impact
groundwater quality even after primary sources have been
remediated.
An aquifer that is not overlain by an aquitard or low-
permeability materials and is recharged by downward
infiltration through the overlying unsaturated materials or
vadose zone is referred to as an “unconfined aquifer” or
“water-table aquifer” (Figure 4.2). Conversely, an aquifer
that is overlain by an aquitard and is primarily recharged
from outcrops or other distal recharges zones is a “confined
aquifer” (Figure 4.2).
The total porosity (θt) of a geologic material is the volume
of void space relative to the material volume and is the space
where groundwater occurs in an aquifer. The total porosity
of unconsolidated materials can range from 20% to 30% or
more, while the total porosity of bedrock aquifers is much
lower.
In most aquifer systems, the vast majority of ground-
water flow occurs in only the most permeable zones and
therefore only in a fraction of the total porosity. This allows
us to separate the subsurface into zones responsible for
groundwater flow and contaminant transport, dominated by
advection–transport zones, from zones responsible for con-
taminant storage or storage zones. The component of the
aquifer porosity where the majority of the groundwater flow
is occurring is referred to as the “mobile” or “migratory
porosity” (θ m), while the porosity in low-permeability zones
where flow is very low is termed “immobile” or “storage
porosity” (θim) (note that θ m + θim = θ t). Figure 4.3 is a fre-
quency distribution of measured mobile porosity (θ m) values
for alluvial aquifers determined from tracer tests completed

Piezometric surface
(in confined aquifer)

Well in
confined aquifer

Water table well

(in unconfined aquifer)

River
Unconfined
aquifer

Confined aquifer
Aquitard (low permeability)
Top of the
confined aqifer

Aquitard (low permeability)

FIGURE 4.2  Illustration of the basic hydrogeologic terms.

Remediation Hydrogeology 109

25 The aquifer permeability, or more precisely hydraulic

conductivity, quantifies the resistance to groundwater flow
20 through the aquifer and is expressed in units of L/T. The
hydraulic conductivity of earth materials varies dramati-
Frequency (%)

15
cally; well-sorted (i.e., uniform grain size distribution) sands
and gravels may exhibit values exceeding 10  cm/s, while
10
fined–grained silts and clays exhibit values orders of magni-
5 tude lower (see Figure 4.4). This dramatic range in hydraulic
conductivity is a root cause for the complexities in contami-
0 nant migration and plume characteristics and the significant

Greater than 0.30

challenge to fully remediating all areas of a site to low drink-
Less than 0.03

0.03–0.06

0.06–0.09

0.09–0.12

0.12–0.15

0.15–0.18

0.18–0.21

0.21–0.24

0.24–0.27

0.27–0.30
ing water quality standards.
As water enters an aquifer through recharge, the total
hydraulic head or simply head, which is the sum of the eleva-
tion head and the pressure head, of the groundwater increases.
Measured mobile porosity, θm The hydraulic gradient (i) is therefore defined as the change in
head per unit of length along a specific flow path direction and
FIGURE 4.3  Frequency distribution of measured mobile represents a vector quantity. The hydraulic gradient represents
porosity (θ m) values for alluvial aquifer types determined from the driving force for groundwater flow as groundwater flows
tracer tests completed at 73 different sites across the United
from higher head toward decreasing head.
States. (From Suthersan, S. et al., Ground Water Monit. Remed.,
34(3), 33, 2014.)
Darcy’s Law, which acknowledges the French civil engi-
neer Henry Darcy’s pioneering work in the 1850s, quanti-
fies the relationship between the groundwater flux (q), K,
at 73 different sites across the United States. The median and i as
value of these data is 10%; a large percentage of values are
less than 5% and only a small fraction of the values are
greater than 20%. q = Ki (4.1)

Igneous and metamorphic rocks

Unfractured Fractured

Basalt
Unfractured Fractured Lava flow

Sandstone
Fractured Semiconsolidated

Shale
Unfractured Fractured

Carbonate rocks
Fractured Cavernous
Clay Silt, loess

Silty sand

Clean sand
Fine Coarse

Glacial till Gravel

10–11 10–10 10–9 10–8 10–7 10–6 10–5 10–4 10–3 10–2 10–1 100 101 102
cm/s

FIGURE 4.4  Hydraulic conductivities of selected rocks and earth materials. (Modified from Heath, R.C., Basic ground-water hydrology,
U.S. Geological Survey Water-Supply Paper 2220, 86pp., 1983.)
110
The volumetric groundwater flow is obtained by multiply-
ing by the aquifer thickness (b) and width perpendicular to
flow (w):
Q = Kibw (4.2)
For some applications, the term transmissivity (T) is used and
is equal to the product of the hydraulic conductivity and the
aquifer thickness (T = Kb) and has units of L2/T. Although
q has the units of L/T, it represents the groundwater flux or
specific discharge, which is the volumetric flow per unit area;
the average linear groundwater flow velocity (n) or advective
velocity is equal to:
q
n= (4.3)
qm
4.2.1.2 Aquifer Building Processes,
Heterogeneity, and Anisotropy
In a simple system, groundwater (and contaminants transported
with the groundwater) will follow the direction of the maximum
hydraulic gradient. However, it is critically important to recog-
nize that all aquifers are built by geologic processes and that
these geologic processes impart a complex structure that con-
trols groundwater flow at a range of scales. The aquifer build-
ing processes create both the spatial variability or heterogeneity
and directional dependence or anisotropy of aquifer properties.
Different geologic depositional environments will have differ-
ent styles of heterogeneity and anisotropy and different ranges
in permeability. Adding to the complexity, multiple, overlap-
ping depositional environments may be present at a single site.
It is outside of the scope of this chapter to provide guidance on
all depositional environments, as entire textbooks have been
published on single depositional environments (7provides an
excellent overview of multiple environments). To illustrate the
complexity of these processes, consider how depositional pro-
cesses in a few of the different commonly encountered geologic
environments lead to different styles of heterogeneity, anisot-
ropy, and permeability ranges. Braided and meandering are two
common river, or fluvial, depositional environments, and each
has a distinctive set of soil types and resulting permeabilities.
Braided rivers consist of multiple overlapping channels, which
deposit mainly gravel and sand, while meandering rivers are
largely confined to a single channel and deposit relatively finer
sediments. Both braided and meandering systems therefore pos-
sess strong anisotropy based on the direction of the fluid move-
ment. Meandering rivers can be further subdivided by different
depositional processes, each with its own distinctive character-
istics: channel deposits, dominated by coarse, gravelly deposits,
point bars with fining upward sequences commonly seen, and
overbank deposits with fine sands, silts, and muds on the flood-
plain. The heterogeneity of these fluvial deposits is compounded
by the fact that they are continually reworked by the stream as
it meanders back and forth across the floodplain, eroding, and
redepositing portions of the sediments. Lake or lacustrine depos-
its may have a large range in grain sizes, as gravels and sands
accumulate at the edges of a lake and finer-grained sediments
Remediation Engineering
accumulate in the middle. While fluvial and lacustrine depos-
its resulted from running water, desert/eolian environments
have been created through wind. The two major types of eolian
deposits are well-sorted sand and windblown silt, called loess.
Glacial deposits may be the most complex environment, as
deposits resulting from the glacier can mix with components of
the other depositional environments (lakes, rivers, and eolian).
The power of an active glacier is tremendous, and as such sedi-
ments can range from clay sized all the way up to boulders. In a
simple sense, glacial deposits can be classified based on whether
they resulted from direct contact with the ice or they resulted
from forces outside the glacier. One common ice-contact deposit
is till, a poorly sorted mixture of clay, silt, sand, and coarser
material created by the force of the advancing glacier. Running
water coming off of the glacier (meltwater) results in more well-
sorted deposits, including the common deposits of glacial out-
wash plains with features similar to those of braided rivers.
Obviously, each depositional environment can lead to a dis-
tinctive style of heterogeneity, anisotropy, and range in perme-
abilities. This complexity can be managed by the remediation
hydrogeologist by linking the scales the depositional processes
operate at with the reflection of the processes in the subsurface.
The scales of the depositional processes can be divided into
the mesoscale, the macroscale, and the microscale. Mesoscale
processes operate at the regional or basin scale and are rep-
resented in the subsurface by regional aquifers and aquita-
rds. Macroscale processes operate at the site scale and are
represented in the subsurface by storage and transport zones.
Microscale processes operate at the particle scale and are rep-
resented in the subsurface by mobile and immobile porosity.
The ability to link processes in the depositional environment to
the resulting features in the subsurface that control groundwa-
ter flow is powerful and demonstrates the critical importance
of the geologist on project teams. The photographs in Figure
4.5a and b highlight the heterogeneity, anisotropy, and struc-
ture imparted on alluvial aquifers as a result of the deposition
and aquifer building processes at two dramatically different
scales. The permeability structure imparted from depositional
processes occurs at a range of scales—Figure 4.5a illustrates
the large-scale heterogeneity created by a braided stream
deposit in Siberia, while Figure 4.5b shows a similar pattern of
heterogeneity but at a much smaller scale.
There are dramatic differences in depositional processes and
the nature of storage and transport zones between different depo-
sitional environments. A meandering stream will have transport
zones in the higher permeability sands and gravels in the channel
and point bar deposits and storage zones in the low-permeability
silts and clays on the floodplain, while an eolian environment
will have transport zones in the windblown sand and storage
zones in the loess deposits. Dramatic differences in permeabil-
ity are present within single depositional environments—a gla-
cial environment must be ­evaluated to determine what glacial
process were active in the area to understand if the anticipated
sediments are likely to be poorly sorted, low-permeability tills or
higher-permeability outwash sand and gravels.
Aquifers comprising rock or consolidated materials rep-
resent a special class of groundwater flow complexity and
Remediation Hydrogeology 111

(a)

(b)

FIGURE 4.5  (a) Aerial photograph of a braided stream in Siberia, highlighting the aquifer building process and the large-scale structure
that can result. (b) Aerial photograph of a stream deposit in California, showing the smaller scale structure that results from the aquifer
building process. Pebble in upper right of photo is approximately 2 inches long. (Photo courtesy of Dan Rogers.)

include some of the most problematic and challenging sites
to remediate, because they often are characterized by extreme
spatial heterogeneity and anisotropy, high groundwater flow
velocities, and large storage porosities.8 The terms “bedrock”
and “rock” refer to the consolidated geologic materials and
formations that occur below the soil or “overburden”; how-
ever, many of the concepts also apply in fractured overburden
units, such as some clay and glacial till formations. The term
“fracture” refers to any break in bedrock that is still open and
not filled with precipitated minerals. Fractures occur due to
brittle deformation of the rock; the forces that cause fractur-
ing typically result from plate tectonics, regional compression
or extension, and uplifting or cooling/shrinking in the case of
lava flows. Fractures can align with planes of weakness that
occur along the rock fabric as a result of bedding or foliation
and often occur in orthogonal sets—one parallel to the pri-
mary direction of stress and one orthogonal.
Any fracture in rock is potentially a permeable pathway that
can facilitate fluid flow. Although the ease of fluid flow varies
as a function of fracture width or “aperture,” fractures are much
more permeable than the unfractured portion of the rock or
“matrix” and therefore usually control the flow paths and direc-
tions of contaminant transport (Figure 4.6). Many rock forma-
tions contain one or more groups of parallel fractures known as
112
(a)
FIGURE 4.6  Photographs of drill cores collected from a granitic aquifer with limited fracturing and essentially no matrix porosity (a)
and a highly fractured sandstone aquifer with relatively high matrix porosity (b). (Courtesy of Tom Vespalac and Craig Divine (Arcadis).)
(a) (b)
FIGURE 4.7  Flow complexity at fracture intersections. (a) Diverging flow (dispersion), (b) converging flow (flow focusing), and (c) flow
redirection. (Courtesy of Craig Divine (Arcadis).)
“fracture sets”; multiple crosscutting fracture sets are also com-
mon. Although individual fractures may have limited length, the
combination of intersecting fractures and fracture sets produces a
composite “fracture network” that behaves as an interconnected
flow system. Because plumes will orient themselves with the
regional fracture network, it is critical to understand the geologic
history, structure, and stresses that created the fracture network.
The various bedrock types each exhibit common types
of fracture patterns. For example, sedimentary rocks, which
are formed by the deposition and subsequent cementation of
sedimentary materials, form in horizontal stratigraphic layers
(“beds”) during the deposition of sediments or precipitation of
saturated minerals from solutions. The contacts between beds
are often planes of weakness, and sedimentary rocks commonly
have bedding plane fractures parallel to the layers; however, they
also often have crosscutting fractures that form at a high angle
to the beds. Metamorphic rocks, which result when existing
rock is subjected to extreme heat and pressure, also commonly
have a planar fabric known as “foliation” due to the alignment of
mineral crystals. Metamorphic rocks with obvious foliation may
fracture preferentially parallel to the planar fabric; however, they
also often have crosscutting fractures that form at a high angle
to the foliation. Igneous rocks, such as basalt and granite, are
formed by the cooling and solidification of molten rock material.
These rock types may exhibit fracture patterns that are parallel
to the surface of the rock or they may have fractures that are
oriented in a variety of directions depending on regional stresses
and granular composition.
Fracture hydraulic conductivities are generally much
higher than those of porous media. Consequently, groundwa-
ter velocities in fractured rock are generally much higher than
Remediation Engineering
(b)
Flowing fracture
Solute flow direction
(c)
in unconsolidated porous media and are often in the range of
tens to hundreds of feet per day. Groundwater flow pathways in
fractured bedrock are particularly complex and are controlled
by the orientation, spacing, aperture and interconnectedness of
fractures and fracture sets, and the direction of the hydraulic
gradient (Figure 4.7). These factors highlight the importance
of characterizing fractures and fracture sets on a site-specific
basis, where solute transport analysis is required.
4.2.2 Contaminant Transport Processes
The study of the behavior and transport of contaminants in
water separates remediation hydrogeology from classical
water supply hydrogeology. Contaminants can be introduced
into the environment as either “point” sources or “nonpoint”
sources. Nonpoint sources are sources distributed over a large
spatial area, like agricultural fertilizers or urban runoff. Point
sources refer to contaminants originating at a specific loca-
tion. Point sources could range from a simple spill of a con-
taminant at the ground surface that works its way down to
the water table to more complex sources that may introduce
contaminants at depth, including leaking underground stor-
age tanks, hazardous waste disposal (e.g., buried waste-filled
drums), septic systems, and leaking landfill liners.
Once contaminants are introduced to the groundwater,
they are transported by one of the following three processes:
1.
Advection: Transport with the bulk fluid movement
2.
Dispersion: Transport resulting from different
groundwater velocities and pathways in the aquifer
3.
Diffusion: Transport based on concentration gradients
Remediation Hydrogeology
For years, the advection–dispersion model of contaminant trans-
port has been used, which states that contaminants generally travel
with the advective groundwater but “spread” based on velocity
differences. This “spreading” would be seen in tracer data as a
smooth, Gaussian-shaped breakthrough curves. However, this
ideal behavior was not observed in real-world tracer tests. Instead,
tracer test data show nonsymmetrical breakthrough curves with
long tails following breakthrough, which is caused by diffusion,
indicating that contaminant transport should be thought of as
advection–diffusion rather than advection–dispersion.
4.2.2.1 Advection
As groundwater flows across a site, contaminants travel
with the bulk fluid movement in a process called advection.
Conceptually, advection is analogous to leaves floating down a
stream or fine dust blowing in the wind. If all other transport
phenomena are relatively insignificant, the average rate of solute
movement equals the average linear groundwater flow velocity
(n). It is important to remember that at the local scale, geologic
heterogeneity and anisotropy cause significant variability in
the magnitude and direction of the groundwater flow velocity,
and therefore contaminant transport behavior due to advection
is strongly controlled by the local hydrogeologic conditions. As
such, transport via advection should be reconsidered as hetero-
geneous advection, where a spectrum of advective velocities
occur, including permeable transport zones with velocities in
the range of tens of feet per year, as well as less permeable slow
advection zones, where velocities are in the range of 1–10 ft/
year. Due to these high velocities, advection dominates mass
transport; however, the transport behavior is strongly influenced
by the interaction between advection and diffusion, as discussed
in the following section. Contaminant transport velocity by
advection can be estimated by Darcy’s law and other flow and
transport models, but it is most reliably determined by a direct
measurement technique such as tracer testing.
4.2.2.2  Dispersion and Diffusion
Dispersion is a general term that has been used to describe the
tendency for solute plumes to spread and become diluted as they
travel away from a source. For example, contaminant arrival
or breakthrough at areas downgradient from a release point is
not “sharp” but instead is usually characterized by a relatively
gradual and smooth increase over time (Figure  4.8,  “A”). As
contaminant sources are remediated, contaminant cleanup or
elution at downgradient areas is also characterized by a rela-
tively smooth and gradual curve; furthermore, the cleanup
curve often exhibits notable “tailing” (Figure 4.8, “B”).
There are two general mechanisms that cause this spreading
behavior: hydrodynamic dispersion and diffusion. Hydrodynamic
dispersion is the result of local-scale variations in advective veloc-
ities, whereas diffusion is the process of solute transport due to
concentration gradients. Hydrodynamic dispersion is commonly
attributed to pore-scale bifurcation of groundwater flow paths
created by geologic heterogeneities and bulk water mixing.9 In
contrast, diffusion is the mass transfer mechanism driven by
concentration gradients and random molecular motion alone.
Diffusion is commonly described by Fick’s laws of diffusion.
113
C100
Normalized concentration
A
B
0
Time
FIGURE 4.8  Conceptual contaminant arrival (breakthrough) and
cleanup (elution) characteristics at a point located down gradient
from a source area and remediation system. (Courtesy of Craig
Divine (Arcadis).)
Historically, hydrodynamic dispersion (i.e., variations in
advective velocities) was believed to be the primary mecha-
nism behind the observed smooth nature of contaminant break-
through and lateral plume spreading, but recent advances in
contaminant transport research9 have indicated that diffusion is
a more significant process than hydrodynamic dispersion. The
question of the underlying process driving contaminant transport
is not academic: it influences the decisions we make on charac-
terization and remediation strategies at every site. For example,
if dispersion was a significant process, then plumes would be
easier to characterize, as one would not need to be concerned
about “missing” a plume that is traveling in-between monitor-
ing wells; in situ, injection-based remedies could take advantage
of transverse dispersivity to distribute reagents. Yet observation
has repeatedly shown us pencil-thin plumes frequently missed
by monitoring well networks and that injection reagents must be
distributed laterally during the injection event. Additionally, the
importance of diffusion leads to another important realization
that significant mass can be stored in low-permeability zones,
and these storage zones act as long-term sources.
4.3 EVOLUTION OF REMEDIATION
HYDROGEOLOGY
Although the field of remediation hydrogeology is relatively
young, dramatic shifts in thought have occurred over its short
history. Remediation hydrogeology emerged in the second half
of the twentieth century, with its origins rooted in water supply
engineering and with many early remedies based on ground-
water extraction and the advection–dispersion theory of con-
taminant transport. Subsequent advances in our understanding
of contaminant flow and transport along with poorly perform-
ing groundwater extraction systems led to a refined approach
called remediation hydraulics. Remediation hydraulics recog-
nized that fine-scale permeability changes create contaminant
mass storage zones and mass transport zones and moved to an
advection–diffusion model of contaminant transport.
4.3.1 Pre-1950s: The Water Supply Origins
of Hydrogeology
The importance of groundwater to humanity cannot be over-
stated. Groundwater is the most extracted raw material on the
114
planet, and it is estimated that groundwater accounts for more
than 98% of domestic water supplies in the United States.10,11
Therefore, it is not surprising that the early development of
hydrogeology as an applied science was highly influenced by
questions related to bulk groundwater flow, water yield, and the
hydrologic cycle. Consequently, the most well-established con-
cepts, investigative tools, and quantitative techniques in hydro-
geology are most relevant to water supply problems that involve
time and distance scales that are much greater than typical
site-specific groundwater remediation problems. For example,
some of the most seminal and paradigm-shifting contributions
to hydrogeology and water resources by Józeph Tóth focused on
the controls and characteristics of basin-scale groundwater flow
and drainage,12 while the typical remediation project is usually
more than 1000 times smaller than this area.
4.3.2 1950s–1980s: Early Developments
in Remediation Hydrogeology
Prior to the 1970s laws and regulations related to groundwater
were focused primarily on water rights and management of water
resources. As industrialization greatly increased after World War
II, the use and distribution of refined fuels and synthetic chemicals
also significantly increased (Figure 2.9). Unfortunately, because
groundwater is unseen and therefore often forgotten (“out of sight,
out of mind”), there was a great lack of understanding and apprecia-
tion for the connection between waste management, land use prac-
tices, and groundwater quality. For example, it was often assumed
that liquid wastes discharged to pits or ponds would simply disap-
pear through evaporation; furthermore, it was widely believed that
aquifers could effectively filter and treat most chemicals. However,
in the early and mid-1970s, several situations gained high pub-
lic profile where communities (e.g., Niagara Falls, New York;
Seymour, Indiana; Woburn, Massachusetts) were greatly impacted
by groundwater contamination caused by the inappropriate storage
and disposal of industrial chemicals. Ultimately, these situations
and others resulted in the creation of many new waste management
and environmental regulations specifically intended to restore
and protect groundwater. The recognition of the importance and
unique challenges of groundwater restoration provided the critical
driver for the development of site-scale investigation techniques,
solute transport concepts, and remediation technologies. Many of
the early developments in remediation hydrogeology were cap-
tured in a number of landmark books,12–14 which were utilized as
university classroom texts for a generation of hydrogeologists and
quickly became standard resources for practitioners.
4.3.3 1980s–2000s: The First Generation
of Remediation Hydrogeology
The first generation of applied remediation hydrogeology relied
primarily on pump and treat as the presumptive remedy—
between 1982 and 1992, 73% of the cleanup agreements at
Superfund sites specified the use of pump-and-treat technol-
ogy to treat contaminated groundwater15,16 (see Chapter 5 for
additional discussion of the history and application of pump
and treat). This strategy fit well with the water supply origins
Remediation Engineering
Concentration in groundwater
Theoretical
removal Removal with
tailing in reality
Pore volumes removed
FIGURE 4.9  Theoretical removal curve showing the number of
pore volumes of groundwater that must be pumped to remove the
contamination.
of the science, as groundwater extraction was applied on large
scale and based on bulk averages of aquifer properties deter-
mined through pumping tests and capture zone analysis. The
appeal of groundwater extraction as a remedial strategy was
due to its simplicity: groundwater is physically extracted from
the subsurface and treated; system effectiveness can be evalu-
ated by calculating the mass of contaminants removed from
the subsurface.
However, as groundwater extraction was being applied
more commonly, practitioners began to find weaknesses in the
approach. Pump-and-treat systems had been originally proposed
as approaches to restore groundwater to concentrations less than
the maximum contaminant level (MCL) in a defined timeframe
(often around 20 years), but most pump-and-treat systems would
reach the target date for restoration to MCLs with asymptotic
contaminant concentration trends indicating MCLs would not
be reached for decades or longer (see Figure 4.9), with costs
continuing to increase linearly. This “tailing” phenomenon
had two important results. First, it influenced the economics of
remediation into considering alternate remediation approaches
that could achieve target concentrations in a shorter timeframe.
These “forever pump and treats” were designed thinking that
they were the lowest cost remedy, but the prospect of decades
more of extraction and treatment was leading to total costs far
higher than had been originally considered. The second devel-
opment, which perhaps is more important, prompted practitio-
ners to reexamine the foundations of remediation hydrogeology
and led to the developments of remediation hydraulics.
4.3.4  2000s–Present: Remediation Hydraulics
The most recent advances in remediation hydrogeology have
been the ideas of remediation hydraulics, which posits that
small-scale geologic heterogeneities create contaminant mass
storage zones dominated by diffusion and mass transport
zones dominated by heterogeneous advection. The distribu-
tion of these storage and transport zones can only be mapped
by integrating the site depositional history using the princi-
ples of hydrostratigraphy. The mass transport in these zones
Remediation Hydrogeology
is better represented using mass flux that measures plume
strength by integrating the permeability of the contaminant
storage or transport zone rather than by concentration alone,
which is only a measure of contaminant mass per unit volume.
Furthermore, the model of contaminant transport is reshaped
based on advection–diffusion instead of advection–dispersion.
The remediation hydraulics concepts make it possible to apply
flux-based characterization and remediation strategies that tar-
get the mass that moves—which is the mass that creates risk.
4.3.4.1  Heterogeneous Advection and Diffusion
At the most fundamental level, the developments of remediation
hydraulics require us to revise our conceptual model of contami-
nant transport. The classical approach to transport is based on
advection–dispersion, but we now realize that the contributions
of dispersion to plume spreading are limited.9 Instead, plume
spreading is a result of either time-dependent spreading (molecu-
lar diffusion), pore-scale flow-dependent spreading, or spread-
ing due to aquifer heterogeneities. This realization has replaced
advection–dispersion with advection–diffusion as the mode of
contaminant transport. The new model of contaminant transport
also led to the classification of aquifer zones as transport zones
dominated by advection and storage zones dominated by diffu-
sion. The transport/storage zone model was a major step forward
for remediation hydrogeology but was limited by the classifica-
tion of all soils as either transport or storage. There is a broad
range of permeabilities in the subsurface; the highest permeabil-
ity zones (sands and gravels) will act as pure transport zones,
and the lowest permeability zones (silts and clays) will act as
pure storage zones. But there are also intermediate permeability
zones—interbedded sand–silt–clay mixtures—that are currently
lumped and classified as storage zones. We call these “slow
advection” zones, and they will have both diffusion and advec-
tion occurring in them. Notably, while their advection rates are
far lower than the rates in a pure transport zone, their advection
rates are still far higher than the diffusion rate in the zone (het-
erogeneous advection and slow advection zones are discussed in
more detail in Chapter 5).
4.3.4.2  Stratigraphic Flux
The transport, slow advection, and storage zones are best
evaluated using an approach we call stratigraphic flux, which
combines the principles of hydrostratigraphy and mass flux.
Hydrostratigraphy is the approach by which we can evaluate the
aquifer permeability distribution by linking it to the aquifer dep-
ositional environment. As discussed previously in this chapter,
the geologic processes that deposited soils create heterogene-
ity and anisotropy of the aquifer properties. The hydrostratig-
raphy approach accounts for heterogeneity and anisotropy and
moves beyond the simple layer-cake depictions of geology that
are unfortunately all too common in remediation hydrogeology.
Instead, the type of depositional environment is identified and
the resulting style of heterogeneity, anisotropy, and permeability
ranges are applied to the interpretation of the aquifer at the site.
For example, recall again the differences between the aquifer
properties resulting from different depositional processes: a gla-
cial till deposit resulting from the advancing glacier will have a
115
1000
Wellhead impact
(μg/L): More impact
100
100
Plume mass discharge (g/day)
10
10 1
0.1
1
0.1
0.01
Less impact
0.001
1 10 100 1000
Receptor flow rate (gpm)
FIGURE 4.10  Relationship between plume mass discharge and con-
centration at a down gradient pumping well or surface water receptor as
a function of receptor flow rate (i.e., supply well or surface water body).
The isolines represent exposure point concentrations based on complete
plume capture and complete mixing at the receptor. (From Suthersan,
S. et al., Ground Water Monit. Remed., 30(1), 36, 2010.)
poorly sorted mixture of silt, clay, sand, and coarser particles,
while running water flowing off the glacier will create a well-
sorted, higher-permeability deposit.
The other half of the stratigraphic flux approach is to apply
a mass flux perspective to the site. Mass flux is the product of
contaminant concentration and volumetric flow, per unit cross-
sectional area. Multiplying mass flux by the cross-sectional
area of flow results in the total mass discharge or mass loading
rate. Because they integrate both concentration and flow, mass
flux and mass discharge provide a measure of source strength
and potential risk to receptors. Figure 4.10 presents an example
nomograph that demonstrates the utility of mass discharge by
evaluating the potential contaminant concentration at a pump-
ing well or a surface water body assuming full plume capture.17
As shown on the nomograph, a trichloroethene mass discharge
of 1 g/day might represent a concern for a low-capacity sup-
ply well because exposure point concentrations could exceed
100 µg/L. However, the equivalent contaminant mass discharge
to a high-capacity well or high flow surface water body poses
much lower risk because dilution may reduce the exposure point
concentration below detection limits.
Figure 4.11 demonstrates how geologic heterogeneity cre-
ates in significant spatial variability in mass discharge and how
a relatively small fraction of the aquifer pore space may partici-
pate in the majority of advective transport.9,17 The left side of
Figure 4.11 shows a simulated aquifer that is based on a braided
river channel environment with a permeability range of 2 orders
of magnitude (blue is high, white is low). The right frame shows
fluid flow density—dark shading reflects flow focusing in high-
permeability channels. More than 90% of groundwater flow is
concentrated in 20% of the aquifer volume, while less than 10%
of the flow occurs in more than 80% of the aquifer.
On their own, hydrostratigraphic analysis and mass flux
are powerful approaches that advance our understanding of
116 Remediation Engineering

400 ft

300 ft
(a) (b)

FIGURE 4.11  Geologic heterogeneity results in significant spatial variability in mass discharge, and a relatively small fraction of the
aquifer pore space may participate in the majority of advective transport.9,17 (a) The image is a simulated aquifer based on a braided river
depositional environment; blue corresponds to higher permeability and white to lower permeability and the water elevation contours are
shown at 0.5-foot intervals. (b) The image shows the fluid flow density, with the darker shaded portions representing flow focusing in high-
permeability channels. Notably, more than 90% of the groundwater flow occurs in 20% of the area.

the subsurface. By combining the two, we can develop a strati-
graphic flux framework that shows how the aquifer depositional
history leads to the distribution of permeability at the site, which
can be interpreted using a flux-based framework to classify soils
as transport, slow advection, and storage zones. The result is a 3D
description of the aquifer architecture that describes the subsur-
face in terms of transport potential. The advantage of this approach
is that it builds on sequence stratigraphy methods and provides
insights regarding how permeability distributions within elements
of the aquifer architecture control contaminant transport, cleanup
duration, and realistically achievable end points. This process is
different from the conventional stratigraphy approach in which it
uses relative flux to classify the system and provide a quantitative
metric to rank and prioritize remediation efforts.
The stratigraphic flux approach consists of the following
elements:
• Depositional framework and stratigraphic logging:
The first step is to develop hydrostratigraphic classi-
fications with knowledge of the depositional environ-
ment and use the appropriate characterization tools
for permeability mapping. The permeability mapping
tools must be matched to the depositional environ-
ment; as discussed in the next section, there are a
variety of permeability mapping tools suited for dif-
ferent permeability ranges. The relative permeability
is then mapped in terms of the mass flux–based inter-
pretations. This approach provides hydrostratigraphic
units that will enable correlation with permeability
and enable use of classical stratigraphy methods to
interpret trends between the boreholes to map the
aquifer architecture. Downhole geophysical methods
can be used to support facies trend analysis and bore-
hole to borehole interpretations.
• Quantify concentration and permeability: The next
step is to develop a quantitative distribution of con-
centration and permeability across the aquifer. The
contaminant concentrations must be mapped using
tools that provide quantitative data rather than screen-
ing level data and at a resolution that matches the scale
of the depositional environment heterogeneities iden-
tified in the first stage. The continuous relative perme-
ability mapping that was created in the first stage is
now converted to a quantitative representation of per-
meability by correlating hydrostratigraphic unit trends
with permeability estimates (from grain size analyses,
hydraulic testing, etc.) to a stratigraphic flux mapping
that links transport zones, slow advection zones, and
storage zones with permeability ranges.
• 3D stratigraphic flux model: The final stage is to
integrate groundwater contaminant concentrations
and permeability estimates in the transport, slow
advection, and storage zones to derive a 3D mapping
of relative flux and aquifer architecture. The model
output can be a series of transects, fence diagrams, or
3D solids that graphically depict the relative flux and
enable one to readily understand the geometry and lat-
eral connectivity of the transport zones (Figure 4.12).
The stratigraphic flux model uses a multiple lines of
evidence approach, integrating available information
Remediation Hydrogeology 117

HPT-15
HPT-01 HPT-14
HPT-02 HPT-13
HPT-12
HPT-03 HPT-11
HPT-04 HPT-10
HPT-05 HPT-06 HPT-09
HPT-07 HPT-08

80

70

60

50 2,175,500

2,175,700
40
2,175,900
349,000
348,900 30 2,176,100

348,800
20 2,176,300
348,700

348,600 10 2,176,500

348,500 0
2,176,700
348,400
–10

–20

FIGURE 4.12  Example output from a 3D stratigraphic flux analysis. Colors represent higher and lower flux zones.

including geochemistry, hydraulic testing, and reme- 4.3.4.3 Flux-Focused Investigation and

diation performance data to enable further refinement
of the flux-based model. The stratigraphic flux model
can then be used to refine existing groundwater flow
and solute transport models or as part of a dynamic
remedy implementation program to optimize soil and
groundwater treatment performance.
Remediation Strategies
A stratigraphic flux perspective leads to the ability to employ
flux-based investigation and remediation strategies. The concep-
tual evolution of plume maturity from a source through trans-
port and storage zones illustrated in Figures 4.13 and 4.1417 can
be used to understand the advantages of a flux-based approach.

ge
ent g ed
tio
n pm din
ec elo lea
s d ev e
me me Plum
plu lu
ring rlyp
atu Ea
M

Expanding
dissolved-phase
contaminant plume

Contaminant
source mass,
placed in the
aquifer at t = 0 Location of
“clean water” traveling
Groundwater transport direction
from source at t = 0

FIGURE 4.13  An expanding plume (pre–mass flux reduction), with advective transport in the higher permeability segments
(mass flux zones), which enables faster transport of the contaminant mass. (Modified from Suthersan, S. et al., Ground Water Monit.
Remed., 30(1), 36, 2010.)
118
ion
ec
t elo
s ev
me
plu
ring
atu
M
Contaminant
source mass
removed
Contracting or
detached
dissolved-phase
contaminant
plume
Groundwater transport direction
FIGURE 4.14  A contracting plume (post–mass flux reduction), with higher concentrations now present in the low-permeability areas in
the source zone. (Modified from Suthersan, S. et al., Ground Water Monit. Remed., 30(1), 36, 2010.)
Figure 4.13 shows an expanding plume at three transects at dif-
ferent distances from the source: the leading edge, early plume
development, and maturing plume, with relative concentration
shown in a pink to red color scale. As the plume travels from
the source, flow is concentrated in the most permeable aquifer
segments, but mass also diffuses into the matrix around these
most permeable aquifer segments. This diffusive mass trans-
fer retards the plume advancement, which results in a “clean
water” front that travels farther than the fast-moving, concen-
trated plume. In Figure 4.14, the same conditions and conven-
tions are used, but now the contaminant source mass has been
removed. Upon source removal, the most permeable aquifer
segments near the source clean up first, but the mass that has
diffused into storage remains as a long-term source.
The continuum of maturity along a plume from the source
to the leading edge may support the application of different
characterization and remedy strategies in different portions of a
plume.17 The leading edge of a plume is where dissolved phase
mass flux mapping is the preferred characterization method and
where pump-and-treat remedies may be applied cost-effectively.
Closer to the source, relatively high concentrations may persist in
the mass storage zones even after successful initial remediation
of the mass flux zones. In the source zone, it is difficult to map
mass using the same methods as the leading edge of a plume,
as the mass resides in low-permeability zones that are difficult
to sample using groundwater vertical aquifer profiling. Instead,
the preferred characterization method is whole-core saturated
soil (WCSS) sampling, which directly measures stored mass.
Following aggressive source treatment, diffusive mass trans-
fer from storage zones can result in significant “rebound”, so at
least some treatment of mass storage zones may be necessary to
achieve meaningful mass flux reductions. Mass storage zones
are hydraulically inaccessible; therefore, treatment of these
zones by injected fluid-based techniques requires adequate con-
tact time and longevity of in situ chemical or biological treat-
ment processes as discussed in Chapter 6.
Remediation Engineering
nt ge
e g ed
pm din
ea
el
me
d m
lu Plu
rlyp
Ea
Location of
“clean water”
traveling from
source at t = 0
4.4  SITE CHARACTERIZATION
With the advent of remediation hydraulics, it became neces-
sary to rethink how we investigate sites. Smart Characterization
methods are now favored in place of traditional methods, as they
integrate dynamic, real-time, high-density soil, and groundwater
sampling with hydrostratigraphic interpretations and permeabil-
ity mapping in three dimensions.18 By correlating high-resolu-
tion concentration data with hydrostratigraphy and permeability
data, it is possible to map and distinguish contaminant mass
transport zones from mass storage zones. This approach enables
real-time classification of the scales of variability that control
mass transport in the source and distal segments of ground-
water plumes. This mass flux–based perspective is the founda-
tion of the Smart Characterization approach. When the Smart
Characterization approach is applied in the proper framework, it
helps to significantly reduce the life-cycle remediation costs and
provide a return on investigation (ROI).
4.4.1 Limitations of Traditional Site
Investigation Methods
Traditional site investigation methods rely on a linear process of
iterative work plans, soil and groundwater sampling, geologic
and hydrogeologic testing, and analysis of data and reporting.18
The typical approach might include soil borings with interval
split spoon soil sampling to evaluate stratigraphy and soil con-
taminant concentrations above the water table, less frequent
split spoon sampling of soil beneath the water table to evaluate
soils and hydrostratigraphy, and much less frequent groundwa-
ter sampling via monitoring wells, which are often placed at
arbitrary depth intervals in thick aquifers (e.g., at the water table
and middle and bottom of the aquifer). Historical approaches to
site characterization tended to artificially separate soil sources
from groundwater impacts, unless light or dense nonaqueous
phase liquids (LNAPLs or DNAPLs) were  present. This was
Remediation Hydrogeology
Nested wells
Nondetect
50 ppb Inferred plume from monitoring wells (50 ppb)
Nondetect
High-resolution boring
ND
ND Actual plume
1000 ppb
5000 ppb
1000 ppb
ND
FIGURE 4.15  A comparison of plume characterization using monitoring wells and high-density vertical aquifer profiling from a site
where a 5,000 ft long TCE plume was missed by the conventional approach.
mainly because regulatory frameworks often required separate
regulated units for soil and groundwater. As a result of soil reg-
ulatory limits based on the risk of leaching to groundwater, soil
contamination sampling was limited to the vadose zone, while
groundwater and NAPLs were evaluated using monitoring
wells. Historically, significant emphasis was placed on preci-
sion of the testing and laboratory methods to ensure reproduc-
ibility of groundwater samples. The unintended consequence
has been to limit the number of well locations due to the cost
associated with rigorous laboratory quality assurance. As a
result, practitioners were often forced to make CSM interpreta-
tions based on sparse data, with limited horizontal and vertical
resolution that often lacked important geologic and hydrogeo-
logic context necessary to accurately interpret the data. This
skewed our perspective on sources and source behavior and
limited our ability to develop reliable remedial strategies to
cost-effectively meet groundwater cleanup objectives.
Monitoring wells are the most commonly applied site inves-
tigation tool. The primary limitation of relying on conventional
monitoring wells for groundwater investigations is that they
simply provide a transmissivity-weighted average dissolved
phase concentration that reflects the influence of the most per-
meable segments within the screened interval.9 While wells
are ideally suited for reproducibility, they often provide an
inaccurate assessment of dissolved-phase distributions at the
fine scale within a screened interval. Facies-related changes
119
Water level
Flow
Water level
Previously inferred
50 ppb plume contour
in permeability can lead to several orders of magnitude vari-
ability in concentration over less than a meter.19 Figure 4.15
shows a comparison of plume characterization using monitor-
ing wells and high-density vertical aquifer profiling from a
site where a 5000 ft long TCE plume was missed by the con-
ventional approach. While the data from the monitoring wells
were precise and reproducible over many rounds of sampling,
the result was not representative of site conditions because the
arbitrary well placement missed the core of the plume that was
later mapped with vertical aquifer profiling. The lesson learned
is that monitoring wells are reliable for monitoring, once the
geometry and distribution of the plume has been determined
through appropriate sampling.
Additionally, wells provide little or no direct information
regarding the presence and amount of nonaqueous, sorbed,
or vapor phase contaminants; nor can they elucidate the dis-
tribution and mass stored in less permeable storage zones.9,20
The limitations of the conventional approach is obvious when
one considers the challenges of using monitoring wells to
accurately characterize the vertical distribution of LNAPL
mass in the context of a fluctuating water table. The Interstate
Technology and Regulatory Council’s and ASTM’s approach
to LNAPL CSMs have shown that “measured” LNAPL thick-
nesses in wells depend on the maturity of the release and
water table fluctuations relative to hydrostratigraphy and well
screen placement.21,22 This approach has correctly shifted our
120
perspective from LNAPL distribution similar to pancakes,
with uniform NAPL floating on the water table, to shark fins,
with vertical variations in NAPL saturation based on water
table fluctuation and hydrostratigraphy. It is important to note
that LNAPL accumulation in a well is only part of the story,
much like dissolved phased concentrations are in monitoring
wells. If one understands the distribution of mass relative to
hydrostratigraphy before the well is installed, mobility and
migration assessments will be much more effective and reli-
able. Similarly, the better definition of potential exposure path-
ways will also help in the evaluation of risk-based methods to
determine whether LNAPL management is a cost-effective
and equally protective solution instead of active remediation.
4.4.2 Smart Characterization: A New
Way of Investigating Sites
The Smart Characterization approach utilizes new high-res-
olution tools in a technical and economic decision making
framework designed to maximize the ROI through reduced
total cost of remediation, better definition of uncertainty and
risk, and understanding achievable end points before remedia-
tion commences.18 The Smart Characterization tools described
in the following sections are geared toward providing quantita-
tive mappings of the distribution of relative permeability and
contaminant concentrations in real time and at high resolution,
thus enabling development of 3D, flux-based CSMs. The key
is to select the right tools to ensure that the data collected will
meet the data quality objectives of the project. Screening level
tools are appropriate for source prospecting but are not likely
to enable delineation to meet groundwater quality standards.
Conversely, quantitative sampling at the outset of a new proj-
ect when little is known about potential sources can be cost
prohibitive and inefficient. The bottom line is that investments
in Smart Characterization may be one of the most powerful
economic tools we have today to continue to improve the reli-
ability and cost-effectiveness of remediation projects.
Traditionally, high-density sampling and high-resolution
site characterization are largely viewed as synonymous with
high cost investigations. The reality is that it is fundamentally
cheaper and more reliable to use Smart Characterization to
map a plume and develop a quantitative CSM that focuses the
remedy on the mass that matters than it is to develop a remedy
based on an inaccurate site understanding. Smart character-
ization leads to ROI because our experience has found that
the majority of the mass that moves is concentrated in a rela-
tively small portion of impacted aquifers. Understanding how
the mass in the transport zones interacts with storage zones
enables one to focus on the mass that matters most. Targeting
transport zones for remediation increases mass removal effi-
ciencies and reduces the duration of remedies, so that poten-
tial risks can be addressed more quickly and cost-effectively.
Knowing whether mass reduction in storage zones will reduce
mass flux or reduce cleanup time is critical in determining if
it is technically feasible and economically viable to do so or
whether a management strategy is a better allocation of lim-
ited remediation dollars. The ROI that can be achieved from
Remediation Engineering
the implementation of Smart Characterization methods can
be measured in three primary ways:
1. First, high-resolution mapping of contaminant
concentration, hydrostratigraphy, and permeabil-
ity enables quantitative CSMs, where contaminant
transport is defined based on reliable plume geom-
etry, flux, and maturity.
2. Second, Smart Characterization reduces overall site
investigation costs through dynamic planning and
stakeholder engagement and minimizes the repeated
cycle of work plan, investigation, and reporting. In
addition, the number of monitoring wells is signifi-
cantly reduced, which also reduces long-term moni-
toring costs.
3. Third, the flux-based approach focuses remedies on
the mass that matters, maximizing treatment effi-
ciencies and minimizing total life-cycle cost. Smart
characterization enables plume maturity evaluations
by quantifying the interaction between mass storage
and mass transport zones. This enables the optimiza-
tion of the remedy at different segments of the plume
and establishes reliable end points and period of per-
formance before design and construction.
4.4.2.1  Permeability Characterization
The geology comprising most sites is complex, and tradi-
tional approaches to permeability characterization are insuf-
ficient to enable interpretation of the flow and transport
pathways. Traditionally, geologic logging and soil classifi-
cation are completed using the Unified Soil Classification
System (USCS), which was developed by engineers with
the intent of understanding the geotechnical properties of
soil. Because the USCS approach is based on engineering
properties instead of sedimentary processes, it lumps soils
in broad categories that provide little insight regarding the
permeability of the soils or the hydrostratigraphy at these
sites. USCS descriptions often broadly group the soils, with
limited emphasis on the depositional elements and facies
trends that are diagnostic of the aquifer architecture and are
critical in interpreting the lateral and vertical connectivity of
the most permeable units where transport occurs. In contrast,
Smart Characterization methods provide high-resolution,
quantitative data on aquifer permeability and can generally
be divided into methods that provide a continuous, high-
resolution record of relative aquifer permeability or ­methods
that provide a discrete (not continuous) lower-resolution
record of absolute aquifer permeability. There is no “perfect”
method that will work at all sites; every site presents a unique
set of data quality objectives that must be used to tailor the
ideal characterization strategy.
4.4.2.1.1  Permeability Profiling Methods
Cone Penetrometer Testing  Cone penetrometer testing
(CPT) methods have been used for decades in the geotech-
nical and environmental industries. While CPT methods
were originally developed for geotechnical applications,
Remediation Hydrogeology 121

the Department of Defense Site Characterization and
Analysis Penetrometer System program lead to more wide-
spread application in the environmental industry.23 During
CPT, a cone is pushed into the subsurface and the resulting
soil behavior is logged, without physically retrieving a soil
sample. The CPT soil behavior parameters are collected at
high resolution (measurements approximately every 1 in.)
and include tip stress (resistance to penetration), sleeve fric-
tion (friction along the wall of the cylinder of the probe),
and pore pressure (hydrostatic pressure surrounding the
probe). CPT is a useful method for mapping hydrostratigra-
phy, because the method discriminates between transport
zones (sands and gravels) and storage zones (silts and clays)
due to the way the sensors respond to soil characteristics.
For example, tip stress generally correlates with increas-
ing grain size, and pore pressure will track the hydrostatic
pressure gradient in higher permeability sands and grav-
els that readily dissipate the pore pressure increase caused
by the advancing probe. Therefore, portions of a CPT
boring with high tip stress and pore pressure near hydro-
static can be interpreted as higher-permeability transport
zones, while portions with low tip stress and excess pore
pressure can be interpreted as lower-permeability storage
zones. An additional benefit of CPT is the availability of
supplemental tools that can be added to the CPT to allow
screening level assessments of water quality (laser-induced
fluorescence [LIF] for aromatic hydrocarbons, membrane
interface probe [MIP] for a variety of volatile organic com-
pounds, as shown in Figure 4.16).
One of the most common methods for interpreting CPT
data is to use the soil behavior type methodology.24–26 The soil
behavior type is an empirical calculation of soil type based on
a simple chart that plots the tip resistance and friction ratio.
While the soil behavior type classification chart is useful as a
frame of reference, the divisions are generally more applica-
ble to engineering classification than hydrostratigraphy.9 We
favor making manual correlations of the CPT parameters to
develop site-specific interpretations.
The utility of the CPT logging technique is that, once cali-
brated to site conditions, it is possible to use the tip stress, sleeve
friction, and pore pressure responses in the vertical profile to
identify storage and transport zones and use the supplemental
contaminant profiling tools to map relative mass flux in a single
boring. Figure 4.16 shows a CPT log where the CPT parameters

CPT tip stress (tsf) CPT pore pressure (psi) MIP log
0

10

20
Depth (ft)

30

40

50

60
0 100 200 0 10 20 30 40 50 1e+6 1e+7
Tip stress (tsf) Pore pressure (psi) ECD detector (μv)

FIGURE 4.16  Example of high-resolution stratigraphic mapping using cone penetrometer testing (CPT) and membrane interface probe
(MIP) with an electron capture detector (ECD) for chlorinated solvents in a source zone. The panels on the left and center show CPT pore
pressure and tip stress sensor readings that were used to interpret relative permeability. The shaded area represents a low-permeability
interbedded sand–silt–clay zone. The panel on right shows elevated MIP ECD response in interbedded zone, which was shown to contain
several hundred parts per million total VOCs. Sands above and below show concentrations are 1–2 orders of magnitude lower. Based on
permeability and mass distribution, more than 90% of the contaminant mass is contained in a low-permeability zone that contributes less
than 10% of the groundwater flow. (After Suthersan, S. et al., Ground Water Monit. Remed., 30(1), 36, 2010.)
122
have been interpreted into a sequence that includes a shal-
low and deep sand unit, separated by an interbedded zone of
silts, clays, and sands.17 Contaminant concentrations collected
through groundwater vertical aquifer profile sampling and MIP
discussed in a later section profiling indicated that the highest
contaminant levels are present in the low-permeability inter-
bedded zone (several hundred parts per million), while concen-
trations in the sand units above and below were 10–100 times
less. The result is that over 90% of the contaminant mass is
present in a zone that is responsible for less than 10% of the
mass flux.17 Therefore, the geometry of the low-permeability
storage zone was critical to map in three dimensions, as it was
the primary reservoir for contaminant mass.
Direct-Push Injection Logging Tools  Direct-push injection
logging (DPIL) tools are similar to CPT, as they also provide a
continuous profile of relative soil permeability at the centimeter
scale. There are two commonly used DPIL tools: the Waterloo
Advanced Profiling System (APS) by Stone Environmental/
Cascade Drilling and the hydraulic profiling tool (HPT) by
Geoprobe Systems. Both tools provide a profile of relative per-
meability that can be used to correlate hydrogeologic units across
a site and be used as a guide for conducting groundwater sam-
pling. The tooling is advanced through an aquifer using a stan-
dard direct-push drilling rig. The DPIL equipment is attached
at the end of a drill string and enables a continuous metered
injection of small volumes of water (typically between 200 and
Corrected HPT press.
(psi)
0
5 Sand to silty sand
10
15
20
25
Low-permeability
clay and silt
Depth (ft)
30
35
40
45
High-permeability
50 coarse sands
55
60
Low-permeability
65
clay aquitard
0 50 100
FIGURE 4.17  Example hydraulic profiling tool (HPT) data, show-
ing elevated HPT pressure in the low-permeability clay and silt and
no excess HPT pressure in the higher permeability coarse sand.
Remediation Engineering
300 mL/min) during advancement of the probe. At the same
time, the fluid back pressure due to injection into the formation
and the flow rate are measured and logged at a high frequency.
The changes in flow and pressure are proportional to the aquifer
relative hydraulic conductivity: low-permeability zones corre-
late to increased pressure/decreased flow and high-permeability
zones correlate to decreased pressure/increased flow.
An example of HPT data is shown in Figure 4.17. Note in
Figure 4.17 that in the permeable transport zones, little to no
pressure is built up, while in the lower-permeability storage
zones, pressures are elevated. Similar to CPT, responses must be
calibrated against continuously sampled soil borings to ensure
accurate interpretation. We recommend completing these cali-
bration borings at the beginning of each investigation, so that
the hydrofacies present in the continuously sampled boring can
be identified in the DPIL curves.
DPIL is a valuable tool in the Smart Characterization tool-
box, because it provides high-quality, high-resolution data on
one of the key parameters in remediation hydraulics: the aqui-
fer’s capacity to transmit water. Because of the simplicity of
interpretation of DPIL data, DPIL tools are gradually replacing
CPT for many sites as the preferred method of permeability pro-
filing. However, both tools are only applicable within a specific
window of permeability ranges—the range for CPT is generally
around 10 –5 to 10 –3 cm/s and for DPIL is generally around 10 –4
to 10 –2 cm/s. Future versions of the DPIL may bridge the divide
between relative-continuous permeability and absolute-point
permeability: an advanced version, which can conduct point
permeability injection tests to measure an absolute K, has been
developed27,28 but is not yet commercially available.
4.4.2.1.2  Point Permeability Methods
High-Resolution Direct-Push Slug Testing Hydraulic
­testing using slug tests is a well-established method for mea-
suring permeability.29 Slug tests provide data more consistent
with the remediation hydraulics paradigm, because they are
of a shorter duration than a typical pumping test. Large-scale,
long-term, steady-state pumping tests result in an average per-
meability for the portion of the aquifer providing water to the
pumping well during the test. As such, a long-term pumping
test will be biased low with respect to the mobile porosity,
whereas short-term tests like slug tests allow better isolation
of hydrostratigraphic units where the majority of mass flux
is present.9 The traditional approach to slug testing is to con-
duct the testing at permanent monitoring wells, but this only
provides a single permeability estimate for the entire aquifer
thickness at the location. For sites where the vertical changes
in permeability are important to capture, it is possible to con-
duct slug tests at multiple depth intervals during drilling using
a temporary screen point. An example of the result of this
method is shown in Figure 4.18. The value of high-resolution
slug testing is clear when compared to traditional slug tests
on a permanent well. If the location shown in Figure 4.18 had
a permanent well screened from 100 to 110 ft, the traditional
slug test at the permanent well would only see a single value
for permeability, but the permeability across the well screen
varies by 4 orders of magnitude.
Remediation Hydrogeology
20
30
40
50
60
Depth (ft)
70
80
90
100
110
120
1.00E–05 1.00E–04 1.00E–03
Permeability (cm/s)
FIGURE 4.18  Example of high-resolution slug testing profile, showing approximately 4 orders of magnitude variation.
Grain Size Analysis  Another method for estimating perme-
ability at a specific depth is to use high-resolution sieve data
to correlate hydrostratigraphic units and permeability. It is
important to target sample collection from the different hydro-
stratigraphic units present at the site rather than composit-
ing or collecting samples that span different units. Laboratory
sieve analysis should be run using sieves that correspond to the
Udden–Wentworth classification approach rather than with the
minimal number of sieves associated with a basic USCS clas-
sification. In lower-permeability zones with silt and clay, meth-
ods like Shelby tube sampling and permeameter analysis can
provide quantitative data on storage zones. Once the data are
collected, there are several empirical formulas that provide a
reliable means of estimating hydraulic conductivity from grain
size distribution data, provided that the formation does not con-
tain abundant fines, which result in cohesive or plastic behavior
or cobble-sized grain size distributions.30 A valuable addition
is the availability of simple programs for evaluating grain size
distribution and estimating permeability by various methods.31
4.4.2.2  Concentration Mapping Tools
There are a variety of different Smart Characterization tools for
mapping contaminant concentrations”. Some methods like verti-
cal aquifer profile sampling or sampling from a DPIL tool provide
high-resolution, quantitative groundwater concentrations. Other
methods like MIP provide high-resolution, qualitative screening
data on bulk dissolved phase concentrations. And finally, WCSS
sampling is a method that measures the total mass in a storage
zone, which makes it well suited for source zone investigations.
4.4.2.2.1  Vertical Aquifer Profile Sampling
Vertical aquifer profile sampling is a family of methods that are
used to collect discrete, vertically dense groundwater samples
during drilling activities. The different methods all use some
123
1.00E–02 1.00E–01 1.00E–00
type of discrete screen or sample interval that can be advanced
into the subsurface during drilling activities, and groundwater
is collected from the device. It is outside of the scope of this
book to describe each potential drilling method and sampling
process, but Table 4.1 presents some of the potential options
based on site conditions and drilling methods.
Some of the DPIL methods covered in the earlier section on
permeability profiling are also capable of groundwater vertical
aquifer profile sampling. The Waterloo APS is able to pause at
prescribed depths, reverse the flow of water, and collect ground-
water samples directly into VOA vials in-line with the APS
tooling. Similarly, Geoprobe produces a modified HPT, called
an “HPT–GW,” which is capable of collecting groundwater
samples. Both of these methods are better suited for sites with
permeable geology where groundwater samples will be easy to
collect from the relatively small screen interval of the tools.
Case Study  Permeability profiling and VAP sampling
were applied at a site with a pump and treat system with
more than 20  years of operation with likely another
20–30  years of pumping remaining.18 The key question
was whether the capital investment related to expanded
source treatment would meet the business objectives of
the organization. A Smart Characterization program was
applied with exit ramps to evaluate whether the groundwa-
ter extraction system could be optimized. While the tra-
ditional characterization based on concentration indicated
widespread impacts, the Smart Characterization mapped
mass flux that was found to be concentrated in a small seg-
ment of the aquifer cross section (Figure 4.19). Evaluation
of the mass flux transect downgradient of the source
area cost $100,000 based on the difficult drilling condi-
tions but showed that moving the existing pumping well
would enhance capture of contaminant mass and decrease
124 Remediation Engineering

TABLE 4.1
Drilling Methods and Groundwater Sampling Approaches
VAP Sampling Method
Drilling Depth (ft) Drilling Method Example Relative Cost Notes
<50 Small direct-push machine Screen point $ Relatively fast method for shallow systems; limited
(e.g., Geoprobe 6620) by cobbles, till, bedrock. Small footprint.
<100 Larger direct-push machine Screen point $$ Similar to small direct-push speed and limitations.
(e.g., Geoprobe 8040)
<150 Minisonic Push-ahead sampling $$$ Uses dual casing to reach target depth, sealing off
devices borehole.
May require addition of water during drilling, which
can affect subsequent groundwater sample integrity.
>150 Full-sized sonic Sonic: push-ahead $$$$ Similar limitations to minisonic.
sampling devices
Large footprint (requires support vehicle).
>500 Rotary methods Rotary: hydropunch $$$$$ Unlike the previous methods, a high-quality
sampler inside of drilling continuous soil core is not generated. Soil types and
equipment relative permeability data are obtained through
cuttings, split spoon sampling, or borehole
geophysics following completion of the boring.

the long-term operation (Figure 4.19). A second stage of
Smart Characterization was then applied to evaluate the
viability of potential source treatment and found that while
source treatment was viable, the payback period was too
long relative to the responsible party’s cash flow stream for
the current groundwater extraction system. An optimized
pumping well limited the capital costs compared to the
aggressive source treatment strategy and the ROI on the
“Smart Characterization” was gained by the significantly
increased capture of contaminant mass and the resulting
reduction in operational costs, due to the overall improve-
ment of system performance.
4.4.2.2.2  Membrane Interface Probe
Geoprobe Systems’ MIP is a direct-push investigation tool that
is designed for rapid, screening level evaluation of volatile con-
taminants in the vadose and saturated zones.32 The probe con-
sists of a semipermeable membrane, a heater block, inert tubing/
carrier gas stream, a series of detectors (up-hole), and typically
an electrical conductivity sensor for relative soil type mapping.

1025

1000

975
Elevation (ft)

950

925

900

0 50 100 150 200 250 300

Distance (ft)

FIGURE 4.19  Mass flux transect for case study. Colored plume shows the zone where the majority of the CVOC flux is occurring; gray-
outlined area represents approximate extent of CVOC concentrations.
Remediation Hydrogeology
The probe works by heating the soil to induce volatilization of
contaminants from the soil and diffusing contaminants across
the membrane, into the carrier gas line, where the gases are
carried up-hole to the detectors—commonly a photoionization
detector for aromatic compounds like BTEX, a flame ioniza-
tion detector for general hydrocarbon detection, and either an
electron capture device (ECD) or a halogen specific detector for
chlorinated VOCs.33,34
Since the mid-1990s, the MIP has been used to qualita-
tively screen and map the distribution of volatile contaminants,
including petroleum hydrocarbons and chlorinated volatile
organic compounds, at hundreds of sites in the United States.
The MIP represented a major leap forward in VOC plume
characterization, as for the first time we were able to iden-
tify significant mass stored in low-permeability zones.20 Later
enhancements to the MIP, such as the halogen-specific detec-
tor and the combination with an HPT probe to simultaneously
map VOCs and relative permeability, made the tool even more
useful. While these improvements to the MIP are valuable, our
experience has found that MIP should be used for screening-
level applications and not applied as a quantitative tool to map
groundwater concentrations at the MCL, or to design remedies.
This is because there are a number of different factors that can
influence the response of the MIP,35 and because of these fac-
tors, MIP is best applied as a screening tool.20,36
MIP will continue to be an important method in the Smart
Characterization toolbox. However, each site requires a care-
ful look at data quality objectives to define the ideal approach.
In simple terms, if one imagines a DNAPL source zone as a
fire and the downgradient plume as the smoke, MIP sees the
smoke but not the fire. Therefore, for large sites with limited
PCE soil concentration (μg/kg)
1,000,000
2,000,000
3,000,000
4,000,000
5,000,000
0
29.0
29.5
30.0
30.5
Depth (ft bgs)
31.0
31.5
32.0
32.5
33.0
FIGURE 4.20  Data from a whole-core saturated soil sampling source zone investigation where concentrations changed by orders of mag-
nitude over very small vertical distances—changes that would have been missed if traditional methods were being used.
125
subsurface data, MIP may be an excellent method to screen
large areas to find the “smoke” coming off of source areas and
then zoom in later with more quantitative methods, like WCSS
sampling (discussed in the next section). If using MIP, it is
always prudent to systematically evaluate the MIP response
at each site and when geologic conditions or composition of
contaminant mixtures change across a site.
4.4.2.2.3  Whole-Core Saturated Soil Sampling
WCSS sampling, which consists of collecting vertically dense
soil samples below the water table and analyzing the total con-
taminant mass present, is frequently the preferred characteriza-
tion approach in low-permeability source zones. Groundwater
vertical aquifer profile sampling in source zones provides high-
quality, quantitative data but is typically a time-consuming
process due to the low-permeability soils commonly present.
The MIP provides data much faster than vertical aquifer profile
sampling but provides qualitative data only as discussed in the
previous section. WCSS is often the best method for character-
izing source zones because it provides the best of both worlds:
rapid and quantitative data. When investigating a source zone
with WCSS, samples may be collected at intervals as small
as 1 or 2 ft to accurately identify the zones where the high-
est concentrations are present. Figure 4.20 shows data from a
WCSS source zone investigation where concentrations changed
by orders of magnitude over very small vertical distances—
changes that would have been missed if traditional methods
were being used. In a 2 ft interval concentrations changed by
4 orders of magnitude, from 11 to 6,500,000 ppb, and then 2 ft
later concentrations had dropped by over 5 orders of magni-
tude, down to <5 ppb. To capture this critical vertical variation,
6,000,000
7,000,000
Competent till
Sand
Competent till
126
MIP detector responses (µV)
1.E + 05 1.E + 06 1.E + 07
0 0
10
Depth (ft)
20
30
ECD
PID
FID
40
(a)
FIGURE 4.21  The difference between the qualitative data of the membrane interface probe (MIP) and the quantitative data of the whole-
core saturated soil (WCSS) approach. The figure is showing co-located borings in a chlorinated VOC source where MIP and WCSS were
both completed; (a) shows the MIP detector responses and (b) shows the co-located whole-core saturated soil samples zone.
a typical source zone investigation may result in hundreds of
samples, which makes the WCSS approach ideally suited for
use of a specialized, high-throughput mobile lab, which can
cost-effectively analyze 50 or 100 samples per day.
Figure 4.21 illustrates the difference between the qualita-
tive data of the MIP and the quantitative data of the WCSS
approach. The figure is showing vertical profiles of co-located
borings in a chlorinated VOC source zone where MIP and
WCSS were both completed; the left side of the plot shows the
MIP detector responses and the right side of the plot shows
the co-located saturated soil sample concentrations. As illus-
trated in the figure, the ECD detector is at its maximum value
for most of the boring, but the WCSS data i­ndicate that there
is significant variability across the boring. The PID and FID
detectors correlate slightly better with the WCSS data, with the
detectors reaching peak value at the same depth as the WCSS
peak concentration. The bottom five feet of the boring has low
concentrations in the WCSS sample, but the PID, FID, and
ECD detectors show no significant difference from the interval
around 18 ft bgs where the highest concentrations were present.
An added bonus of the WCSS approach is the ability to add
dye testing to screen for the presence of DNAPL, which was
detected in the sample with the highest concentrations. By con-
ducting dye testing to screen for DNAPL, it was also possible to
identify the presence of DNAPL at around 18 ft.
4.4.2.2.4 Laser-Induced Fluorescence
NAPL Mapping Tools
Conventional approaches (like using monitoring wells) to
map the extent of both LNAPL and DNAPL provide low-
resolution data that fail to accurately map the heterogeneous
Remediation Engineering
Mobile lab whole‐core soil TCE
concentration (mg/kg)
1.E + 08 0 2000 4000 6000 8000
10
Positive
NAPL result
20
30
40
(b)
extent of NAPL in the subsurface and fail to reveal the loca-
tions of NAPL at residual saturations that can serve as long
term sources. The family of LIF tools provide high-resolution,
real-time information on the extent of NAPL. LIF is a tech-
nique that uses laser light to excite fluorophores—fluorescent
molecules—that exist in NAPLs such as petroleum fuels/
oils, coal tars, and creosotes. The NAPL’s inherent fluores-
cence can be logged with depth at high resolution to map the
extent of NAPL. As with any Smart Characterization tool,
it is important to match the project data quality objectives
with the proper tool, as there are different versions of LIF for
petroleum-range LNAPLs, tars, and chlorinated DNAPLs.
LIF Overview  The most widely applied version of LIF con-
sists of a probe with a clear sapphire window that is pushed
through the soil column by either direct push or CPT. As this
sapphire-windowed probe is advanced steadily into the soil
column at approximately 2 cm/s, pulses of laser light are sent
down the rod string via fiber optic, where they exit the sap-
phire window and shine onto the soil passing the window. A
portion of the resulting fluorescence and/or scattered laser
light that comes back into the window is brought up-hole by
a second fiber, where the light is processed and analyzed in
real time. The logs indicate in real time where NAPL fluores-
cence is occurring, with major differences in the fluorescence
color and lifetime due to differing NAPL types, weathering,
or false positives.37 Different versions of LIF are available,
including rapid optical screening tool (ROST®™), ultraviolet
optical screening tool (UVOST®), and the fuel fluorescence
detector (a similar optical technology but not laser-based).
There is also a version of LIF designed specifically for coal
Remediation Hydrogeology
Depth (ft)
0.0
Waveforms
100
80 5.0
60
40
20
4.24–5.16 ft 10.0
32.2% RE (s 20.2)
15.0
20
15
10
5 20.0
17.51 ft
15.6% RE
FIGURE 4.22  Example laser-induced fluorescence log. (From Randy St. Germain, personal communication.)
tars and creosote NAPLs that have heavier PAHs relative
to petroleum LNAPL, called the tar-specific green opti-
cal screening tool (TarGOST®).38 The primary difference
between LIF for petroleum-range NAPL and coal tar/creosote
NAPL is the wavelength of the laser—LIF designed for petro-
leum NAPL typically has a laser wavelength between 280 and
310 nm, while LIF designed for coal tars and creosote NAPL
has a longer wavelength of over 500 nm. Additionally a new
LIF-style probe has recently been developed by Geoprobe
Systems, called the Optical Image Profiler (OIP), which
works by inducing fluorescence through ultraviolet light, and
the resulting fluorescence is captured by a down-hole camera.
As of writing, the OIP is not widely available.”
An example LIF log is shown in Figure 4.22. In the main
window of the log, total fluorescence versus depth is logged
and colored based on the relative contribution of different
wavelengths of fluorescence, which can be diagnostic of the
type of NAPL. Depth specific callouts to the left of the main
plot contain both spectral and temporal fluorescence data that
provide additional information on the relative contribution
and lifetimes of the different wavelengths of fluorescence.
The value of LIF for LNAPL characterization is illustrated
in Figure 4.23. The monitoring well shown in the figure regu-
larly contains over 10 ft of LNAPL. However, the UVOST
boring advanced directly next to the well (within 3 ft) indi-
cated only a thin seam of LNAPL is present in the formation.
Other UVOST borings in the area showed the same pattern,
127
Signal (% reference
emitter) 350 400 450 500
with an approximately 1 ft thick LNAPL zone in the forma-
tion. Figure 4.23 also demonstrates how LIF provides a rich
dataset that can be used for more than simple indications of
thickness. The shallow portion of the UVOST boring shows
a fluorescence response similar in magnitude to the LNAPL
seam at depth. However, because the LIF instrumentation
records both fluorescence magnitude and the underlying
waveform, it is possible to screen out false positives, such as
the shallow response on the log, which has a different wave-
form than the LNAPL at depth and was instead found to be
related to shallow roadbed fill material in the area.
LIF for Chlorinated DNAPL Mapping  LIF as discussed in the
previous section is a successful, mature technology, with wide
application for mapping NAPL. However, LIF was limited only
to petroleum LNAPL and tar-based DNAPLs until the recent
development of the dye-enhanced laser-induced fluorescence
(DyeLIF) by Dakota Technologies. DyeLIF combines standard
LIF technology with injection of a fluorescent dye ahead of
the LIF window to render nonfluorescent NAPLs fluorescent
in situ.39 The probe functions by injecting an aqueous delivery
fluid containing a proprietary hydrophobic dye through a small
injection port that is situated below the LIF window. As the
probe is advanced through the subsurface, the injected dye con-
tacts the soil and quickly partitions into any DNAPL present.
A slightly modified TarGOST is used to detect the fluorescence
of the dye-labeled chlorinated solvent DNAPL. An additional
128
Depth (ft) Signal (% reference
emitter) 350 400 450 500
0
5.0
10.0
15.0
20.0
LNAPL
thickness
25.0 in well
30.0
LNAPL
thickness in
35.0 formation
40.0
45.0
0.0 5.0 10.0 15.0
FIGURE 4.23  Comparison of laser-induced fluorescence and
monitoring well data. The monitoring well shown in the figure regu-
larly contains over 10 ft of light nonaqueous phase liquid (LNAPL).
However, the ultraviolet optical screening tool boring advanced
directly next to the well (within 3 ft) indicated only a thin seam
of LNAPL is present in the formation. (From Randy St. Germain,
personal communication.)
benefit of the approach is that the pressure associated with the
injection of the dye is logged during probe advancement and
can be used to interpret changes in relative permeability, simi-
lar to the commonly available DPIL tools in the market. By
simultaneously interpreting both the relative permeability and
the DyeLIF log, it is possible to identify DNAPL presence and
the relative transport potential in the same boring.
LIF Case Study  By applying the correct Smart Characterization
tool, significant ROI savings were achieved at a remediation site
because the Smart Characterization revealed that aquifer volume
with chlorinated solvent DNAPL impacts was significantly less
than the apparent thickness provided by conventional methods.18
Despite 20 years of conventional investigation and monitoring,
the actual thickness and extent of DNAPL in the subsurface was
not clearly identified. Conventional techniques had been used
for site characterization, and wells in the source area contained
up to 8 ft of measured DNAPL. Remedial strategies for manage-
ment of the DNAPL were based on traditional data and were
well in excess of $10M. As a result, a Smart Characterization
approach was implemented to evaluate potential treatment and
management strategies for the DNAPL present at the site.
Remediation Engineering
Using DyeLIF, we were able to delineate the extent of
DNAPL in the source zone in a single mobilization, thanks to
the adaptive strategy and real-time DyeLIF data evaluation.
The DyeLIF data resulted in a significant change to the CSM.
Monitoring wells from the area had up to 8 ft of measured
DNAPL and the adjacent MIP boring indicated the maximum
ECD or PID responses were approximately 5–10 ft thick.
However, DyeLIF borings at the same locations revealed that
the DNAPL in the aquifer is present in thin seams 6–12 in.
thick, as shown in Figure 4.24. The monitoring wells exag-
gerated the apparent thickness due to confined conditions in
the thin sand seams, while the MIP could not resolve the true
nature of the DNAPL distribution. Three-dimensional inter-
pretation of the hydrostratigraphy and DyeLIF results showed
that the actual DNAPL impacted volume in the formation is
almost 99% less than previously believed. The DyeLIF results
were supported by subsequent NAPL bail down and recovery
testing, which suggested that the NAPL was not mobile and
that a risk-based approach to management would be appropri-
ate. The ROI at this site became very clear when less than
$35,000 of DyeLIF reduced the DNAPL impacted volume to
less than 1% of what was understood to be present prior to the
investigation.18
Figure 4.24 also demonstrates that qualitative tools such
as MIP are limited in ability to distinguish NAPL-bearing
zones from high dissolved phase concentrations. LIF is
capable of reliably identifying NAPL-bearing zones, but it is
often not possible to use relative sensor response to differen-
tiate residual from mobile NAPLs. The ideal approach is to
combine LIF with quantitative Smart tools such as saturated
soil sampling and analysis via a high-capacity mobile lab.
This provides quantitative data on the chemical composi-
tion and concentration that is necessary to evaluate poten-
tial remedy options. Screening and quantitative tools can
be combined in phases to develop more quantitative CSMs.
However, it is often more cost-effective to characterize a site
in a single attempt using quantitative data rather than char-
acterize it once with qualitative tools and a second time with
quantitative tools to “calibrate” the response of the qualita-
tive tools.
4.4.2.3  Direct Flux Mapping
One of the foundations of remediation hydraulics is the idea
that mass flux is more important than concentration alone, and
the Smart Characterization tools outlined so far are designed
to map the two most important elements of mass flux: per-
meability and concentration. By mapping permeability and
concentration in high resolution, one can take the product of
the two to evaluate relative mass flux. However, for sites with
monitoring wells installed in the proper locations and depths
in the dissolved phase plume, passive flux meters (PFMs) pro-
vide another way to directly measure mass flux.40–42
Each PFM is a nylon mesh tube filled with a mixture of
sorbent (activated carbon) and tracers (alcohols). PFMs are
designed to fit snugly inside monitoring well screens and pas-
sively intercept groundwater flow. The tracer inside of the
PFM leaches from the sorbent as groundwater flows through
Remediation Hydrogeology 129

Monitoring well MIP DYE-LIF

0 0 0

5 5 5

10 10 10

No DNAPL

15 15 15
Depth (ft)

20 20 20
DNAPL
DNAPL

25 25 25
No DNAPL

30 30 30
1.E+05 1.E+06 1.E+07 1.E+08 2% 4%

Measured ECD response (uV) DYE-LIF signal (%RE)

DNAPL in well PID response (uV) Positive DNAPL
FID response (uV)

FIGURE 4.24  Comparison of dense nonaqueous phase liquids (DNAPL) thickness using dye-enhanced laser-induced fluorescence
(DyeLIF) and monitoring wells. While the monitoring well has approximately 8 ft of DNAPL present and the membrane interface probe
electron capture device sensor indicates an elevated response over approximately 10 ft, the DyeLIF found significantly less DNAPL present
in the formation. (Modified from Suthersan, S. et al., Ground Water Monit. Remed., 35(3), 25, 2015.)

the PFM, and the sorbent inside the PFM retains dissolved 4
contaminants present in the groundwater. After several weeks
inside the monitoring well, the PFM is removed and sampled.
The sorbent is analyzed to determine the mass of the con-
6
taminants retained by the PFM, and the tracer is analyzed to
determine how much tracer is remaining. The mass of con-
taminant on the sorbent is used to calculate a time-averaged
contaminant flux, and the remaining tracer mass is used to 8
calculate cumulative groundwater flux. By inserting baffles
into the PFM prior to deployment, a single PFM can be used
Depth (ft)

to understand the range of mass flux across the well screen. 10

If a transect of PFMs perpendicular to the plume is deployed,
then it is possible to estimate mass discharge of contaminant
rather than just mass flux. Figure 4.25 provides an example 12
profile of mass flux calculated from a PFM.

4.4.2.4  3D Visualization
14
To understand the CSM for a site with Smart Characterization
tools, it is imperative to use a 3D model. The conventional
approach to viewing and interpreting data relies on 2D databox
figures, which were adequate when characterization datasets 16
only consisted of a small number of permanent monitoring 0 500 1000
wells. However, a Smart Characterization project may yield lit- Carbon tetrachloride flux (mg/m2/day)
erally anywhere from hundreds to tens of thousands of individ-
ual measurements, which quickly overwhelm any traditional FIGURE 4.25  Example mass flux data from a passive flux meter,
approach to evaluation. Software like Earth Visualization showing significant variation in mass flux across the well screen.
130
Studio (by CTech Corporation) and RockWorks (by RockWare
software) allow 3D viewing of hundreds of high-resolution
borings simultaneously, as well as construction of 3D solid
models of groundwater plumes and geologic units (see the fig-
ures in Section 4.4.2 for examples of 3D model output).
We recommend that 3D models be employed on more projects
but only by the scientists and hydrogeologists that are building
and testing the CSM. It is now common to see 3D visualization
provided as a commodity service by the vendor when one con-
tracts for MIP or LIF services. While an attractive option, the
resulting narrative has little value without geologic constraints
and human intervention. DNAPL source zones are inherently
complex because subtle variations in permeability have a signif-
icant impact on DNAPL mobility and transport rates in aquifers.
Considering most aquifer systems exhibit more than 3 orders of
magnitude in permeability v­ ariability, it is easy to understand
how 3D DNAPL structure is controlled by aquifer architecture.
Common industry practices for 3D visualization are providing
inaccurate CSMs of DNAPL source zones, because MIP, LIF,
and analytical data are typically contoured independent of the
geology and transport processes.
The key to success is to use the hydrostratigraphy of the site
to interpret the contaminant data before interpolation. We rec-
ommend an approach for plume interpretation that is founded in
the most robust geologic interpretation methods: manual inter-
pretation to constrain the interpolation algorithm combined with
hypothesis testing to verify the accuracy of the result rather than
reliance on the software and automated error analysis.
4.5  CONCEPTUAL SITE MODELS
The ultimate goal of site characterization is to construct a
CSM. The CSM is the most critical piece of information for
any remediation site, as it is the basis for all decisions made
for the site. The following sections describe the core ele-
ments of a CSM, strategies for constructing the CSM, and
case studies demonstrating how to use the CSM to optimize
characterization and remediation approaches. For additional
detail on the CSM process, there are many excellent sources
available.9,40,43,44
4.5.1 Elements of a Conceptual Site Model
A CSM can be constructed by answering the questions of
when, how, what, and where: When and how did contaminants
enter the subsurface? What are the contaminants? Where are
the contaminants in the aquifer today and where will they
travel? While every site will require a unique CSM, in gen-
eral, there will be common elements to all CSMs. In order to
evaluate when and how the contaminants entered the subsur-
face, the facility history and operations must be understood.
The facility history and operations will also help answer the
question what are the contaminants, but additional informa-
tion will be required to understand how the contaminants
behave once they are in an aquifer. Finally, the geology and
hydrogeology must be evaluated on both regional and local
scales to understand where the contaminants are today and
Remediation Engineering
where they will travel in the future. There is no such thing
as a “final” CSM; it is best to consider the CSM a continuous
evolution of our understanding of site conditions. The CSM is
dynamic, and the best CSMs are continually tested, reviewed,
and revised at all stages of the project. Figure 4.26 illustrates
how in the early stages of development the CSM is qualitative
and, as additional data are collected and analyzed, the CSM
progresses to a quantitative framework.
4.5.1.1  Site History and Operations
The history and operations at the site are critical to understand
and to define where potential contaminant sources are located,
as well as when any releases occurred, which allows estimates
of the likely limits on the extent contamination has traveled.
There are many locations that should be evaluated, like where
chemicals were stored, transferred, or used, where wastes were
disposed (infiltration lagoons, etc.), areas of stressed vegetation,
or where documented or undocumented practices could have
led to releases. It is also important to understand if boundar-
ies have changed through time, to better understand if histori-
cal source areas could be present outside of the current area of
the site. Historical aerial photography is now widely accessible
online and can provide valuable interpretive support.
4.5.1.2 Contaminants
Potential contaminants will be related to the site history and
operations established in the first stage of the CSM. The spe-
cies of contaminant are important to identify, as the proper-
ties of different compounds (solubility, vapor pressure, density,
etc.) lead to dramatically different styles of behavior in the
subsurface (see Chapter 2). In addition to common contami-
nants like chlorinated solvents, the next challenge in our indus-
try is emerging contaminants, which are persistent and/or
have potentially deleterious human or ecotoxicological effects.
Notable examples of emerging contaminants include perchlo-
rate, methyl tertiary butyl ether, flame retardants, pesticides,
1,4-dioxane, 1,2,3-trichloropropane, per-/polyfluoro alkylated
substances, and dechlorination/disinfection by-products—all
of which persist in the environment. These groups of contami-
nants may be considered less “mainstream” in terms of the
nature of their occurrence, or because our understanding of
their impacts is still in the early stages of development.
As discussed in Section 4.4.2.4, it is time to move away from
the traditional approaches to contaminant data evaluation, based
on 2D databox figures, which are quickly overwhelmed by the
thousands of individual measurements that can be collected dur-
ing Smart Characterization and toward 3D visualization meth-
ods. Three-dimensional visualization methods provide a way
to fuse together multiple big datasets to gain predictive insights.
Big data fusion is needed because the high-density data collected
must be organized into a stratigraphic flux framework, where
permeability and concentration data are combined to provide an
indication of mass flux. If only groundwater data are considered
and auto-interpolated, the resulting picture provides a distorted
view of the mass distribution in the source zone. Groundwater
sampling is inherently biased toward the most permeable zones
in the aquifer, so in a source zone groundwater sampling misses
Remediation Hydrogeology 131

Remedy completion

Quantitative
Remedy operation
and monitoring

Adaptive design

Design basis

Remedy pilot Injection tracer

testing testing
Data-driven evolution

Remedy selection
Hypothesis testing

Exposure Regulatory
assessment framework

Contaminant mass
transport analysis

Contaminant Superficial flow

distribution mapping characterization

Develop preliminary
conceptual model
Conceptual

Depositional environment Regional hydrogeology

Facility operating history Contaminant release data

Define project objectives

FIGURE 4.26  The process of conceptual site model development, from the initial definition of project objectives through remedy comple-
tion. (From Payne, F.C. et al., Remediation Hydraulics, CRC Press, Boca Raton, FL, 2008.)

a key indicator of plume maturity: mass present in storage
zones and slow advection zones. Thus, in a mature source zone,
groundwater data alone will underestimate contaminant mass. In
contrast, interpolation of groundwater data alone for the down-
gradient leading edge of a plume is also misleading, because
automated interpolation that ignores the permeability structure
will interpolate mass into storage zones even though the mass is
present almost exclusively in transport zones. These limitations
are overcome using big data fusion and interpreting groundwater,
WCSS, and permeability data simultaneously using the concepts
of plume maturity. Most importantly, the interpretations should
be made by a hydrogeologist familiar with the overall CSM.
4.5.1.3 Geology
The geology should be evaluated starting at a regional scale, by
identifying the surficial unconsolidated deposits and bedrock
in the area and their depositional environment. These regional
observations set limits on the aquifer parameters (permeabil-
ity, heterogeneity) that will control contaminant transport at the
site scale. With the regional setting established, the site-specific
expression of the regional depositional environment can be
interpreted. The site-specific expression of the regional depo-
sitional environment is developed with a focus on developing
flux-based descriptions of the different hydrostratigraphic units
(transport, slow advection, and storage zones). Cross sections
should be created that show the thickness and extent of hydro-
stratigraphic units across the site; as with the extent of contami-
nation, 3D visualization models are one of the most powerful
tools available to interpret the site geology, as they can integrate
the contaminant datasets at the same time.
4.5.1.4 Hydrogeology
In the CSM, the hydrogeologic description of the site will
describe how groundwater moves within the geologic units
132
underlying the site. Similar to the geologic evaluation, the
hydrogeology should be evaluated starting at a regional scale,
by identifying the regional discharge boundaries for ground-
water flow and then zooming to the site scale. At the site scale,
the geologic cross sections (or 3D model) developed for the
CSM should incorporate the water elevations. Plan-view water
elevation contours should be developed, but as stated earlier
for concentration contouring, contours must be developed by
a trained hydrogeologist familiar with the CSM. The plan-
view contours can be used to estimate groundwater hydraulic
gradients and groundwater velocities, and the geologic cross
sections can be used to evaluate saturated and unsaturated
formations, whether aquifers are confined and identify trans-
port, slow advection, and storage zones.
4.5.2 Digital CSMs: The Next Frontier
Just as our approach to characterization and remediation
has changed based on our better understanding of contami-
nant transport, so must our approach to building and using
CSMs. The first CSMs developed were essentially static docu-
ments, based on an accumulation of monitoring data. Later,
there was a change from static CSMs to dynamic CSMs, as
CSMs were updated to include performance monitoring data.
Despite this improvement, these CSMs were still “trapped” in
the reporting documents for the site. The next stage of evolu-
tion of the CSM is to the concept of a dynamic, digital CSM.
In this chapter we have described moving from a perspective
based on concentration to one based on mass flux, and the
resulting shifts in our approach to characterize sites (through
high-resolution Smart Characterization). This shift in char-
acterization strategies has meant that we must collect and
analyze “big data” in our CSMs, which is only possible in a
digital CSM, rather than one trapped in a report. These digital
CSMs are more than just adding a 3D model to the CSM: they
enable functional linkage between geospatial data and tem-
poral data. We are able to change how we engage and inform
stakeholders by enabling them to see interpretations as well as
examine the underlying boring logs and sample results, all of
which can be cloud-based and accessed by stakeholders. The
digital CSM is a paradigm shift in how we report: rather than
develop reports with dozens of figures, we are now develop-
ing digital CSMs using 3D models that show all of our data
simultaneously-hydrostratigraphy, permeability, and concen-
trations. Future developments in the technology sector like
augmented reality applications will advance the digital CSM
even further. But already today, application of digital CSMs is
leading to improved performance, cost controls, and regula-
tory engagement on our projects.
4.5.3 Using the CSM to Guide Investigation and
Design and Optimize Remediation Systems
The following case studies are offered as examples of some
of the lessons learned through construction and testing of
CSMs. In the first case study, we see the importance of con-
structing a robust CSM to support a complex investigation
Remediation Engineering
and remediation project that consists of soil and groundwa-
ter impacts in unconsolidated and bedrock units across over
200 acres for a redevelopment deadline of under 2 years. The
second case study shows the importance of critically testing a
CSM, as conventional characterization at the site had missed
a 1 mile long, 10 ppm VOC plume that was revealed by the
Smart Characterization conducted at the site.
4.5.3.1  Case Study 1
The first case study examines three former General Motors facil-
ities that operated on a 250 acre site beginning in the early twen-
tieth century and continuing through 2007 in Lansing, Michigan.
Following decommissioning of the plants and the bankruptcy of
General Motors in 2009, the Revitalizing Auto Communities
Environmental Response Trust was created from the bankruptcy
process to complete the environmental remediation of the site.
A limited site investigation initiated in 2011 identified more than
65 areas of interest (AOIs) that needed to be investigated, includ-
ing two LNAPL areas, a former hexavalent chromium plating
area, and several known issues with VOCs and metals. Due to
an existing agreement with the municipality, the site investiga-
tion was required to be completed in a period of 18 months. The
investigation began in earnest in the spring of 2012.
The Lansing area obtains its drinking water from the
regional bedrock aquifer underlying the site. The site straddles
two wellhead protection areas with numerous municipal water
supply wells located within a half mile. The goals of the inves-
tigation were to assess on-site and off-site risk associated with
the existing soil and groundwater contamination and, most
importantly, determine if soil and groundwater contamination
posed a significant risk to the bedrock drinking water aquifer.
The investigation relied on the use of a Smart Characterization,
real-time adaptive strategy that allowed for rapid characterization
of the AOIs. The real-time results were used to focus the investiga-
tion on areas determined to be of greatest potential risk to off-site
receptors or to the underlying bedrock aquifer. Rather than conduct
a traditional phased investigation with a formal sequence of work
plan, investigate, and report, a dynamic work plan approach was
used that defined the data quality objectives and prescribed deci-
sion rules for adaptively characterizing each AOI. The Michigan
Department of Environmental Quality and other stakeholders were
updated and engaged at key “milestones” during the investigation.
This stakeholder partnership has been key to timely buy-in and
approval of the approach and investigation results.
The adaptive approach implemented a targeted toolkit of
investigation and sampling methods to delineate the nature
and extent of soil, groundwater, and LNAPL impacts at the
site. Three-dimensional analysis and visualization was used
to refine the CSM and guide the ongoing investigation.
The characterization of the hydrostratigraphy was crucial
to understanding the risk to the underlying bedrock aquifer.
HPT was used to produce a continuous profile of relative per-
meability at locations across the site. This understanding of
the hydrostratigraphy was used to focus groundwater sampling
on the transport zones in the aquifer and used as a line of evi-
dence to bolster the CSM. Groundwater was encountered in a
perched zone on top of till, at the base of the unconsolidated
Remediation Hydrogeology
formation at a portion of the site where bedrock was deep, and
in the weathered bedrock zone.
The investigation included approximately 500 soil bor-
ings with the collection of more than 2300 soil samples and
more than 400 vertical aquifer profile groundwater samples to
assess and delineate impacts at 65 AOIs. The initial phase of
the investigation required coordinating up to five drilling rigs
working simultaneously and an on-site mobile laboratory to
analyze the soil and groundwater samples in real time. At each
AOI, a set number of borings were completed to characterize
soil and groundwater impacts, followed by adaptive step-outs
based on the results provided by the mobile laboratory. Based
on the real-time data, sampling grids were optimized to pro-
vide delineation with the smallest number of borings possible.
Two areas of LNAPL were delineated using an adap-
tive grid of more than 80 LIF borings to define the extent of
LNAPL impacts. The qualitative LIF data were used as a basis
for a more thorough LNAPL assessment that focused on the
characterization of LNAPL composition and mobility. The
results of the mobility testing indicated the LNAPL transmis-
sivity was 1–3 orders of magnitude below the threshold the
regulatory agency considered as potentially recoverable. As
a result, a risk management-based remedy was designed to
largely manage the LNAPL in place.
At one location, 1,4-dioxane was detected within the deep
overburden and weathered bedrock beneath an area where the
glacial till had been excavated as part of the plant construction
activities. As a response, a series of deep vertical aquifer pro-
file transects successfully delineated the 2600 ft long plume
at high resolution within a couple of months (Figure  4.27).
Follow-up investigation identified a depleted source in the
perched zone and a relatively small source foot print in the
deep overburden and weathered bedrock.
Lower 1,4-dioxane
FIGURE 4.27  Example of 3D model output from case study 1, showing the groundwater plume mapped during the high-resolution
investigation.
133
Once impacts were fully defined, monitoring wells
were installed in the perched zone, the deep overburden,
and weathered bedrock formations to enable plume sta-
bility and monitored natural attenuation (MNA) analysis.
When sufficient monitoring data were collected, statistical
analysis was used to demonstrate stability of the perched
zone VOC and 1,4-dioxane impacts. Geochemical analy-
sis demonstrated the elevated metals in groundwater were
stable, spatially limited, and the result of minor shifts in
site geochemistry.
The approach led to the successful delineation of 65 AOIs
within a 2-year time period. The high-resolution data collected
for the site demonstrated that impacts are isolated within the
perched zone, deep overburden, and weathered bedrock and
pose little threat to the underlying bedrock; interim ground-
water monitoring activities and several localized investiga-
tions are currently being used to support the CSM. Metals
detected above criteria across the site were shown to be
related to variable geochemistry and not likely to migrate.
Additionally, it was successfully demonstrated that the two
areas of LNAPL are not mobile and have limited recover-
ability. As of 2015, preengineering studies are underway to
develop the final remedy for the 1,4-dioxane plume located in
the weathered bedrock.
4.5.3.2  Case Study 2
In our second case study, we can see the importance of
critically evaluating a CSM and the value of the Smart
Characterization approach. The site is a former manufactur-
ing facility, with an industrial history dating back to the early
1900s. Site activities included but were not limited to former
automotive parts manufacturing and furniture manufactur-
ing, with potential chlorinated VOC sources including vapor
Perched 1,4-dioxane
134
degreasers and wastewater lagoons. Historically, investiga-
tions at the site for chlorinated VOC concentrations had only
used conventional methods, with monitoring well screens
placed at arbitrary depths in the aquifer. The original CSM
at the site was based on monitoring well data and suggested a
TCE groundwater plume in the low hundreds of micrograms
per liter was present. The Smart Characterization approach
was applied to develop a high-resolution, flux-based CSM and
improve understanding of the nature and extent of the chlo-
rinated solvents in groundwater. The approach used CPT and
the HPT to develop a 3D interpretation of hydrostratigraphy
and differentiate high-permeability transport zones from less
permeable storage zones. The dissolved-phase plume was
mapped using vertical aquifer profile groundwater sampling
nominally every 5 ft. A specialized mobile lab using direct
sampling ion trap mass spectroscopy was used for high-res-
olution saturated soil sampling in the source area and fine-
grained matrix in the downgradient plume to evaluate mass
contained within the storage zones.
During the initial phase of work near the source, a
10  ppm+ CVOC plume was discovered at a depth interval
midway between intermediate and deep monitoring wells,
indicating that the core of the plume was missed with the
monitoring well network and suggesting a significant poten-
tial for off-site migration. During the subsequent two phases
FIGURE 4.28  Case study 2 CVOC plume and fence diagrams showing higher permeability sands (yellow) and lower clay aquitard (blue).
Creek
Organic
soils
TCE >10,000
Lower silt
FIGURE 4.29  Case study 2 cross-sectional view of plume and geology.
Remediation Engineering
of work, HPT and vertical aquifer profile sampling was
performed to enable expedited access and expansion of the
downgradient investigation. As the investigation adaptively
mapped the plume, it resulted in approximately 150 verti-
cal aquifer profile borings, 90 HPT borings, and more than
600 WCSS samples.
Ultimately, a 10 ppm CVOC plume core was mapped
nearly 5000 ft downgradient of the site, beneath a residential
neighborhood and discharging to a stream. Soil, groundwa-
ter, and permeability data were analyzed in a 3D model to
map the complex distribution of the compounds at the site
(see Figure 4.28 for an example view from the model). The
3D model was a critical tool in constructing the CSM and
agreement from the regulatory agency on the CSM elements.
The rapid site characterization resulted in significant
updates to the CSM, including the following:
• Identification that the majority of CVOC mass is
present in a low-permeability storage zone, mapped
using a combination of permeability profiling and
WCSS sampling.
• Mapping of a 5000 ft long VOC plume with concen-
trations greater than 10,000 µg/L in the plume core
(Figure 4.29). The plume is located in a thin segment
(<10 ft thick) at the aquifer base (deeper than 80 ft
Site
Upper sand
TCE >5 μg/L
μg/L
Basal clay
~1000 ft
Remediation Hydrogeology
Cree
k
1,000
Plume 4
5
>10,000
100
Site plume
Plume 3
1,00
0
Plume 2
1,000 ft Site
FIGURE 4.30  Case study 2 results, showing map view of the four
plumes in the area. TCE Concentrations in µg/L.
below ground surface) and is traveling beneath a
residential neighborhood.
• Identification of three other distinct groundwater
VOC plumes in the area that are not associated with
the subject property, including one plume that origi-
nates upgradient of the subject property and flows
through it (Figure 4.30). Due to the detailed charac-
terization, it was possible to clearly distinguish the
other groundwater plumes based on unique depths
and chemical fingerprints.
• Through strategic collection of soil and groundwater
samples during the characterization phase, demonstra-
tion that the soil and groundwater conditions at the site
pose no vapor intrusion risk to the residents of the area.
• The detailed stratigraphic mapping using HPT iden-
tified a thick sequence of organic rich soils surround-
ing the stream north of the site. As the plume passes
through this zone, it was found that the plume is nat-
urally attenuating more than 90% prior to discharge,
resulting in no need for an active remedy to manage
the groundwater-surface water interface at the dis-
charge point.
One of the most important lessons from this site is to use the
proper tools for characterization. More than 50 wells had
been installed at the site in arbitrary, depth-based intervals
and had been monitored for nearly 10  years. However, the
characterization revealed that the groundwater plume was
135
missed by the monitoring well network, in an example of how
monitoring wells have excellent precision but poor accuracy.
While the data from the monitoring wells were precise and
reproducible over many rounds of sampling, the result was
not representative of site conditions because the arbitrary well
placement missed the core of the plume that was later mapped
with vertical aquifer profiling. The lesson learned is that mon-
itoring wells are reliable for monitoring, once the geometry
and distribution of the plume has been determined through
appropriate sampling.
REFERENCES
1. Fetter, C.W. Jr. 1980. Applied Hydrogeology. Merrill,
Columbus, OH, 488pp.
2. Freeze, R.A. and J.A. Cherry. 1979. Groundwater. Prentice
Hall, Inc., Englewood Cliffs, NJ, 604pp.
3. Darton, N.H. 1903. Preliminary report on the geology and
water resources of Nebraska west of the one hundred and third
meridian (Vol. 17). Govt. Print. Off.
4. Dennehy, K.F. 2000. High plains regional ground-water study:
U.S. Geological Survey Fact Sheet FS-091-00. United States
Geological Survey: Reston, VA.
5. Suthersan, S., C. Divine, E. Cohen, and K. Heinze. 2014.
Tracer testing: Recommended best practice for design and
optimization of in  situ remediation systems. Ground Water
Monitoring and Remediation 34(3), 33–40.
6. Heath, R.C. 1983. Basic ground-water hydrology. U.S. Geological
Survey Water-Supply Paper 2220, Reston, VA, 86pp.
7. Boggs, S. 2006. Principles of Sedimentology and Stratigraphy.
Pearson Prentice Hall, Upper Saddle River, NJ.
8. National Research Council. 2013. Alternatives for Managing
the Nation’s Complex Contaminated Groundwater Sites.
National Academies Press, Washington, DC, 407pp.
9. Payne, F.C., Quinnan, J.A., and Potter, S.T. 2008. Remediation
Hydraulics. CRC Press, Boca Raton, FL.
10. Margat, J. and J. van der Gun. 2013. Groundwater around the
World. CRC Press/Balkema, Leiden, the Netherlands.
11. Maupin, M.A., J.F. Kenny, S.S. Hutson, J.K. Lovelace, N.K.
Barber, and K.S. Linsey. 2014. Estimated use of water in the
United States in 2010. U.S. Geological Survey Circular 1405,
Reston, VA, 56pp. http://pubs.usgs.gov/circ/1405/.
12. Toth, J. 1963. A theoretical analysis of groundwater flow
in small drainage basins. In Proceedings of Hydrology
Symposium No. 3, Groundwater, Queens Printer, Ottawa,
Ontario, Canada, pp. 75–96.
13. Bear, J. 1972. Dynamics of Fluids in Porous Media. Elsevier,
New York, 764 pp.
14. Domenico, P.A. and F.W. Schwartz. 1990. Physical and
Chemical Hydrogeology. John Wiley & Sons, New York,
824 pp.
15. National Research Council. 1994. Alternatives for Groundwater
Cleanup. National Academy Press, Washington, DC.
16. Kelly, M. M. February 1994. Applying innovative tech-
nologies to site contamination: Historical trends and future
demand. In Presented at Haz Mat South ‘94, Orlando, FL.
17. Suthersan, S., C. Divine, J. Quinnan, and E. Nichols. 2010.
Flux-informed remediation decision making. Ground Water
Monitoring and Remediation 30(1), 36–45.
18. Suthersan, S., J. Quinnan, and N. Welty. 2015. The new ROI:
Return on investigations by utilizing smart characteriza-
tion methods. Ground Water Monitoring and Remediation
35(3), 25–33.
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19. Guilbeault, M.A., B.L. Parker, and J.A. Cherry. 2005. Mass
flux distributions from DNAPL zones in sandy aquifers.
Groundwater 43(1), 70–86.
20. Sale, T., B.L. Parker, C.J. Newell, and J.F. Devlin. 2014.
Management of contaminants stored in low permeability
zones—A state of the science review. Strategic Environmental
Research and Development Program, ER-1740.
21. ITRC (Interstate Technology and Regulatory Council). 2009.
Evaluating LNAPL remedial technologies for achieving proj-
ect goals. LNAPL-2. Washington, DC: Interstate Technology
and Regulatory Council, LNAPLs.
22. ASTM E2531-06. 2014. Standard Guide for Development
of Conceptual Site Models and Remediation Strategies for
Light Nonaqueous-Phase Liquids Released to the Subsurface.
ASTM International, West Conshohocken, PA.
23. Myers, K.F., W.M. Davis et al. 2002. Tri-Service site char-
acterization and analysis system validation of the mem-
brane interface probe. E. Laboratory, US Army Corps of
Engineers, Engineer Research and Development Center,
Vicksburg, MS, p. 62.
24. Robertson, P.K. 1990. Soil classification using the cone pen-
etration test. Canadian Geotechnical Journal 27(1), 151–158.
25. Robertson, P.K. and R.G. Campanella. 1983. Interpretation
of cone penetration tests: Sands and clays. Canadian
Geotechnical Journal 20(4), 719–745.
26. Robertson, P.K., R.G. Campanella, D. Gillespie, and J. Greig.
1986. Use of piezometer cone data. Use of in-situ tests in
geotechnical engineering (GSP 6), ASCE, Reston, VA,
pp. 1263–1280.
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assessment of the direct-push permeameter for characterizing
vertical variations in hydraulic conductivity. Water Resources
and Research 44, W02432.
28. Butler, J.J., Jr., P. Dietrich, V. Wittig, and T. Christy. 2007.
Characterizing hydraulic conductivity with the direct-push
permeameter. Ground Water 45(4), 409–419.
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of Slug Tests. Lewis Publishers, New York, 252pp.
30. Carrier, W., III. 2003. Goodbye, Hazen; Hello, Kozeny-
Carman. Journal of. Geotechnical and Geoenvironmental
Engineering 129(11), 1054–1056.
31. Devlin, J.F. 2015. HydrogeoSieveXL: An excel-based tool
to estimate hydraulic conductivity from grain size analysis.
Hydrogeology Journal 23(4), 837–844.
32. ASTM D7352-07. 2012. Standard Practice for Direct Push
Technology for Volatile Contaminant Logging with the
Membrane Interface Probe (MIP). ASTM International, West
Conshohocken, PA.
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33. Geoprobe. 2012. Geoprobe membrane interface probe
(MIP) standard operating procedure. Technical Bulletin No.
MK3010. Revised April 2012.
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geoprobe.com/mip-membrane-interface-probe. Accessed
July 2, 2016.
35. Rossi, M., S. Pitkin, and M. Jordan. 2014. Limitations and
appropriate use of MIP in HRSC. In Ninth International
Conference on Remediation of Chlorinated and Recalcitrant
Compounds. Session E7, Evolution and Applications of High-
Resolution Site Characterization Technologies, Monterey, CA.
36. Adamson, D.T., S. Chapman, N. Mahler, C. Newell, B. Parker,
S. Pitkin, M. Rossi, and M. Singletary. 2014. Membrane inter-
face probe protocol for contaminants in low-permeability
zones. Groundwater 52(4), 550–565.
37. Grundl, T., J. Aldstadt, J. Harb, R. St. Germain, and
R.  Scheweitzer. 2003. Demonstration of a method for the
direct determination of PAHs in submerged sediments.
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38. Coleman, A., D. Nakles, M. McCabe, F. DiGnazio,
T. Illangasekare, and R. St. Germain. 2006. Development of a
Characterization and Assessment Framework for Coal Tar at
MGP Sites. EPRI, Palo Alto, CA, p. 1010137.
39. St. Germain, R.W., M.D. Einarson, A. Fure, S. Chapman, and
B. Parker. 2014. Dye based laser-induced fluorescence sens-
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Third International Symposium on Cone Penetration Testing,
Las Vegas, NV.
40. ITRC (Interstate Technology and Regulatory Council). 2010.
Use and measurement of mass flux and mass discharge.
MASSFLUX-1. Washington, DC: Interstate Technology and
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J.A. Cherry, and P.S.C. Rao. 2005. Field-scale evaluation
of the passive flux meter for simultaneous measurement of
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and Technology 39(18), 7194–7201.
42. Hatfield, K., M.D. Annable, J. Cho, P.S.C. Rao, and
H. Klammler. 2004. A direct passive method for measuring
water and contaminant fluxes in porous media. Journal of
Contaminant Hydrology 75(3–4), 155–181.
43. ASTM E1689-95. 2014. Standard Guide for Developing
Conceptual Site Models for Contaminated Sites. ASTM
International, West Conshohocken, PA.
44. ITRC (Interstate Technology and Regulatory Council). 2015.
Integrated DNAPL site characterization and tools selection
(ISC-1). Washington, DC: Interstate Technology and Regulatory
Council, DNAPL Site Characterization Team.
 5 Dynamic Groundwater Recirculation
5.1 INTRODUCTION
Pump and treat is the earliest groundwater remediation tech-
nology and still remains one of the most commonly employed
approaches. In the 1980s and early 1990s, over 70% of
groundwater remediation projects relied solely on pump and
treat,1,2 and even today, pump and treat continues to be an
essential element of most remediation projects. However,
there are few technologies that are less maligned or polar-
izing than pump and treat. End users typically consider pump
and treat to be a failed technology, and industry performance
supports this assessment. Pump and treat is successful in
achieving cleanup objectives at some sites, but at most sites,
systems operate long after the original cleanup projections
are passed. The rare pump and treat successes look to be due
to luck rather than design, but closer inspection has revealed
that hydrogeology rather than serendipity divided projects
between success and failure.
The conceptual model of contaminant transport has
undergone a paradigm shift over the last decade. The early
applications of pump and treat relied on the concept of the
representative elemental volume (REV), in which the sub-
surface could be treated as an equivalent homogeneous
system using large-scale bulk averages.3 This concept was
developed from groundwater resources management, for
water supplies, as a means to address aquifer heterogeneity.
The REV is an innovative approach that works well for water
supply because flow pathways are less important than flow
quantity. The importance of this distinction has long been
recognized, but data to understand this distinction have only
recently been widely available. Tracer studies reveal that con-
taminants move much faster than previously thought, while
plume profiling methods reveal that contaminants move
through only a small fraction of the aquifer (as demonstrated
in Chapter 4). In this chapter, we explore the effect of these
conditions on pump and treat performance and determine
what ­hydrogeologic features are important during predesign
investigations and how they can be exploited using dynamic
groundwater recirculation (DGR).
5.2 A NEW MODEL OF CONTAMINANT
TRANSPORT
Our understanding of contaminant transport has evolved
greatly in the past 20 years, and it is time to transform it again.
The 1990s was the era of parameter parsimony emphasizing
the importance of reducing complexity to describe plume
conditions and behavior. The theory of the approach assumes
the effect of transport processes as a plume moves through
an aquifer results in a uniformity of conditions, smooth-
ing concentrations, and mass flux with time and distance
from sources. This concept supported the belief that adequate
characterization of the distal plume is achieved with less
investigative points as plumes expand. Collectively, these
ideas support the use of data averaging and application of
REVs, the minimum scale at which averaging groundwater
flow hydraulic analysis is effective. The limitations with the
REV model were revealed in the early 2000s by advances in
site characterization. Tracer studies performed in sand and
gravel aquifers showed that the effective porosity was usu-
ally less than 10% (typically 7.5%; Figure 4.3), much differ-
ent from the specific yield estimated from long-term pumping
tests (typically 25%). This contrast in testing results was fur-
ther investigated using aquifer-profiling methods across and
along plumes to assess large-scale plume behavior. These
investigations found that our plumes were not mixing across
aquifers with distance but rather were moving through net-
works of small-scale pathways in higher permeability zones.
Conceptually, these networks are consistent with the geologic
processes that created our aquifers (e.g., see Figure 4.5). An
anastomosing stream network filling a valley with fluvium
will create aquifers with anastomotic hydraulic conductivity
patterns. Collectively, these observations showed that con-
taminant transport needs to be assessed at a smaller scale than
the REV so that important fine-scale geologic heterogeneities
controlling flow and transport could be included.
The effect of real soils on plume movement produces unex-
pectedly fast arrival of concentrations as well as a delayed
flushing of contaminants. This behavior, when observed in
monitoring wells, is analogous to the breakthrough curves
observed when incomplete mixing occurs in chemical reac-
tors. This process was described in depth in the 1950s4–6 as
caused by velocity differences generated by the drag or shear
stress of vessel walls and baffles on fluids as they move through
vessels. The effect of this process is well approximated using
the three-parameter model representing the advective frac-
tion of the vessel, the static fraction of the vessel (slow advec-
tive zones approximated as being static), with mass transfer
between zones.7 Others8 extended these works to solute trans-
port through porous media presenting the differential capaci-
tance model, known today as the dual-domain model (DDM),
and demonstrated the applicability of the DDM using column
data. The DDM matched breakthrough data significantly bet-
ter than the simple ADE equation, allowing quantification of
dead-end pores in soils, and the effects of velocity on mass
transfer through this space.
The division of the soil into two compartments, one immo-
bile and the other mobile exchanging mass through a mass
transfer coefficient, was an important step in advancing our
ability to represent heterogeneities in our transport models.
It also created a clearer distinction between the concepts of
groundwater supply and solute transport. For example, the
137
138
specific yield representing water storage is not the fraction
of the aquifer representing plume movement, but occasion-
ally, each parameter may have similar values. The addition
of a third parameter, mass transfer coefficient, also permitted
adjustments in calculations to represent observed declines in
remedial performance. Collectively, the concepts of transport
and storage zones along with a mass flux–based perspective
and hydrostratigraphic analyses allowed a much more real-
istic representation of contaminant movement in the subsur-
face, thus improving our ability to clean up sites. Although
the DDM has improved our ability to clean up sites dramati-
cally, this storage/transport zone model is a simplification of
the subsurface, lumping broad ranges of permeability classes
within each soil fraction. These simplifications are clearly
evident when we assess high resolution aquifer studies. These
mass flux mappings repeatedly demonstrate that the majority
of flux occurs in a small fraction of the cross sectional area;
typically, over 80% of the flux occurs in less than 20% of the
cross section.9,10 Because the majority of the mass flux occurs
exclusively in the most permeable sections of the aquifer, the
distribution of flux implies that 20% of the flux is in the low
permeability storage zones. These low permeability storage
zones are commonly thought of as representing silt and clay,
where advection is negligible and diffusion is the dominant
process, essentially creating static zones where mass is not
moving. However, if 20% of the mass is present in zones that
1 × 10–5 2 3 5 1 × 10–4
0
10 Measured soil
concentrations
Depth below land surface (ft)
20
30
40
50
0 10 20
FIGURE 5.1  High-resolution soil concentration and hydraulic conductivity profile, demonstrating the majority of the aquifer is unaffected
by contaminants.
Remediation Engineering
are static, it may not be possible to ever reduce concentra-
tions in a meaningful, long-term sense at some sites without
a costly, brute force approach. The distribution of mass flux
and our preconceived limitations on accessing that 20% of
the mass is a consequence of how we have conceptualized the
subsurface into a binary system of either transport or storage
zones. In reality, there are a range of permeabilities in the
subsurface; the highest permeability zones (sands and gravels)
will act as pure transport zones, and the lowest permeability
zones (silts and clays) will act as pure storage zones. But there
are also intermediate permeability zones—interbedded sand–
silt–clay mixtures—that are currently lumped and classified
as storage zones. We call these “slow advection” zones, and
they will have both diffusion and advection occurring in them.
Consider Figure 5.1 that presents groundwater concentrations
and hydraulic conductivity data collected using a vertical pro-
filing tool through a plume. The data show the majority of the
aquifer is unaffected by contaminants. Figure 5.2 presents the
relative mass flux (product of hydraulic conductivity and con-
centrations) with the aquifer concentration data. This analysis
illustrates that the majority of the mass flux moves through a
fraction of the contaminant zone, but equally important, the
figure shows the mass flux is variable. Notably, there are por-
tions where the advection rates are far lower than the rates
in a pure transport zone with advection rates that are still far
higher than the velocity of diffusion.
Hydraulic conductivity (cm/s)
2 3 5 1 × 10–3 2 3 5 1 × 10–2
Hydraulic
conductivity
Sand and
gravel
Silt
Sand and gravel
Clay
30 40 50 60 70 80 90 100
Soil concentration (mg/kg)
Dynamic Groundwater Recirculation 139

Relative mass flux

0 0.01 0.02 0.03 0.04 0.05 0.06 0.07 0.08 0.09 0.1
0

10
Measured soil
Depth below land surface (ft) concentrations

Sand and
20 Mass gravel
flux

30 Silt

Sand and gravel

Clay
40

50
0 10 20 30 40 50 60 70 80 90 100
Soil concentration (mg/kg)

FIGURE 5.2  Relative mass flux was calculated for the soil and hydraulic conductivity data from Figure 5.1. Note that although soil con-
centrations are present across 15 ft of the subsurface, the majority of the mass flux is present in a segment less than 5 ft thick.

These examples are intended to emphasize that contami- advection zones in our model of transport allows us to make
nant storage zones are often misconceptualized as static. The meaningful cleanup progress at sites where previously it was
proper description is that they appear to be static. While a not thought possible; we can affect contaminant mass in slow
portion of these zones are static, the majority of the immo- advection zones while restoration of storage zones will always
bile or static aquifer fraction is slowly moving. By recogniz- be limited by diffusion. In this chapter we will revisit contam-
ing this distinction, we establish a framework for enhanced inant transport, evaluate how we can improve pump-and-treat
performance. Table 5.1 proposes a three compartment model performance, and introduce a new approach to groundwater
based on hydraulic conductivity ranges. The inclusion of slow extraction we call dynamic groundwater recirculation (DGR)
that provides significant performance improvement over tra-
ditional pump and treat.
TABLE 5.1
Three-Compartment Model of the Subsurface 5.3 DESIGN CONCEPTS AND REMEDIAL
Advective zones: Pure advection STRATEGIES
Sands and gravels (mobile fraction)
Hydraulic conductivity >10−2 cm/s A traditional pump and treat system design is built upon a
Advective/storage zones: Slow advection
premise that aquifer systems at large scale behave as equiva-
lent homogeneous systems. This framework emphasizes the
Sands mixed with silts and clays (immobile fraction)
importance of monitoring wells to understand contaminant
10−5 cm/s <Hydraulic conductivity <10−2 cm
behavior and risk, ultimately guiding remedial decisions.
Storage zones: Static water/storage
Extraction wells are typically located downgradient of source
Silts and clays (storage fraction) areas with an expectation that steady operation will achieve
Hydraulic conductivity <10−5 cm/s
performance objectives.
Source: Potter, S.T. et al., Large plume remediation: Quantifying the effects These concepts are explored further by evaluating pump
of scale on remedy design and operation, Remediation Technology and  treat performance at the manufacturing site shown in
Summit (RemTEC15), Denver, CO, March 1–4, 2015. Figure 5.3. The site is underlain by approximately 50  ft of
sand and gravel with 5 ft of fine silty sand present in the
140 Remediation Engineering

A
Wastewater lagoon Cross-section A–A΄
Leakage rate = 2 gpm 45
22 22
40
35 Lagoon
Factory
30
21.5 Water table Supply well
21.5 25
Northing (ft)

20

Elevation
15 Sand and gravel
21 21
Point B 10 Hydraulic conductivity—100 ft/day
ma

5
re

Fine sand/hydraulic conductivity—10 ft/day

St

Supply well 20.5 20.5 –5

15 gpm Sand and gravel
–10
Hydraulic conductivity—100 ft/day
–15

A΄ –20
0 500 1000 1500 2000 2500
Eastings (ft) Distance

FIGURE 5.3  Site conditions for the case study of pump-and-treat performance. A manufacturing facility had a leaking wastewater lagoon
north of the main building, and contaminants began to show up in the supply well to the south. The subsurface consists of a medium-to-
coarse sand, with a 5 ft thick silty sand layer. The facility extraction well is screened only in the lower sand unit.

middle of the aquifer and groundwater present around
20–25 ft. The average hydraulic conductivity of the shallow
and deep portions of the aquifer is approximately 100 ft/day
(0.0353 cm/s), while the silty sand has an average hydraulic
conductivity of 10 ft/day (0.00353 cm/s). Ambient groundwa-
ter moves from north to south at an average hydraulic gra-
dient of 0.001, naturally discharging to two small streams
south of the factory (Figure 5.3). The manufacturing facil-
ity is extracting groundwater at 15 gpm in the southern area
of the property to support general factory operations. The
extraction well is screened across the lower 20 ft of the aqui-
fer. Facility wastewater is temporarily stored in a lagoon at
the north end of the site before treatment and discharge to
the small tributary at the south end of the site (Point B). The
wastewater has an average TCE concentration of 100  µg/L.
The lagoon had an unidentified leak not recognized until
TCE was detected in the groundwater extraction well at the
south end of the site. Investigations revealed the lagoon had
been leaking for approximately 10 years, and a groundwater
plume extended approximately 1000 ft downgradient from the
lagoon (Figure 5.4a and b). Contaminant mass is present in all
three aquifer units, with the most widespread, highest concen-
trations in the water table sand unit (up to 100  µg/L), while
the low permeability unit has up to 100  µg/L and the deep
groundwater unit has up to 30  µg/L. The discovery of TCE in
the groundwater extraction well resulted in the lagoon being
remediated and the source removed, approximately 15 years
after the leak began.
The remedial challenge is the groundwater plume: 250 ft
wide, extending over 1100 ft downgradient from the lagoon,
and affecting 30 million gallons of groundwater. As with
all large plumes, remedial strategies are driven by the mass
flux. Two basic strategies are assessed. The first is a conven-
tional pump and treat approach at the toe of the plume. Two
extraction wells are operated, one shallow and one deep at
10 gpm each. Given the plume developed over 10 years under
the influence of a single 15 gpm supply well, it is a reason-
able premise that groundwater will flush out in a similar time
frame under the influence of 20 gpm of pumping. The second
approach is a DGR system. The DGR system incorporates
four extraction wells and seven injection wells, recirculat-
ing treated groundwater at 21 gpm designed to minimize the
travel time of contaminants to extraction wells. The following
sections compare the performance of each strategy.
5.3.1 Pump and Treat
The performance of the conventional pump and treat
approach is shown in Figure 5.5a through d. In this scenario,
two extraction wells are present, one in the water table aquifer
and one in the deep aquifer, each pumping at 10 gpm. The
remedial objective is to reduce concentrations from 100  µg/L
to less than 1  µg/L. Investigations determined that the mobile
fraction is approximately 0.1, the total porosity is 0.35, and
TCE has a retardation factor of 1.0 (i.e., no adsorption). Solute
transport is approximated with the DDM using MT3DMS.12
A mass transfer coefficient of approximately 2.5 × 10−4 was
assigned based upon the discretization and hydrogeology.
The results after 5 years show noticeable improvement in the
water table layer and the deep groundwater, with only modest
Dynamic Groundwater Recirculation 141

Water table Low “K” unit Deep groundwater

21.5 21.5 21.5

21.0 21.0 21.0

20.5
20.5 20.5
N N N
Feet Feet Feet

0 100 200 300 0 100 200 300 0 100 200 300

TCE concentration (μg/L)

(a) 1 10 20 30 40 50 60 70 80 90 100

Water table Low “K” unit Deep groundwater

21.5 21.5 21.5

21.0 21.0 21.0

20.5

20.5 20.5
N N N
Feet Feet Feet

0 100 200 300 0 100 200 300 0 100 200 300

TCE concentration (μg/L)

(b) 1 10 20 30 40 50 60 70 80 90 100

FIGURE 5.4  (a) Development of the groundwater TCE plume, approximately 5 years after the start of the leak in the wastewater lagoon.
Pink circle represents location of the pumping well. (b) Development of the groundwater TCE plume, approximately 10 years after the start
of the leak in the wastewater lagoon.
142 Remediation Engineering

Water table Low “K” unit Deep groundwater

21.5 21.5 21.5

21.0 21.0 21.0

20.5

20.

20
.5
5
N N N
Feet Feet Feet

0 100 200 300 0 100 200 300 0 100 200 300

TCE concentration (μg/L)

(a) 1 10 20 30 40 50 60 70 80 90 100

Water table Low “K” unit Deep groundwater

21.5 21.5 21.5

21.0 21.0 21.0

20.5

20.

20
.5
5

N N N
Feet Feet Feet

0 100 200 300 0 100 200 300 0 100 200 300

TCE concentration (μg/L)

(b) 1 10 20 30 40 50 60 70 80 90 100

FIGURE 5.5  The results of pump and treat applied to the TCE plume, in the three hydrostratigraphic units; pink circles represent pumping
well locations. (a) Five years after the start of pump and treat; (b) 10 years after the start of pump and treat. (Continued)
Dynamic Groundwater Recirculation 143

Water table Low “K” unit Deep groundwater

21.5 21.5 21.5

21.0 21.0 21.0

20.5

20

20
.5

.5
N N N
Feet Feet Feet

0 100 200 300 0 100 200 300 0 100 200 300

TCE concentration (μg/L)

(c) 1 10 20 30 40 50 60 70 80 90 100

Water table Low “K” unit Deep groundwater

21.5 21.5 21.5

21.0 21.0 21.0

20.5

20

20
.5

.5

N N N
Feet Feet Feet

0 100 200 300 0 100 200 300 0 100 200 300

TCE concentration (μg/L)

(d) 1 10 20 30 40 50 60 70 80 90 100

FIGURE 5.5 (Continued )  The results of pump and treat applied to the TCE plume, in the three hydrostratigraphic units; pink circles
represent pumping well locations. (c) 20 years after the start of pump and treat; (d) 30 years after the start of pump and treat.
144
improvements in the lower-K middle unit. After 10 years, the
water table and deep groundwater units have limited mass
remaining, but the low permeability unit still has concen-
trations similar to the start of pump and treat. After 20 and
30 years of pump and treat, the plume continues to persist in
the low permeability unit. The persistence of the contaminants
is caused by the permeability contrast between soil layers and
the simultaneous extraction of groundwater both shallow and
deep; the pump and treat strategy of a uniform withdrawal of
water effectively isolates less permeable zones from primary
pathways even though the contrast is only 10:1. Even with this
limited permeability contrast, it takes approximately 50 years
of pump and treat to entirely remove the plume. By extension,
this effect becomes greater with typical soil profiles as greater
permeability contrasts usually vary from 1,000:1 to 10,000:1.
With traditional pump and treat, we are constrained by the
ambient hydraulic gradient and aquifer hydraulic conductiv-
ity and are unable to decrease the period of performance. The
time to clean up is also unchanged if the pumping rate on
the extraction well is increased. This is because if the pump-
ing rate is increased, the groundwater flow rate through the
plume is unchanged; the pumping well capture zone merely
increases in size. One key lesson, then, is that pumping harder
does not reduce cleanup time.
The alternate scenario shows how DGR can dramati-
cally reduce cleanup times (Figure 5.6a through e). This
is achieved by increasing the actual groundwater flow rate
through the plume, which we can achieve by extracting
Water table Low “K” unit
21.5
21.0
N N
Feet Feet
0 100 200 300 0 100 200 300
TCE concentration (μg/L)
(a) 1 10 20 30 40 50
FIGURE 5.6  The results of dynamic groundwater recirculation (DGR) applied to the TCE plume, in the three hydrostratigraphic units;
pink circles represent extraction wells and green squares represent injection wells. (a) Initial conditions at start of DGR. (Continued )
Remediation Engineering
water along the plume spine, and injecting water at the edges
of the plume to create a simple DGR system (Figure 5.6a).
The total injection and extraction rate is 21 gpm, approxi-
mately matching the total extraction rate of 20 gpm of the
pumping wells in the previous scenario. The flow between
layers is slightly unbalanced, extracting more in the shallow
and injecting more in the deep, in order to create upward
head differentials between the water table and the deep
zone. These conditions are opposite of those during plume
development where in the infiltration from the lagoon (slight
mounding of the water table above the middle layer) and
deep extraction (drawdown and water level declines in the
deep aquifer) created a pathway for TCE to invade the lower
permeability zone. The hydraulic gradients from the unbal-
anced flows drive the flow through the lower permeability
zone enhancing flushing. While the traditional pump and
treat required decades to make meaningful cleanup prog-
ress, the DGR system makes noticeable progress after a
year (Figure 5.6b), and the entire plume has been cleaned up
within 10 years (Figure 5.6e). After 7 years of DGR opera-
tion, the injection and extraction flow rates were altered to
focus efforts on the portion of the aquifer where the plume
was still present. The  injection and extraction wells in the
northern portion of the plume were shut down, and the wells
in the southern portion of the plume pumped at higher rates.
The optimization could be more effective if an injection was
well installed below the recalcitrant portion of the plume to
increase vertical gradients and flushing.
Deep groundwater
21.5 21.5
21.0 21.0
N
Feet
0 100 200 300
60 70 80 90 100
Dynamic Groundwater Recirculation 145

Water table Low “K” unit Deep groundwater

21.5 21.5 21.5

21.0 21.0 21.0

N N N
Feet Feet Feet

0 100 200 300 0 100 200 300 0 100 200 300

TCE concentration (μg/L)

(b) 1 10 20 30 40 50 60 70 80 90 100

Water table Low “K” unit Deep groundwater

21.5 21.5 21.5

21.0 21.0 21.0

N N N
Feet Feet Feet

0 100 200 300 0 100 200 300 0 100 200 300

TCE concentration (μg/L)

(c) 1 10 20 30 40 50 60 70 80 90 100

FIGURE 5.6 (Continued )  The results of dynamic groundwater recirculation (DGR) applied to the TCE plume, in the three hydrostrati-
graphic units; pink circles represent extraction wells and green squares represent injection wells. (b) A year after the start of DGR. (c) 4 years
after the start of DGR. (Continued )
146 Remediation Engineering

Water table Low “K” unit Deep groundwater

21.5 21.5 21.5

21.0 21.0 21.0

N N N
Feet Feet Feet

0 100 200 300 0 100 200 300 0 100 200 300

TCE concentration (μg/L)

(d) 1 10 20 30 40 50 60 70 80 90 100

Water table Low “K” unit Deep groundwater

21.5 21.5 21.5

21.0 21.0 21.0

N N N
Feet Feet Feet

0 100 200 300 0 100 200 300 0 100 200 300

TCE concentration (μg/L)

(e) 1 10 20 30 40 50 60 70 80 90 100

FIGURE 5.6 (Continued )  The results of dynamic groundwater recirculation (DGR) applied to the TCE plume, in the three hydro-
stratigraphic units; pink circles represent extraction wells and green squares represent injection wells. (d) 7 years after the start of DGR;
(e) 9 years after the start of DGR.
Dynamic Groundwater Recirculation
This example demonstrates that conventional pump and
treat systems can be reengineered and enhanced as an effec-
tive remediation strategy. The key to success is to focus on the
following critical elements:
• Site-specific hydrogeology and the conceptual site
model (CSM)
• Contaminant distribution and mass flux
• Extraction and reinjection well configuration com-
bined with adaptive operation linked to remedial
progress
• Short- and long-term performance objectives: adjust-
ing the system to maximize contaminant removal
rates, clearly defining remedial endpoints, and pri-
oritizing schedule compliance to meet the targeted
remediation time frame
We define this concept of enhanced groundwater flushing and
the technology to implement it as DGR.
Implementation of DGR can achieve endpoints that his-
torically were considered impossible or not cost-effective
to reach with the conventional approach to pump and treat.
The use of an enhanced flushing-based solution is a necessity
to address large plumes and difficult-to-treat contaminants
because of the complexities and related costs of large-scale
implementation of in situ technologies. Historically, the pre-
sumptive assumption toward large plume remediation is that it
cannot be done, and the best approach is to control the plume
movement. However, the effectiveness of DGR combined
with mass flux–based solutions can enable stakeholders to
plan for site closure with both relatively shorter time frames
and reduced costs.
(a)
FIGURE 5.7  (a, b) The natural geologic processes that deposit sediment impart a permeability structure to the subsurface. The photo on
the left shows the Teklanika River in Denali National Park. This style of deposition leads to an aquifer structure like the image shown on
the right. Water flows through both systems in a similar fashion, with the majority of the water flowing in small-scale features of the overall
system. (Photo courtesy of Scott Potter.)
147
5.3.2 Complex Heterogeneous Systems
The simple example in the previous section illustrates the
difference between traditional pump and treat and DGR
for a site with relatively simple conditions; however, most
aquifer systems are considerably more complex. The com-
plexity of real-world systems can be divided into a static
component derived from the permeability distribution in
the aquifer, and a dynamic component derived from hydrau-
lic conditions. The static permeability component is due to
the geologic processes that create aquifers. Consider Figure
5.7a taken along the bank of the Teklanika River in Denali
National Park. The river is a network of braided and anasto-
mosing streams, with an ever-varying discharge from melt-
ing snow and precipitation events, carrying eroded materials
from adjacent uplands, filling the valley with sediment.
These complex erosional and depositional processes impart
a permeability structure consistent with the braided geom-
etry of the streams as shown in Figure 5.7b. In essence, the
resulting aquifer permeability structure creates a network of
small-scale pathways in higher permeability zones just as in
the original fluvial environment.
As a plume develops in this permeability structure, it is
affected by dynamic conditions from variations in ground-
water levels, hydraulic gradients, and flow directions that
result from seasonality of recharge rates, variations in
river stage, tidal influences, and nonsteady pumping rates
from water supply wells. The dynamic temporal conditions
lead to plume development in all advective pathways and
diffusive storage zones, a process similar to how a breeze
moves through a home with open windows. Consider all
the space inside a home as representing a potential pathway
(b)
148 Remediation Engineering

to move and circulate air. As air enters through a window,
the configuration of interior walls and doors act to baffle
airflow differently through each room. As the direction
of the wind changes, airflow through each room of the
home changes as well. This process is analogous to how
plumes develop and advance through our aquifers. In an
aquifer, high permeability zones focus groundwater flow,
while low permeability zones deflect groundwater flow.
The dynamic influence of seasonal changes in water levels
and hydraulic gradients gradually introduce contaminants
across all permeable portions of an aquifer downgradi-
ent of the source. And by extension, the concentration
gradients between high and low permeability materials
along these primary pathways induce forward diffusion of
contaminants into less permeable zones over time. These
processes and the analogy earlier bring to light a critical
observation that large plumes are created over decades of
varying hydraulic conditions and changing principal flow
paths. Figure 5.8 illustrates the development of a plume in
the permeability structure created by the braided stream
shown in Figure 5.7. It is this temporal variation in aquifer
hydraulics, coupled with sorption and diffusion into low
permeability zones that acts as the primary mechanism
behind transverse plume spreading. Sites where aquifer
hydraulics vary less tend to have long, thin, and relatively
uniform plumes; conversely, sites with highly varying
hydraulic conditions tend to have wider plumes with more
irregular contaminant distribution. Researchers in chaos
­t heory describe this element of transport as plume stretch-
ing and folding.13–16
In summary, the process of plume development occurs
in a complex permeability structure under the influence of
constantly varying hydraulic conditions. The problem with
traditional pump and treat is that it is static and continually
draws water from the same permeable pathways in the aqui-
fer. The contaminant mass located off these main pathways,
emplaced through complex plume development, is isolated
and never affected by clean water drawn through the plume.
The most efficient way to clean up a plume, therefore, is to
unravel the complex distribution of contaminant mass by
mimicking the process of plume development through vary-
ing the hydraulic conditions in a similar manner. This is
why DGR is so successful: the dynamic application forces
water through all pathways in the subsurface rather than
just the primary static pathway. As demonstrated in the
case study earlier, a minor reconfiguration of the DGR after
several years of operation flushed additional pathways and
reduced the cleanup time.

Source area Source area

(a) (b)

Extraction well Extraction well

Injection well Injection well
Source area Source area

Source area Source area

(c) (d)

FIGURE 5.8  Groundwater flow and solute transport in a heterogeneous aquifer like the example shown in Figure 5.7. Background shading
represents relative differences in hydraulic conductivity associated with alluvial deposition. Panels a and b represent the effects of seasonal
variation in groundwater flow patterns and contaminant transport during the phase of plume propagation. Panel c represents the plume
configuration sometime after the implementation of dynamic groundwater recirculation (DGR) technology. Panel d represents DGR recon-
figuration and restoration that has taken place. (After Suthersan, S. et al., Ground Water Monit. Remed., 35(2), 23, 2015.)
Dynamic Groundwater Recirculation
5.4 CASE STUDY 1: FORMER REESE
AIR FORCE BASE
In this case study we examine how DGR facilitated
groundwater cleanup at an unprecedented scale and time
frame. A large groundwater plume in the sole-source aqui-
fer beneath former Reese Air Force Base (AFB) was over
three miles long with a footprint of over 700 acres. The
performance-based contract required reducing contami-
nant concentrations to below maximum contaminant levels
(MCLs) in less than 10 years. The available time for active
remediation is roughly half of the 10 years, as 3 years are
required for postclosure monitoring to ensure restoration,
and 2 years are needed to develop a remediation strategy,
obtain regulatory approval, and for system construction.
Therefore, this schedule on an incremental basis necessi-
tated that 2–3 acres of the 700 acre plume needed to be
cleaned up each week for the 5-year period of active reme-
diation. In order to meet this aggressive cleanup rate, an
approach was needed that could cost-effectively improve
the short-term efficiency, reliability, and performance of
the remedy, while at the same time enhancing the pace of a
plume-wide cleanup. At the scale of the plume’s footprint,
an approach focusing on mass flux hinged on adaptive
operation and optimization using real-time performance
data seemed necessary. This strategy would require treat-
ment system components that could be relocated or aug-
mented to adjust treatment configurations and drive the
overall rate of cleanup—in contrast with the fixed opera-
tional configuration typically employed to control plumes
of this magnitude.
This adaptive approach was what ultimately yielded suc-
cess. The collective process required to achieve a cleanup
at Reese included upfront revisions to the CSM based on
mass flux rather than REVs, optimizing the existing remedy
based on the revised CSM, designing combined remedies
while repurposing existing infrastructure for efficiencies,
and adaptive operation of that remedy through constant
feedback from analysis of the plume-wide performance
data. The outcome was a reduction of contaminant concen-
trations to MCLs over the three mile plume and restora-
tion of a sole-source aquifer to unrestricted use in less than
10 years.
5.4.1  Background
Former Reese AFB, located approximately 10 miles west
of Lubbock, TX, opened in 1941. It had a flight training
mission for pilots until its closure in 1997 under the Base
Realignment and Closure Act. Contamination consisting
mainly of petroleum hydrocarbons and chlorinated solvents
that had been used to clean aircrafts stood in the way of
the transfer and redevelopment of the base property. The
main challenge was an extensive TCE plume in groundwater
that extended off-base, covering a total distance of approxi-
mately 3 miles. The aquifer involved is the sole drinking
water source for the local area, so while considerable in
149
both scale and lithologic complexity, restoring the aquifer
to unrestricted beneficial reuse was the primary goal of the
restoration effort.17
In 2004, the Air Force kicked off an effort to complete
the cleanup of the Reese AFB TCE plume within 10  years.
The concept of accelerating plume-wide groundwater cleanup
at Reese AFB from a baseline of 100–1000 µg/L across the
bulk of the plume to less than the TCE MCL (5 µg/L) within
a 10-year time frame was initially met with a healthy dose of
skepticism. The water table is 150 ft deep, and the plume con-
figuration was complicated by the presence of paleochannels,
changes in depositional environments, 30–50 ft of caliche in
the vadose zone, operating supply wells, and the presence
of multiple, independent contaminant sources with different
release histories. On top of this, there was the challenge of
collecting and interpreting data from over 700 monitoring,
remedial extraction, irrigation, and domestic wells to make
remedial decisions. Prior to adjusting the strategy, the most
recent 5-year review concluded there was at least 50 years of
further remediation required.
5.4.2 The First Step: Refinement of the
Conceptual Site Model
An honest refinement of the CSM, unburdened by alle-
giance to historic precedent, was integral to the success
of the Reese project. As discussed earlier in this chapter,
historically, the concept of a CSM had much narrower defi-
nition and was grounded in the belief that complex systems
could be adequately represented by simple equivalents—
the REV—but modern CSMs incorporate the importance
of fine-scale processes on contaminant transport. The
Reese CSM provides a good illustration of this shift, as
when the initial CSM for Reese was developed in the early
1990s; contaminant data and water levels were organized
to indicate that plume movement was entirely consis-
tent with groundwater potentiometric maps. This was an
expected outcome considering the concepts of contaminant
transport and groundwater modeling applications at the
time. This CSM intrinsically assumed that soil complexi-
ties could be effectively averaged to reproduce behavior at
all wells, in spite of all soil borings showing a complex soil
profile varying from clay to gravel. This interpretation was
extended to subsequent wells and boring locations as inves-
tigations expanded, inadvertently screening the potential to
observe certain types of behavior. Anisotropy is typically
framed as a property of soils, where permeability affect-
ing the movement of water and contaminants is different
depending upon direction; however, anisotropy can also be
an effect driven by the larger scale hydrostratigraphy of
the geology. The initial CSM concluded the aquifer was
effectively isotropic at the plume scale and that there was
no preferred pattern of plume movement largely because
asymmetrical drawdown local to extraction wells was not
identified. This interpretation became the basis for the
initial positioning of the pump and treat extraction wells
and was also used to identify private wells potentially at
150 Remediation Engineering

flow
dw ater
G roun

40°

Gro
und
wat
er g
rad
ient

Miles
0 0.5 1

FIGURE 5.9  Groundwater flow is not aligned with the potentiometric gradient. The anisotropic plume movement resulted from the perme-
ability structure in the aquifer. (After Suthersan, S. et al., Ground Water Monit. Remed., 35(4), 27, 2015.)

risk. It  was not until after remedy implementation when
perimeter monitoring wells were found to contain VOCs
consistent with the core of the plume and extraction wells
immediately downgradient of the plume were not extract-
ing any mass, that it became evident that there were defi-
ciencies with the CSM.
The early CSM had resulted in a failure to achieve an
operating properly and successfully designation as required
by the ROD even though the project was 5  years into the
remedy. In 2004, the transition of the project to a program
whose goal was to complete the cleanup in a 10-year time
frame created the opportunity to rethink both the CSM and
the existing remedy. A careful review of the historic con-
taminant data and plume-wide hydrostratigraphy yielded
some important findings relative to the previous interpreta-
tion; most notably, the groundwater plume appeared to be
moving in a direction that was approximately 40° of the
observed hydraulic gradient (Figure 5.9). In addition, it was
also observed that at approximately 3000–5000 ft intervals
along the plume axis, contaminant transport and mass distri-
bution patterns changed.
These observations drove the evolution of the CSM from
a single simplified system to a macrosystem comprising
several small interconnected systems. This conclusion was
also a logical fit with the scale of the plume—noticeable
differences should be expected in the depositional environ-
ment over a distance of 18,000 ft. As a result, the refined
site-wide CSM reflected anisotropy driven by geologic
structure, and was revised to include five different areas
with their own conceptual model based on unique geology,
distance from source areas, and contaminant distribution
(Figure 5.10).

me 5
in plu
Ma
4

Primary 3
2
sources
Landfill 1 km
5+

FIGURE 5.10  The refined site-wide conceptual site model was divided into five distinct areas based upon geology, distance from the
source area, and contaminant distribution. (After Suthersan, S. et al., Ground Water Monit. Remed., 35(4), 27, 2015.)
Dynamic Groundwater Recirculation
The distance from the source affects how long contami-
nants have been present at a location, which in turn affects the
degree to which contaminants have been able to diffuse into
immobile fractions of the aquifer. This means the way plumes
appear does not always reflect the processes by which they
were created. For example, contaminants in the aquifer near-
est source areas were almost uniformly distributed not because
contaminants were moving uniformly but because 50  years
of exposure allowed coarse and fine grained soils (soils with
higher and lower permeability) to become impacted at similar
concentrations through heterogeneous advection and diffu-
sion. At the leading edge of the plume, where contaminants
had been present for the least time, the plume tended to be
limited to the most permeable channels conveying the mass
flux. This contrast in conditions naturally leads to a realiza-
tion that different remedial approaches would likely be more
effective in different portions of the plume.
5.4.3 The Second Step: Optimization
of the Existing Remedy
As part of the base closure process, a regulatory order issued in
the 1990s required implementation of a conventional pump and
treat system to achieve plume containment. Air stripping with
carbon adsorption was employed to treat the extracted water,
and the treated water was reinjected into the aquifer. Location
of extraction wells and pumping rates were influenced by the
previous interpretation of plume structure and driven by con-
ceptualizations built from solutions to the advection–disper-
sion equation in homogeneous settings. Operated between
1997 and 2004, the limitations of the CSM had resulted in the
ongoing operation of multiple extraction wells outside of the
plume footprint, and during this period of operation, there was
little change in plume footprint (Figure 5.11).
Extraction
well
Injection
well
FIGURE 5.11  Extraction, treatment, and reinjection system in 2004 prior to system optimization (total extraction rate was 651 gpm).
Pumping distribution was based on potential plume movement inferred by water level elevations. The symbol sizes shown are proportional
to the flow rate of the well. (After Suthersan, S. et al., Ground Water Monit. Remed., 35(4), 27, 2015.)
151
Recognition of the anisotropy in the flow system sup-
ported a significant reengineering of the capture approach.
High contaminant concentrations downgradient of the source
could only be present if they were hydraulically connected to
source areas, and these were the zones where pumping was
focused. The new strategy was simple: focus on the contami-
nant mass flux through the preferred pathways. A numerical
model was developed using MODFLOW with a supplemental
piece of MODALL software18 to consider the current site data
and support a change on how groundwater was extracted and
reinjected. The resulting modifications took a 650 gpm sys-
tem with 32 extraction wells and nonstrategic reinjection and
reduced it to a 300 gpm system with 20 extraction wells and a
more strategic reinjection. While groundwater extraction was
reduced by nearly 60%, the overall mass removal increased by
25% (Figure 5.12). These changes resulted in immediate sav-
ings and created flexibility to consider further modifications of
the remedy to more effectively drive restoration of the aquifer.19
5.4.4 The Third Step: Adaptive Implementation
of a Revised Remedy Strategy
5.4.4.1  Strategy
When regulatory decision documents were developed
throughout the 1980s and 1990s, they frequently focused on
selecting a single remedy for any given site. Responsible par-
ties, remediation practitioners, and regulatory stakeholders
now almost wholly embrace the value of a combined rem-
edy approach since the pendulum of technology selection has
swung significantly. For complex remediation sites, multiple
technologies are brought to bear to utilize the unique ben-
efits of each individual technology to expedite bulk source
mass removal, initiate sustaining treatment chemistries, and
enable ongoing mechanisms to both eliminate mass flux and
Miles
0 0.5 1
152
Extraction
well
Injection
well
Primary flow
path
FIGURE 5.12  Extraction, treatment, and reinjection system in 2009 after system optimization (350 gpm). Pumping distribution was based
on mass flux and preferred groundwater flow paths. (After Suthersan, S. et al., Ground Water Monit. Remed., 35(4), 27, 2015.)
achieve remedial goals. Benchmark Record of Decision docu-
ments now reflect not only the regulatory-approved treatment
remedies but also the sequencing and adaptive methodology
through which the remedy train can be deployed.
Selection of a combined remedy approach was integral to
the potential for success at this site by providing a flexible
framework to meet the contractual objective to clean up the
entire plume in less than 10 years. This was a critical element
of the revised strategy, given that the 700 acre footprint of the
plume made it necessary to restore an average of 2–3 acres of
aquifer per week.
The individual components of the revised remedy devel-
oped for Reese AFB were directly tied to the CSMs of the
sequential plume segments and different approaches to
address source mass and diffuse plume areas. Recognition of
the complex structure of the plume and the need to comple-
ment the modified pump and treat system necessitated the
implementation of different remedies within each subarea of
the plume. Figure 5.10 shows the reassessed plume map with
all five areas in the CSM. Area 1 had two hot spots of TCE
co-mingled with petroleum hydrocarbons undergoing par-
tial reductive dechlorination. Extraction wells were installed
in the center of each hotspot, and the extracted water was
treated with GAC and reinjected with added organic carbon
to enhance complete dechlorination of TCE. Injected reagents
were distributed within Area 1 via natural and extraction-
controlled hydraulic gradients. Area 2 was less impacted than
Area 1, and there was no reductive dechlorination occur-
ring. Presence of TCE was concentrated in a narrow channel
flowing from west to east where three extraction wells were
installed. Extracted groundwater was treated with GAC and
reinjected to enhance natural gradients.
Area 3 was approximately a quarter of a square mile and
contained the majority of the TCE mass within the plume.
A continuous reagent delivery system was implemented to
engineer enhanced reductive dechlorination within this area.
Remediation Engineering
Miles
0 0.5 1
Contaminated groundwater was extracted at 240 gpm from
12  wells, treated with GAC, amended with organic carbon,
and reinjected via 36 wells distributed within the Area 3
plume. Based on the continuum of maturity along the plume
axis and a high density of the residential supply wells, ground-
water extraction and reinjection were the preferred remedial
solutions within Areas 4 and 5.
Insights into the soil heterogeneities drove the approach to
remedy operation. While additional direct permeability map-
ping of preferential contaminant transport pathways would
have yielded a wealth of additional information, it was cost
prohibitive. Instead, a monitoring philosophy was developed
that utilized analytical data to support routine (i.e., quarterly)
modification of the remedy operation to maintain progress.
This approach maintained the focus on areas with higher con-
taminant concentrations that directly correlated to the overall
rate of plume change.
The following discussions provide more detail on the design
and operation of the two primary remedial technologies used
at the site: DGR and enhanced reductive dechlorination.
5.4.4.2 DGR
The most important design innovation that drove the suc-
cess of the Reese AFB project was the reliance on DGR to
overwhelm aquifer heterogeneities and overcome the impacts
of matrix-controlled back-diffusion through enhanced flush-
ing. Faster cleanup rates (2–3 acres/week) were achieved
by creating the conditions to accelerate contaminant mass
flushing by strategically moving more pore volumes (PVs)
of water. This was achieved by manipulating the water levels
to create gradients across less permeable zones and estab-
lish flow through zones where contaminant mass was stored.
The combined result is the enhancement of advective con-
taminant transport that occurs through the mobile fraction of
the aquifer while also increasing mass recovery from storage
zones through advection and diffusion. This awareness led
Dynamic Groundwater Recirculation
to the most important component of the Reese plume rem-
edy, which included a dynamic treatment approach reliant
on routine monitoring data to continually focus groundwater
extraction from wells containing the most mass. In addition,
well design specifications included the placement of injection
and extraction well screen intervals across multiple fine- and
coarse-grained stratigraphic layers to overwhelm the natural
heterogeneity of the aquifer and ensure contaminant removal.
We followed an adaptable implementation of DGR from an
analysis of dynamic conditions of contaminant concentrations
and hydraulic data and thus continuously focused on enhanc-
ing the rate of clean up. Figure 5.13 shows a plot of total foot-
print (area) and the rate of aquifer cleanup versus time.
The circles identify each instance where the rate of cleanup
declined necessitating a change to be made to the system to
drive restoration rates and maintain momentum toward the
endpoint. This plume cleanup was successful primarily
because we were able to incorporate the temporal and spatial
changes in aquifer hydraulics and contaminant concentrations
as a key element of remediation system operation. The sys-
tem in Areas 4 and 5 were designed to maximize contaminant
mass removal rates by extracting from high concentration
areas while enhancing flushing by injecting clean water on the
plume periphery. The DGR design was also based upon man-
aging the transit times between injection wells and extraction
800
700
600
Total plume area (acres)
500
400
300
200
100
0 0.0
1/1/05 1/1/06 1/1/07
FIGURE 5.13  Plume area in acres at the Reese Air Force Base during remediation. The pace of performance (represented by the line)
shows the number of acres cleaned up per week. The circles represent major system optimization events. (After Suthersan, S. et al., Ground
Water Monit. Remed., 35(4), 27, 2015.)
153
wells while maintaining hydraulic control of the plume. It was
also designed to segment the plume by employing multiple
cutoff measures and to actively reduce the plume footprint
along its entire length.
5.4.4.3  In Situ Engineered Reductive Dechlorination
Within Area 3, organic carbon recirculation was implemented
to deliver electron donor throughout the 120 acre treatment
zone and promote development of anaerobic conditions and
TCE dechlorination through daughter products (cis-1,2-DCE,
vinyl chloride [VC]) and end products (ethene and ethane).
The total injection program was completed between April
2007 and December 2009 and required a total of 320,000 lb of
carbon substrate over the life cycle of operation (Figure 5.14).
This delivery system required a well-designed performance
monitoring program to measure hydraulic heads and injection
flow rates and also to evaluate temporal and spatial variations
in aquifer geochemistry, carbon substrate concentrations, and
by-products formation. Another critical challenge that had to
be overcome related to implementing the continuous injection
of organic carbon is the management of well fouling due to
microbial growth, biofilm formation, and mineral precipita-
tion. The zone of fouling can, at times, extend several feet into
the aquifer from a well screen exacerbated by the deposition
of carbonate and other minerals.
4.0
3.5
Plume remediation (acres restored per week)
3.0
2.5
2.0
1.5
1.0
0.5
1/1/08 1/1/09 1/1/10 1/1/11 1/1/12 1/1/13
Date
System optimization and re-engineering
Plume area (acres)
Plume remediation (acres/week)
154 Remediation Engineering

Extraction well Injection well

200΄
400΄

FIGURE 5.14  The layout and performance of the Area 3 in  situ remediation system to achieve complete reductive dechlorination of
TCE and associated by-products. Groundwater with TCE was pumped from the edge of the plume (figure top and bottom), amended with
molasses and injected into the core of the plume. The system operated at 200 gpm for 3 years, treating 370 million gallons of impacted
groundwater to nondetect. (After Suthersan, S. et al., Ground Water Monit. Remed., 35(4), 27, 2015.)

An injection well monitoring and rehabilitation program
was developed and systematically implemented on an ongo-
ing basis. The biofouling challenges became immediately
apparent following initiation of the original carbon delivery
strategy, which relied on the continuous recirculation feed of
a 300 mg/L total organic carbon (TOC) feedstock. Within
weeks of starting the first phase of operation, injection pres-
sure increased by 50 psi to sustain the required injection well
flow rates indicating that this was not a sustainable solution.
This approach was then transitioned to a pulsed injection pro-
gram of 4 hours at 1800 mg/L followed by 20 hours of clean
water injections for 7–10 days, followed by a 2-day shutdown
period. While this approach allowed sustained delivery for
approximately a month, injectability declined and became
untenable. Ultimately, this approach developed through
adaptive operation, balanced system uptime and maximized
recirculation flow rates. While this program did offset biofoul-
ing challenges to a large extent, fouling issues were unavoid-
able. To address these, the injection program was coupled
with strategically timed rehabilitation events that allowed
real-time assessment of individual well performance and sys-
tematic maintenance activities to restore flow. As presented
in Figure 5.15, a simple methodology was developed utilizing
the observed injection well water elevation and flow rate to
determine the timing of necessary rehabilitation events. Each
event was completed using a 35% hydrogen peroxide solu-
tion to eliminate biomass growth within the well screen and
annulus, combined with mechanical scrubbing and pumping
to remove debris, to restore baseline flow. These rehabilitation
events were coupled with the adjustment of organic carbon

Land surface
0 100

15 Depth to 90
Cumulative inj. volume (104 gallons)

water Rehabilitation
30 event 80
(feet below land surface)

45 70
Flow rate (gpm)
Depth to water

60 60

75 Cumulative 50
injection
90 volume 40

105 30

120 20
Flow rate
135 10

150 0
0 7 14 21 28 35 42
Time (days)

FIGURE 5.15  Injection well biofouling causing water level increases in wells. Biomass growth was managed using periodic addition of
hydrogen peroxide. (After Suthersan, S. et al., Ground Water Monit. Remed., 35(4), 27, 2015.)
Dynamic Groundwater Recirculation
1500
Apparent TOC threshold
1350
Minimum design target
1200
1050
Half life (days)
900
750
600
450
300
150
0
1 10
TOC concentration (mg/L)
FIGURE 5.16  Summary of average total organic carbon (TOC) concentrations and TCE degradation rates collected from monitoring wells
within 18 independent active ERD treatment areas. All sites entailed biostimulation alone (no bioaugmentation). Plotted data represent trend analy-
ses derived from data demonstrating an R2 value greater than 0.75. Observed degradation half-lives are generally consistent as long as sufficient
TOC (greater than 10 mg/L) is available to sustain anaerobic conditions and provide excess electron donor. (From Schnobrich, M. et al., Optimized
design of large plume enhanced reductive dechlorination (ERD) systems: An analysis of 85 sites, RemTEC 2011, Platform Presentation, 2011.)
dosing to the recirculation stream to maintain targeted aquifer
geochemical conditions.
The initial objectives of the carbon delivery program were
to sustain delivery of electron donor into the subsurface, and
it was not immediately understood how advantageous con-
tinuous operation was to both the biodegradation and flushing
process. While a completely uniform distribution of TOC was
not achieved throughout the entire reactive zone, a low but
sufficient range was available for enhanced treatment (i.e., at
least 20 mg/L above baseline). As the rate of enhanced bio-
remediation is not electron donor dependent as long as a sur-
plus of organic carbon is maintained (Figure 5.16), the overall
objective was to sustain at least 20 mg/L of TOC within the
reactive area to ensure that sufficient electron donor was
available to drive the dehalogenation processes. Once this was
achieved, organic carbon dosing was removed from the recir-
culation system, and treated groundwater alone was flushed
throughout the treatment area to exhaust residual organic car-
bon stockpiled as biomass and restore aquifer geochemistry.
5.4.5 Performance Metrics
5.4.5.1  Achieving the Cleanup Objectives
Early recognition that preferential contaminant transport was
occurring based on geologic factors allowed the rest of the
CSM and remedy refinements to fall into place. The incre-
mental improvements followed by rapid declines in TCE con-
centrations within the different areas of the plume were from
the aggressive flushing caused by the recirculation. The chal-
lenge was determining the influence of diffusion on remedial
endpoints. Initially, in the flux-focused remediation that was
implemented at this site, the effects of diffusion were masked
by the magnitude of bulk mass removal from advective
155
100 1,000 10,000
transport zones; however, as remediation progresses, it should
be expected that the effects of diffusion will become apparent.
It was widely recognized in 2004 when the remedial strat-
egy was developed and implemented that diffusion would
govern achievable endpoints. In essence, the aquifer would
never be expected in a reasonable time frame to be totally free
of contaminants. The question that could not be answered at
the onset of remediation was whether the achievable endpoint
was higher or lower than the MCL. This quandary is faced at
all sites but should never be used as an excuse for not making
progress and not working toward objectives. Therefore, while
the objective of the project was to achieve MCLs, the focus of
the remediation was always to remove the most mass as effi-
ciently as possible. With finite resources, this strategy focused
team attention away from very low concentration (between 1
and 5 μg/L) areas of the plume toward where the mass flux is
concentrated. Monitoring well concentrations away from the
mass flux began to rapidly decline 4 years into active remedia-
tion (2010), 2 years before goals were met.
Data collected from one of the first monitoring wells
installed at the site are presented in Figure 5.17. This well
experienced all phases of plume evolution and restoration
over a 15-year monitoring period. Figure 5.18 is a concep-
tual illustration of the mass invasion and removal processes
at different stages of the plume lifecycle. The invasion phase
(A) captures the increase in contaminant concentrations as
the plume expands and contaminates the aquifer near the
well. The middle phases (B and C) show the declining con-
centrations as a result of remediation. The rapid decline dur-
ing phase B reflects the first stage of mass removal through
advective processes from the most permeable pathways.
Phase C represents the decreased rate of concentration
reductions due to the inherently slower advective removal
of contaminant mass from the immobile fraction but is also
156 Remediation Engineering

200
A
180 A: Invasion
B: Washout
160
C: Back diffusion
140 B D: Late term

Concentration (μg/L)
120

100

80 C

60

40 D
20

1995 1997 1999 2001 2003 2005 2007 2009 2011 2013
Date

FIGURE 5.17  Fifteen years of monitoring data collected from one well within the Reese Air Force Base plume. TCE data represent
(A) plume changes during invasion and maturation, (B) early stage treatment dominated by advection, (C) late-stage treatment dominated by
advection and back-diffusion, and (D) end-stage treatment where dual-directional diffusion contributed to widespread TCE disappearance.
(After Suthersan, S. et al., Ground Water Monit. Remed., 35(4), 27, 2015.)

Groundwater Mass storage zone

flow
Diffusion processes
Stage A—Invasion

Diffusion processes
Stage B—Advective
washout

Diffusion processes
Stage C—Advective
back-diffusion

Diffusion processes

Stage D—Diffusive
assimilation and
Diffusion processes stasis

Mobile fraction Immobile fraction

FIGURE 5.18  Advection and diffusion mass transfer mechanisms during plume evolution; stages A through D correspond to the same
stages shown in Figure 5.19. Mass transfer between mobile and immobile zones results in contaminant storage, following which diffusion
occurs via both forward and back-diffusion gradients. (From Suthersan, S. et al., Ground Water Monit. Remed., 33, 2013.)

influenced by the effects of back-diffusion. Phase D repre-
sents the final stages of remediation, when mass removal from
the advection-dominated fraction of the aquifer has been
achieved and diffusive processes are the remaining mecha-
nism of mass removal. During this stage, the only contribu-
tion to the observed mass flux is back-diffusion from very low
permeability soils, which are 10,000–100,000 times less than
the historical mass flux in the mobile fraction. Concentration
decline trends represented in Figure 5.17 will have similar
shapes but will have different magnitudes of mass removal
achieved through the phases described earlier.21
Back-diffusion models have traditionally focused on (1)
contaminant penetration during plume invasion/maturation
from zones of high to low permeability and (2) the reverse
discharge of stored mass based on diffusion gradients into
newly treated high permeability zones. This relationship is
captured in Stages A and B presented in Figure 5.17. This
has seemed intuitive based on the 5–6 orders of magnitude
Dynamic Groundwater Recirculation 157

difference between advective and diffusive mass flux in
large plumes. Considering the decade-long time-scales under
which many solvent plumes have evolved and an understand-
ing that heterogeneous advection results in considerable aqui-
fer mass storage capacity, the current assessments of matrix
diffusion do not adequately capture diffusion gradients that
are both forward into the low permeability strata and reverse
into mobile pathways. This process of dual-directional dif-
fusion can result in a bifurcation of diffusive mass transport
that facilitates both back-diffusion tailing effects followed by
contaminant sequestration and stasis (Figure 5.17, stages C
and D). These effects of dual-directional diffusion cannot be
assessed by approaches that use a mass transfer coefficient
(simplifying the diffusion process) because the internal con-
centration distribution in the low permeability zones is not
explicitly represented; rather, it is simply approximated as a
single uniform concentration.
The effects of dual-direction diffusion were explored using
a two-compartment model, one with mobile water (sand/
gravel) and one with static water (silt/clay). The model was
designed to assess the diffusive mass flux of TCE between
compartments, specifically the mass storage from mobile
to immobile strata in Stage A and the back-diffusion dur-
ing Stages B, C, and D. The mass storage during Stage A
assumed constant TCE concentrations in the mobile compart-
ment for the first 90 days. After 90 days, DGR was assumed
to have flushed contaminants from the mobile pathways and
back-diffusion was monitored during Stages B, C, and D. It
was suspected that diffusive behavior could be masked by
modeling assumptions, so the model grid was made very fine
(0.1 mm). The first 90 days of Figure 5.19 represent the inva-
sion period, with maximum concentration gradients observed
between compartments resulting in the highest rates of mass
storage. As concentrations increase in the silt and clay, there
is a significant decrease in the accumulation of mass after
90  days and storage rates have declined by a hundred fold.
After 90 days, clean water begins to flow past the silt and clay,
and back-diffusion begins and extends for 10 additional years.
The mass flux during this period is negative but is shown as
positive for easy comparison with the mass storage phase. The
initial rate of back-diffusion is the same as the initial rate of
storage, but back-diffusion rates decrease rapidly as concen-
trations decline at the interface between the zones. The shape
of the back-diffusion curve for the first 2  years also aligns
with expectations, as rates decrease exponentially and reflect
the exponential tailing of concentrations typically observed
during plume remediation. What is not expected, however, is
the accelerated decline after approximately 800  days. This
transition occurs because mass transport is happening in
two directions, diffusion deeper into the immobile zone and
back-diffusion into the mobile zone. During the early phases
of back-diffusion, a steep concentration gradient at the inter-
face results in a greater rate of diffusive flux into the mobile
phase as compared to the continuing diffusive flux deeper
into immobile zones; however, if the immobile zone is large
enough, there is a time when the mass release from storage
declines as mass is further sequestered, diffusing deeper into
the immobile zones. This process accelerates the flattening

10–1

B and C—early stage

10–2 back-diffusion
A—Invasion
phase diffusion
Mass flux (mass/time)

10–3 Washout
Rate of back diffusion
Invasion
10–4 Rate of storage

10–5

D—late stage
diffusive assimilation
10–6
0.001 0.01 0.1 1 10 100 1,000 10,000
Time (days)

FIGURE 5.19  A two-compartment model simulating dual-direction diffusion between high permeability (sand/gravel) and low perme-
ability (silt/clay) strata. Simulation conducted with TCE loading during first 90 day (followed by clean water) and completed using very
fine model grid (0.1 mm) and very short time steps (5 s). Negative mass flux during back-diffusion stage (B, C, and D) is shown as positive
value for comparison to invasion (A) phase. Exponential decline in back-diffusion rates during stages B and C is consistent with plume
tailing (i.e., days 90–800), following which declining rates of back-diffusion accelerate due to contributions of forward diffusion (gray
circle inflection point and beyond). (After Suthersan, S. et al., Ground Water Monit. Remed., 33, 31, 2013.)
158
of the concentration gradient between mobile and immobile
zones and thereby limits mass release via back-diffusion.
The influence of dual-directional diffusion on contami-
nant storage has not been well quantified to date, due in part
to an imprecise understanding of the process and the lack of
developed procedures that can accurately integrate dynamic
changes in plume concentration with complex heterogeneous
soil architecture. While the general effects of diffusion on
remedy performance and plume behavior are recognized, the
inability of characterization techniques to quantify the scale
of the diffusion process results in diffusion being largely omit-
ted. In flux-focused remediation and risk-based remedies, the
relative magnitude of contaminant sequestration compared to
bulk mass removal from advective transport zones is poten-
tially negligible and of little consequence as advective mass
removal may be sufficient to achieve remedial endpoints.
With regard to achieving contaminant MCLs for large plume
applications, however, the impacts of dual-directional diffu-
sion can be significant.
5.4.5.2  Demonstrating a Complete Cleanup
The saturated groundwater is approximately 50 ft thick below
the site, with the plume being characterized using over 700
wells. Monitoring wells typically had screen lengths vary-
ing from 10 to 20 ft, while remediation extraction wells, pri-
vate wells, irrigation wells, and clean water injection wells
were typically screened across the entire saturated thickness.
These differences in construction and purpose led to multiple
sampling protocols. Low flow sampling methods were used
at monitoring wells, while extraction wells were sampled
during normal operation or after a 3-volume purge. These
approaches, while expected to yield different numeric results,
were acceptable as the overarching objective of the project
was to restore a sole-source aquifer, and a good measure
of that progress is the concentration at extraction wells, the
potential points of future exposure. In most locations, concen-
trations were similar between extraction wells and adjacent
monitoring wells, but at scattered locations, sampling results
varied from nondetect to several hundred parts per billion.
All the available data in the these areas of the plume were
assessed, and after confirming all the wells were appropriately
placed aerially and vertically within the plume, the wells were
tested using all approved methods to understand conditions.
The last method, collecting grab samples with pumps in the
wells, produced some of the more challenging observations:
the concentrations in wells would gradually increase from
nondetect under low flow to hundreds of µg/L when pumped
at 30 gpm. A review of the CSM revealed the patterns of soil
heterogeneities were affecting groundwater flow near operat-
ing wells as drawdown developed. The Ogallala aquifer is an
alluvial system of upwardly fining sequences varying from
gravels to clays with the groundwater flow apportioned pref-
erentially through facies containing the most permeable sands
and gravels. Collectively, these zones of groundwater flow
represent the mobile portion or mobile fraction of the aquifer.
As drawdown develops in a well under pumping conditions,
the pattern of flow through the mobile fraction will change as
Remediation Engineering
shallower portions of the mobile fraction will contribute less
water to the well, and deeper portions of the mobile fraction
will contribute more. The finding obviously had implications
regarding the nature and extent but were also important when
assessing the remedial strategy. If the portion of the aquifer
where the contaminants resided could only be accessed under
pumping conditions, an in situ strategy of injecting reagents
and allowing them to drift with natural gradients would not
be successful as the reagents would not come in contact with
contaminants. It also provided insight on why a dynamic
remedy operation could enhance remedy performance. If we
delivered reagents via continuous pumping and injection, we
could access more contaminants. Similarly, if we simply var-
ied injection and extraction patterns, we could accelerate con-
taminant flushing and aquifer restoration.
In the end, each sampling method was important.
Compliance wells were sampled using the low flow methods as
required by the regulatory framework in the ROD. Domestic
supply wells were sampled using both methods to meet the
regulatory requirements and also to simulate the actual usage
conditions by all the home owners. Samples collected from all
the wells met the regulatory compliance as well as consump-
tion conditions before closure was requested for the site.
5.4.6 Conclusions and Lessons Learned
The scale of the groundwater restoration achieved at Reese
AFB to support unrestricted use of an aquifer formerly
contaminated with TCE over a three mile long footprint is
unprecedented (Figure 5.20).
The site cleanup also made good fiscal sense. The USAF
has estimated the cleanup has saved US taxpayers at least
$22 MM.22 Looking back on the success, there are a few clear
takeaways:
• Honest challenging of the conceptual model allowed
an initial breakthrough with the configuration of the
existing remedy, cutting operational flow rates (and
costs) needed to achieve containment (as required by
the ROD) while increasing the rate of contaminant
mass recovery.
• The application of DGR was extremely successful,
likely due in part to sequestration of contaminant mass
in fine grained aquifer materials by dual-directional
diffusion, driven by the strategic recirculation of clean
water. While the ERD remedy was a success as well,
it likely would have been possible and more cost-
effective to rely on DGR to clean up the entire plume.
• The adaptive operation and frequent modification
of the remedy configuration (including the installa-
tion of new infrastructure) optimized concentration
gradients on a regular basis to drive flushing of the
contaminant mass from the aquifer.
• Sampling in a manner that reflects how the aquifer will
be used is an essential test of true cleanup; however, it
is reasonable to use other more cost-effective methods
to guide remedy operation and assess progress.
Dynamic Groundwater Recirculation 159

April 2005 October 2006

September 2010 May 2012

FIGURE 5.20  Observed reduction in TCE plume over the 8-year remediation period at the Reese Air Force Base. Shaded plume areas
represent plume footprint in excess of the MCL (5 μg/L). (After Suthersan, S. et al., Ground Water Monit. Remed., 35(4), 27, 2015.)

The methods used to clean up the aquifer under Reese AFB
are being replicated in numerous places with tremendous
results. While this will not be true for every site with a large
or complex contaminant plume in groundwater (the site con-
ditions must be conducive, etc.), we are clearly able to achieve
what was unthinkable just a decade ago (Figure 5.20). This
shows that the advancements being made in in situ remedia-
tion are supporting the real possibility of large-scale restora-
tion, in a world where clean groundwater is one of our most
important natural resources.
5.5  DGR DESIGN CONCEPTS
The most important difference between DGR and conven-
tional pump and treat is the reliance on the CSM to develop a
hydraulic flushing framework, a dynamic operation plan, and
the approach for continuous adaption based on actual remedial
performance. DGR systems are designed to maximize contami-
mechanisms are well understood, but the key to success is tied
to dynamic DGR system operation using performance data to
frequently optimize the remedial system.
For example, Figure 5.21 highlights the results of a minor
reconfiguration of a DGR system resulting in a mass recovery
efficiency increase of more than 200%. The increase in mass
recovery efficiency does not reflect a significant increase in
the zone of capture (total groundwater extraction rates were
decreased by about 50%), but rather more efficient recovery
of high concentrations from a former source zone.
The underlying basis for design of a DGR system is the vol-
ume of water contained within the plume and the number of
pore volume flushes (PVFs) required to achieve water quality
goals set forth by the performance objectives. Simple equa-
tions can be applied within the context of the CSM to begin
8
7
VOC mass removal efficiency

nant mass removal rates by extracting contaminants within the

(lb/10,0000 gal extracted)

plume core while treated water is injected at strategic locations 6

to direct contaminants toward extraction wells. This process 5
helps maintain water levels, provides an efficient way to man- 4
System reconfigured
age treated water, and reduces time required for remediation
3
through enhanced hydraulic flushing. System performance is
further enhanced through dynamically varying pumping rates 2
and locations in response to groundwater concentrations in 1
extraction wells to maximize contaminant mass removal rates,
0
while maintaining hydraulic control of the plume. 0 20 40 60 80 100 120 140
Following implementation, the rule of optimization is Cumulative VOC mass removed (lb)
direct: always maximize contaminant recovery by focusing
groundwater extraction from the highest mass flux within the FIGURE 5.21  Increase in VOC mass removal efficiency following
various treatment areas of the plume, while injecting clean dynamic groundwater recirculation reconfiguration at a site. (After
water on the plume periphery to enhance flushing. Flushing Suthersan, S. et al., Ground Water Monit. Remed., 35(2), 23, 2015.)
160
the design process. An estimate of the volume of water needed
to achieve remedial goals can be developed from concepts of
complete mixed reactors often referred to as batch flush or
batch reactor models.23–25 The concept assumes the reactor is
always well mixed, and a fixed volume of contaminated water
flushed with an equal volume of clean water will reduce con-
centrations by 50%. The number of flushes needed to achieve
a specific reduction in concentration can be approximated as
æC ö
N PV = R f ln ç o ÷
è Cg ø
where NPV is the number of PVFs needed to reduce contami-
nant concentrations from observed levels (Co) to concentration
goals (Cg).
The retardation factor (Rf) accounts for additional flushing
that would be needed to address sorbed contaminants. The
retardation factor can be estimated for a saturated soil matrix
from the following equation:
rb K d
Rf = 1 +
n
where
ρb is the bulk density of the soil
Kd is the distribution coefficient of a solute (i.e., a direct
measurement of the partitioning of a contaminant
between the solid and aqueous phases)
n is the total porosity
A typical range for this factor for organic compounds is 1–2.
Once the number of flushes needed to achieve remedial tar-
gets is estimated, the total volume of water within the plume
is calculated by multiplying the volume of impacted aquifer
by the total porosity. While the mobile fraction or mobile
porosity describes how fast water can be exchanged through a
plume, the total porosity is the best estimate of the impacted
volume of an aquifer. A single PV of contaminated groundwa-
ter within the plume is defined as
PV = B ´ n ´ A
where
B is the average thickness of the plume
n is the total or formation porosity
A is the area of the plume
By combining pore flushes with the pore volume, the total
volume of groundwater needed to be exchanged can be esti-
mated based solely on flushing mechanisms of remediation.
Quantifying this value, the representation of how much water
needs to be moved out of the aquifer and treated, is then con-
sidered in the context of the CSM. Specifically, factors such as
ambient groundwater flow, measured injection and extraction
rates, and past changes in plume shape all influence the initial
Remediation Engineering
DGR design that will evolve throughout a project life cycle as
the system is optimized based on field performance.
As discussed, the purpose of DGR is to accelerate plume
PV flushing to maximize contaminant mass recovery via all
advective pathways and diffusive gradients. A measure of the
expected benefit of this process is estimated by comparing
flushing rates to ambient groundwater flow. For example, the
increase in groundwater flow through the plume is compared
to the ambient groundwater flow to derive a performance factor
(e.g., a value of 2 means DGR will flush contaminants at twice
the rate of ambient groundwater). Knowing the total volume
of water to be treated, the target cleanup time frame, and the
hydrogeology, an overall extraction rate and a scale of the treat-
ment system can be estimated. Consider a cleanup time frame
of 5 years and a total treatment volume of 50 million gallons.
The basic remedial design therefore needs to target roughly
20 gpm (50 million gallons over 5 years). The number of wells
needed for this system and their specific locations depends on
the hydrogeology that defines achievable well yields, injection
rates, and the contaminant distribution throughout the aquifer.
An effective DGR design is based upon managing the tran-
sit times between injection wells to the extraction wells while
maintaining hydraulic control of the plume. This is generally in
contrast to conventional containment approaches that are often
designed as cutoff measures to prevent further plume migration
with the plume slowly contracting toward the extraction wells.
A DGR system designed to accelerate restoration will segment
a plume by employing multiple cutoff measures to reduce the
plume footprint along its entire length. Segmentation of the
plume is a natural element in the application of DGR when plac-
ing injection and extraction wells throughout the plume. This
approach allows transit times and PVFs to be managed based
on local concentrations and for mass removal to occur plume-
wide. Consider a site where three PVFs may be needed in more
distal plume areas, while six PVFs may be needed closer to the
source areas. In this case, the injection-to-extraction well tran-
sit times in the higher concentration areas should be about half
those in the more distal less impacted areas for the remedia-
tion time frame to be uniform throughout the plume. This can
be achieved by closer well spacing and/or higher flow rates in
source areas. Minimizing transit flush times will also enhance
back-diffusion (and therefore shorten cleanup times) by maxi-
mizing the concentration gradient between the more perme-
able zones (where injected clean water is flowing) and the less
permeable zones (where there is contaminant mass storage).
Once a general design is complete with the number of PVFs to
achieve remedial objectives and the desired remediation time
frame determined, application of a quantitative groundwater
model is recommended to develop pumping and injection sce-
narios. The model should be used as a tool to evaluate different
well placements and flow rates while weighing site-specific fac-
tors of implementability and capital costs. Various analytical
and numerical modeling approaches are available to evaluate
the system hydraulics. The appropriate tool should be based
upon scale and the site hydrogeology complexity.
Particle tracking methods to assess flow fields are particu-
larly useful for quantifying relative flushing transit times for
Dynamic Groundwater Recirculation
Groundwater
flow
(a) (b)
Injection well
Extraction well
FIGURE 5.22  Conceptual layouts of dynamic groundwater recircu-
lation with groundwater flow vectors. Flow pathways are controlled
by placement of the injection and extraction wells. Panel a illustrates a
2:1 ratio of injection and extraction wells with injection on the plume
periphery and extraction in the plume core. Panel b illustrates a 3:1
ratio of injection to extraction wells with injection positioned on the
plume periphery and within the plume and extraction positioned within
the plume and downgradient. (After Suthersan, S. et al., Ground Water
Monit. Remed., 35(2), 23, 2015.)
different schemes as well as how water can be expected to
move throughout the aquifer. Figure 5.22 shows flow patterns
of multiple injection and extraction well configurations that
can be readily examined to evaluate potential remedial per-
formance and an initial DGR design.
Once implemented, a DGR system should be continuously
assessed using the performance data. Even with a strong CSM
used to aid in DGR system design and implementation, it is
an approximation of reality while performance data repre-
sents the actual response. These data are the backbone of the
decision-making process to manage and optimize the DGR
system by changing flow rates, adding wells, and when to turn
recirculation elements off.
Successful implementation of DGR also requires that per-
meability information be combined with contaminant informa-
tion to understand mass flux. This is not to advocate that every
well needs extensive testing, but a range of methods can be uti-
lized from simple slug tests to short-term pumping tests and
injection tests. Special consideration should be given to injec-
tion rate estimates in design and implementation because of
the practical difficulties of injecting water. It is our experience
that long-term reinjection rates are commonly one-third or less
of the specific capacity for similarly built extraction wells in
equivalent geologic conditions. Tests across the plume footprint
will greatly improve overall system understanding, providing
better insight on how installing additional wells in specific
locations may affect flow pathways and enhance flushing effi-
ciency. Balancing operation in this manner allows the opera-
tor to focus remedial efforts in areas that result in the highest
161
return (i.e., contaminant recovery and mass flux reduction)
while managing the overall scale of the system throughout the
period of active remediation. This can lead to a more focused
remedial strategy and, subsequently, a significant reduction in
lifecycle remedial costs.
5.6 CASE STUDY 2: COMMERCIAL PROPERTY
AND METROPOLITAN SETTING
This case study discusses the application of DGR at a com-
mercial site located in a high property value metropolitan
setting. The contaminants of concerns included TCE and
its breakdown products, cis-1,2-DCE and VC in a 12.1 acre
plume (Figure 5.23). The remedial goal was the achievement
of the applicable water quality standards everywhere—source
area and plume—within 15–18 months of start-up.
The aggressive cleanup time frames could only be achieved
using a remedy founded on a strong understanding of the
hydrogeology, geochemistry, and groundwater flow and trans-
port zones. The remedial approach resulted in a successful
cleanup that exceeded conventional approaches by decades
and achieved remedial goals ahead of the most optimistic
projections.
In the following, sections we provide a summary of the
CSM, remedial design and design consideration, adaptive
implementation, and performance of the system toward the
remedial goals. In the conclusion, we discuss lessons learned
that will help us more efficiently face the challenges associ-
ated with large plume remedial efforts in the future.
5.6.1 Conceptual Site Model
As shown in Figure 5.24, the site has only a few feet of topo-
graphical relief. The geology consists of marine clay overlain
by 3–20 ft of alluvial sand and gravel deposits with varying
amounts of silt. At some locations, increased silt content has
been observed in the zone just above the clay deposits. The
clay surface undulates up to 8 ft, due to erosional channels
in the surface of the marine clay. The sand and gravel aqui-
fer materials are overlain by discontinuous peat and organic
silt deposits, related to a former marsh. The marsh deposits
are covered by up to 10 ft of urban fill. The current ground-
water table is typically located just below the organic silt and
peat deposits. The thickness of the organic silt and peat layers
increases to the northeast, reducing the sand and gravel unit
thickness to a few feet at the downgradient edge of the plume
(Figure 5.24).
The groundwater flow is generally northeasterly; how-
ever, the easterly flow component becomes more pronounced
toward the plume front. The hydraulic gradients range from
0.002 to 0.035 ft/ft and sand and gravel hydraulic conductivi-
ties range from 10 to 300 ft/day, with the average hydraulic
conductivity of approximately 30 ft/day.
The source zone is approximately 2.3 acres and has ground-
water total chlorinated volatile organic compound (CVOC)
concentrations up to 4500  µg/L and concentrations in the
162 Remediation Engineering

A΄

Avenue
Site boundary

Source
zone

Extent of groundwater
exceeding standards
ctio low

A
dire ater f

Small plume
n
w

associated with Monitoring well

und

shallow soil A A΄ Cross section

Gro

impact
0 250

Scale (ft)

FIGURE 5.23  Schematic view of the site, including the source zone, extent of groundwater exceeding the water quality standards, ground-
water flow direction, and cross section A–A′ (Figure 5.24).

A A΄
15 15

10 10

Urban fill
5 5
Elevation

0 0
Elevation, ft

Peat and organics

–5 Sand and gravel aquifer –5

–10 –10

–15 Clay –15

–20

FIGURE 5.24  Cross section A–A′ depicted on Figure 5.23. The cross section summarizes the general geology and depicts the patchy peat
and organic silt layers that thickens in the northeastern portion of the plume and pinches the sand and gravel aquifer. Also shown is the
undulating nature of the clay surface.
Dynamic Groundwater Recirculation 163

underlying clay up to several thousand microgram/kilogram. 5.6.2 Design Considerations

The source area is located adjacent to past releases along for-
mer railway tracks.
The remediation target area extends north below a 5-lane
avenue to an off-site property with approximately one-third
of the plume located off-site. CVOC concentrations up to
1000  µg/L have been observed in the off-site portion of the
plume, and generally consist only of daughter compounds cis-
1,2-DCE and VC. Local groundwater is generally reducing due
to elevated levels of organic carbon from the peat and organic
silts beneath the site, facilitating degradation of TCE to cis-1,2-
DCE and VC. Groundwater contains appreciative dissolved
iron concentrations (up to 30 mg/L) resulting from the reduced
geochemical conditions. DGR was selected as the remedy for
the diffuse plume based on the aggressive remedial schedule,
and challenging access considerations to restore groundwater
beneath subsurface utilities, buildings, roads, and soil borings.
With the exception of the source zone, the silt and clay beneath
the plume contained low concentrations of total volatile organic
compounds (TVOCs). Therefore, back-diffusion was not antici-
pated to be a significant impediment to site closure.
5.6.2.1  Source Zone
An enhanced resistivity heating (ERH) remedy was chosen
for the source zone to address the underlying clay soils where
high concentrations of CVOCs were likely to result in long-
term back-diffusion to the sand and gravel aquifer (2.1 acres
of the total 12.1 acre plume). The DGR system targeted the
sand and gravel aquifer surrounding the ERH area, where
concentrations in clay were lower (less than 50 µg/kg) and not
expected to contribute to groundwater impacts above criteria.
5.6.2.2 Plume
DGR was the best option for meeting the required concentra-
tion reductions and aggressive cleanup time frame. The DGR
design was supported by a groundwater flow model that was
used to assess hydraulic control and flushing through the
plume. Based on access considerations, groundwater con-
centrations, and low yields from extraction wells, the plume
area was divided into 11 flushing zones (Figure 5.25). The
estimated number of PVFs to meet the cleanup goals within

1.75

1.75 2.8
2.8
1.75 2
10
5.6 gpm 1.75
2.2
1.75 2.5 9
3.0 6.7 gpm
8 1.75
1.75 11.5 gpm 1.5
3.0
1.75
1.75 2.5
2.0 3.0 2.5
1.75 2.3 1.75
7 1.75
1.75
2.5
10.3 gpm
3.0 1.75 3.0 1.5
1.75 6
1.75
1.75 6.5 gpm 1.3 1.75
1.75 3.0
1.3
ERH 3.0
5
1.75 2.6 gpm 1.75
1.75 1.75

3.0
4
1.75 1.75 9 gpm 1.75

1.0 1.75 1.3

1.75 1.75
1.75 1.5 3
2.3 gpm
1 1.5 1.75 1.75
3 gpm
1.75
1.75 2
3.5 gpm 1.75

1.75
A
1.75 1.7
1.75
Injection well (gpm)
11 1.3
3.3 gpm Extraction well (gpm)
1.6

1.75 0 250

Scale (ft)

FIGURE 5.25  Depiction of the 11 dynamic groundwater recirculation flushing zones and the theoretical flushing rate required to achieve
site closure within 15 months.
164 Remediation Engineering

a 15-month period was assessed for each zone and is sum-
marized in Tables 5.2 and 5.3. The assessment evaluated the
current contaminant concentration and cleanup goals (TCE,
cis-1,2-DCE, and VC); the volume of water in the sand and
gravel aquifer and the estimated retardation factors of each
contaminant.
As summarized in Table 5.2, the number of required pore
flushes were greatest in the source zone (e.g., Zone 7 with 6.8
flushes), whereas the plume front with lower concentrations
required fewer flushes (e.g., Zone 10 with 3.5 flushes). The
required pore flushes for each zone was used as the basis of
design for the DGR system. The entire system consisted of
29 extraction wells and 59 injection wells. The wells were
constructed with 5–15 ft of 4 in. inner diameter wire mesh
screens (adjusted for aquifer thickness), PVC risers, and 5 ft
of PVC sumps (set 5 ft into the clay). Risers of wells located
in the vicinity of the ERH area were constructed of fiberglass
to withstand elevated temperatures. The bottom of each well
screen is immediately above the clay surface, while the top
of screen is a minimum of 3 ft below the lowest seasonal
groundwater elevation. The top-of-screen placement limited
exposing the screens in the extraction wells to air during
operation reducing the potential for iron precipitation and
well fouling.
Hydraulic testing of each injection and extraction well
was performed concurrent with the well development. Well
development was performed at multiple extraction rates while
monitoring the drawdown across the well network to ensure
the injection and extraction configuration was capable of per-
forming to the design specification (total of 56 gpm for DGR
system—average of 1.9 gpm per extraction well).
The major components of the ex  situ treatment system
included
1. Filtration to address particulates and dissolved iron
2. Air stripping
3. Granular activated carbon to ensure all VOCs were
removed
4. Posttreatment nitrogen stripping to reduce dissolved
oxygen content before reinjection to prevent in  situ
mineral precipitation (bench testing indicated that
flushing with oxygenated water would precipitate
minerals, reducing permeability and the ability to
inject water)
All piping was buried below the frost line and the injec-
tion and extraction wells were completed below ground in
3 ft deep vaults; however, wells that had the potential to be

TABLE 5.2
Dynamic Groundwater Recirculation Design Parameters for Case Study 2
Cleanup Total Retardation
Compound Goal (µg/L) Koc (L/kg) Site foc (%) KD (L/kg) Porosity (%) Bulk Density Factor
Trichloroethylene 5 60.7 0.08 0.05 30 1.86 1.30
cis-1,2-Dichloroethene 20 39.6 0.08 0.03 30 1.86 1.20
Vinyl chloride 2 21.7 0.08 0.02 30 1.86 1.11

TABLE 5.3
The Number of Required Pore Volume Flushes to Meet the Cleanup Goals within a 15-Month Period for Each
of the 11 Zones
Maximum Observed Number of Pore Maximum Rate
Concentration in Zone Flushes Required Maximum Volume Required for
Volume of (µg/L) (NF = −(ln(Co)/C)* Rf) Number of Removal a 15-Month
Groundwater Pore Flushes Required Closure
Zone Area (ft2) (ft3) TCE cisDCE VC TCE cisDCE VC per Zone (ft3) (gpm)
1 32,100 115,560 6.4 3.7 15 0.3 NA 2.2 2.2 257,871 3.0
2 29,300 105,480 46 140 27 2.9 2.3 2.9 2.9 304,368 3.5
3 48,300 173,880 ND 15 5.6 NA NA 1.1 1.1 198,274 2.3
4 61,200 220,320 47 59 48 2.9 1.3 3.5 3.5 775,453 9.0
5 27,000 97,200 8.2 40 16 0.6 0.8 2.3 2.3 223,848 2.6
6 36,300 130,680 25 180 100 2.1 2.6 4.3 4.3 566,175 6.5
7 36,200 130,320 960 720 23 6.8 4.3 2.7 6.8 890,884 10.3
8 58,700 211,320 190 480 57 4.7 3.8 3.7 4.7 999,505 11.5
9 43,700 157,320 3.3 200 57 NA 2.8 3.7 3.7 583,655 6.7
10 39,000 140,400 20 360 4.6 1.8 3.5 0.9 3.5 485,301 5.6
11 29,300 105,480 40 20 13 2.7 NA 2.1 2.7 285,199 3.3
Dynamic Groundwater Recirculation
affected by the heating from the ERH area were completed
with stickup to reduce health and safety concerns associated
with below-grade steam. The injection and extraction wells
were equipped with pressure transducers and automatic shut-
off to ensure operations within the design draw down (extrac-
tion wells) and pressure head (injection wells).
5.6.3  Implementation
5.6.3.1 Plume Adaptive Approach and
Performance Tracking
The DGR performance was tracked on a biweekly basis and
included sampling of extraction wells and selected monitor-
ing wells. This allowed for an adaptive outside–in approach
focusing on concentration reduction, mass recovery, and
hydraulic control. Focus would shift away from an area once
the remedial goals had been achieved. The CSM was updated
based on data from each successive monitoring round, and
the findings were used to inform changes to the injection and
extraction scheme; injection and extraction wells in areas
where the remedial goals were achieved were either turned off
or operated at a lower injection and extraction rate to maintain
a level of hydraulic containment. The result (Figure 5.26) was
a rapid cleanup, exceeding the schedule and requiring signifi-
cantly fewer PVFs than projected.
Source Source
zone zone
Baseline —
before DGR
Source Source
zone zone
DGR 29 weeks
FIGURE 5.26  Reduction of plume after 10, 23, 29, and 38 weeks of dynamic groundwater recirculation.
165
After 6 months of DGR operations the reductions in TCE,
cis-1,2-DCE and VC concentrations were 99%, 93%, and 81%,
respectively, and well above the 60% goal. After 9 months of
operations, water quality met the cleanup goals everywhere
except two wells screened immediately above the clay located
south and east of the source area and in deep monitoring wells
screened just above the clay in a patch just north of the source
area stretching below the avenue. The residual concentrations
in the deep monitoring wells reflect:
• Difficulty achieving sufficient flushing below the
road (deep wells north of the source) due to distance
between injection and extraction wells located on
either side of the road
• Depressions in the clay potentially creating slow
advection zones (north of source)
• Increased silt content in sands in the deeper por-
tions of the aquifer just above the clay creating slow
advection zones (south, east, and north of the source)
The challenges of creating sufficient flushing below the road
and addressing the slow advection zones were met by fre-
quently changing the injection and extraction patterns in the
surrounding DGR wells, and thereby continuously optimizing
the pushing and pulling of clean water through the residual
impacted zones. Figure 5.27 summarizes the concentration
Source
zone
DGR 10 weeks DGR 23 weeks
1–10 × standard
>10 × standard
0 1000
Scale (ft)
DGR 38 weeks
166 Remediation Engineering

1000

cis-1,2-DCE concentration (µg/L)

A
100
A
B

B
C
10

1
0 3 6 9 12 15 18 0 3 6 9 12 15 18 0 3 6 9 12 15 18
Time since DGR start (months) Time since DGR start (months) Time since DGR start (months)

15 months 18 months cis-1,2-DCE 20 µg/L Baseline conc.

projected closure projected closure cis-1,2-DCE conc.

FIGURE 5.27  Representative concentration reduction trend curves for three different monitoring wells.

reduction trends in three monitoring wells. Example 1 is a The injection and extraction well performance was
water table well screened within the higher permeability sand confirmed during well development.
and gravel deposits, which is reflected in the efficient flush- • Performance monitoring in a selected subset of
ing and concentration reduction significantly ahead of the monitoring wells and extraction wells—biweekly
15-month target. Examples 2 and 3 are both deep monitoring monitoring of 7–15 monitoring wells. The num-
wells that are affected by increased silt content and depres- ber of wells included in the biweekly monitoring
sions in the clay layer elevation. Flushing in Example 3 is fur- was reduced as areas met the cleanup goals and
ther challenged by the nearby avenue. Example 1 has met the the monitoring was shifted to areas with residual
cleanup goals 9 months ahead of schedule, whereas Examples CVOC concentrations.
2 and 3 required adjustments to the injection and extraction • Continuously adjusting the injection and extrac-
scheme to accelerate the cleanup. tion scheme to focus on concentration reduction
and mass recovery while maintaining hydraulic
control.
5.6.4 Site Closure and Lessons Learned
After 10  months of DGR operations, the flow has been Only a limited rebound in concentrations has been observed
reduced from the original 56 gpm to approximately 20 gpm in areas where injection and extraction have either been
with the effort primarily being focused on the few areas with reduced or are no longer occurring and concentrations
residual concentrations of CVOCs. The site is on track for clo- remain below the remedial goals. The faster than antici-
sure ahead of the remedial goal; key elements for the success- pated cleanup and limited rebound suggest that the retar-
ful remediation included the following: dation factor used in the assessment of required flushes is
overestimating the importance of storage in the sand and
• Application of DGR in a dissolved-phase plume with gravel aquifer. The retardation factor is based on adsorp-
minimal storage zones (low permeability layers or tion to organic carbon; however, the performance of the
organic carbon for sorption sites. DGR effort (combined with the source zone remedy) sup-
• Design based on quantitative modeling to inform ports that once the high advection zones in the plume have
and optimize DGR well layout and flushing. been cleaned up, desorption- and diffusion-controlled mass
• Careful design of injection and extraction well screen transfer from the storage zones are too limited and slow to
intervals to limit potential for exposed screen during significantly impact the volume of water moving through
pumping and low seasonal groundwater elevation. the mobile fraction.
Dynamic Groundwater Recirculation
5.7  CASE STUDY 3: REFUELING PAD
5.7.1  Introduction
This case study examines the application of DGR at a site
with light nonaqueous phase liquid (LNAPL) and dissolved-
phase impacts. A spill at a helicopter refueling pad resulted in
a 3.6 acre LNAPL source zone and a 2800 ft dissolved-phase
plume, as shown in Figure 5.28. DGR was implemented pri-
marily to prevent further downgradient movement of dissolved-
phase VOCs from the LNAPL source area, through hydraulic
control of the dissolved-phase plume in the source zone, and
contaminant mass treatment and removal through enhanced
oxygenation of the subsurface. In just 18 months, DGR was suc-
cessful at reducing almost 95% of the dissolved-phase mass,
significantly decreasing the dissolved-phase plume footprint.
5.7.2  Geology and Hydrogeology
The unconsolidated deposits at the site are shown in Figure 5.29
and consist of deltaic sand deposits overlying a discontinuous
lacustrine silt and clay unit. This silt and clay unit provides a
semiconfining layer between the upper sand deposits and an
underlying, semiconfined boulder–gravel–sand till unit that is
present at the bedrock interface. The thickness of the semi-
confining unit varies across the site and is very thin or absent
in some areas. The basal boulder till underlying the semicon-
fining silty clay consists primarily of a basal till with a matrix
of coarse sand, gravel, and boulders with some silt and clay.
Although this unit is somewhat compact, it yields significant
amounts of water to wells screened within it. In most areas
of the site, the basal till is confined below the silty clay unit,
and comprises a separate water-bearing unit in contact and
associated with the underlying bedrock aquifer. The bedrock
aquifer consists of fractured upper Ordovician limestone and
Cambrian sandstone units.
The subsurface is divided into an upper unconfined aqui-
fer, consisting of the unconsolidated soils, and a lower aquifer,
A΄
Monitoring well
LNAPL extent
0 250 Approximate regional
groundwater flow direction
Scale (ft)
FIGURE 5.28  Setting for case study 3, including extent of light nonaqueous phase liquid, TVOC concentrations, approximate groundwater
flow direction, and location of cross section A–A′.
167
consisting of the bedrock unit. Groundwater data indicate that
the water table elevation ranges between 40 and 50 ft below
ground surface (bgs). The upper aquifer is generally divided
into two aquifer zones. Aquifer Zone A represents the upper
saturated portion of the aquifer and consists of a poorly sorted,
medium to fine sand, while Aquifer Zone B represents the
lower saturated portion of the aquifer overlying the silty clay
unit and consists of fine, stratified silty sand, with frequent,
thin silt and clay layers.
5.7.3 Summary of Soil and Groundwater Impacts
The site is an active helicopter refueling pad servicing military
aircraft. The fuel point is the endpoint of a fuel distribution and
delivery system that includes two 135,000 gal aboveground
storage tanks, buried distribution lines, pumps, and associated
equipment. JP-8 aviation fuel leaking from a damaged fuel line
leaked into a service pit then entered the subsurface at a depth
of approximately 16 ft bgs, migrating vertically until intercept-
ing the water table at 40–45 ft bgs (Figure 5.29). Upon reach-
ing the water table, the fuel spread radially directly beneath
the release point. Approximately 400,000 gal of LNAPL were
initially estimated to be present at the water table interface;
however, given the large volume of fuel handled at the site, the
volume of the release is uncertain. At the start of the DGR pro-
gram, the measurable LNAPL extended across approximately
4 acres from the vicinity of the service pit to the northeast. The
LNAPL is emulsified in surfactant solution remaining from a
surfactant-enhanced aquifer remediation event that was per-
formed in 2009 in the vicinity of the service pit.
Due to seasonal fluctuations in the water table, an 8 ft
LNAPL smear zone developed at the water table (Figure 5.29).
The area with the thickest interval of petroleum-impacted soil
at the water table interface is beneath the original release at
the service pit.
A dissolved-phase groundwater plume, extending over
2800 ft, formed downgradient of the JP-8 spill (Figure 5.28).
A A΄ Cross section
>100 µg/L TVOC
>1000 µg/L TVOC
168 Remediation Engineering

West East
700 Fuel point pad North ramp 700

680 680

660 660
Feet above mean sealevel (AMSL)

640 640

620 620

600 600
Unconsolidated aquifer
zone A
580 Unconsolidated aquifer 580
zone B
560 560

540 540

520 520
Bedrock source aquifer
0 50 100 200 300

500 Geology Total VOCs in groundwater (2013) 500

Aircraft pad/apron/tarmac Approximate horizontal scale (ft)
Medium to very fine sand <5–50 μg/L Vertical scale 1'' = 30'
LNAPL
LNAPL smear zone Interbedded sand/clay/silt 50–500 μg/L
Water table (dashed where inferred) 500–5,000 μg/L
Silt and clay
5,000–10,000 μg/L
Boulders, gravel, and sand >10,000 μg/L

Bedrock

FIGURE 5.29  Cross section A–A′ for case study 3, illustrating the extent of TVOC concentrations in the aquifer, geology, aquifer zones,
and extent of light nonaqueous phase liquid.

The plume includes petroleum constituents, methyl-tert injection well clusters, three downgradient extraction well
butyl ether, and acetone. The local groundwater flow direc- clusters, and three intermediate performance monitoring
tion, observed to be to the northeast then turning to the east, well clusters (PMWs). The three injection well clusters were
has influenced migration of the dissolved-phase ground- installed within the dissolved-phase plume just inside the
water plume. Although the hydraulic gradient in the vicin- upgradient LNAPL plume edge as established in December
ity of the spill is low (0.003–0.006 ft/ft), it increases steeply 2012. The three extraction well clusters were installed in a
(0.01 ft/ft) farther to the east. Vertically, the dissolved-phase chevron pattern at the northeastern-most corner of the fuel
plume extends from the water table–LNAPL interface to point pad, within the pad apron.
approximately 65–70 ft bgs, with concentrations decreasing Area B is installed within the dissolved-phase plume
downward. across the leading edge area of the December 2012 LNAPL
plume (Figure 5.30). The Area B system consists of three
upgradient injection well clusters, five downgradient extrac-
5.7.4 DGR Description
tion well clusters, and four intermediate PMW clusters. The
The DGR system at the site is operated to hydraulically con- extraction well clusters are installed east of the leading edge
trol and oxygenate the portion of the dissolved-phase plume LNAPL DPE system, in a line extending approximately
beneath the LNAPL source area. The DGR system consists north–south. Based on the pilot system design assessment,
of three independently operating groundwater recirculation additional groundwater extraction beyond the recirculation
cells (A, B, and C), which can be operated in concert to cells was included in the design for Area B to achieve full
direct groundwater flow throughout the area beneath the capture of the dissolved-phase contaminant plume in areas
LNAPL source zone (Figures 5.30 and 5.31). The DGR beneath the LNAPL plume. While not contributing signifi-
system operates in combination with a dual-phase extrac- cantly to the creation of the recirculation cell, the northern-
tion (DPE) system in the LNAPL source area to remediate most and southernmost extraction wells in Area B primarily
the spill and control plume movement downgradient. The function as hydraulic control wells to control and capture
DPE system also includes bioventing to enhance LNAPL downgradient plume movement.
degradation. Expansion Area C was installed to the north of Areas A
Area A, shown in Figure 5.30, is located in the northeast- and B along the northern edge of the source area to expand the
ern portion of the fuel point and consists of three upgradient system to its full-scale capacity and increase dissolved-phase
Dynamic Groundwater Recirculation 169

A΄

Groundwater monitoring
C well
DGR injection well
A DGR extraction well
Performance monitoring
A well
LNAPL extent
0 200
A A΄ Cross section
Scale (ft)

FIGURE 5.30  View of dynamic groundwater recirculation (DGR) system including injection wells (circles), extraction wells (squares),
and DGR Areas A, B, and C.

A A΄
West East
700 North ramp 700

680 680

660 660
Feet above mean sealevel (AMSL)

640 640

620 620

600 600

580 580

560 560

540 540

520 520

500 Well locations Geology

Total VOCs in groundwater (2013) 500
Aircraft pad/apron/tarmac
Monitoring Injection Extraction
LNAPL Medium to very fine sand <5–50 μg/L
LNAPL smear zone
Interbedded sand/clay/silt 50–500 μg/L
Water table (dashed where inferred) Well riser
500–5,000 μg/L
Silt and clay
0 50 100 200 300 5,000–10,000 μg/L
Screen Boulders, gravel, and sand
interval >10,000 μg/L
Approximate horizontal scale (ft)
vertical scale 1'' = 30' Bedrock

FIGURE 5.31  Cross section A–A′, with dynamic groundwater recirculation system overlain.

treatment in that area (Figure 5.30). The Expansion Area C being treated. The areas have the following design elements
system consists of two injection well clusters installed in the in common:
fuel point pad at the upgradient LNAPL plume extent and two
downgradient extraction well clusters installed to the north of • The injection and extraction wells are screened
the pad, to the northeast of those for Area A. across two 20 ft depth intervals within the shallow
Each DGR area consists of upgradient injection wells to aquifer zone. The shallow interval extends 20 ft
deliver oxygenated water to the subsurface and downgradi- below the smear zone, from approximately 60–80 ft
ent extraction wells to control groundwater flow through the bgs. The deep interval extends to the base of aquifer
treatment zone and movement of the portion of the plume Zone A, from approximately 80–100 ft bgs.
170
• Reinjection of the groundwater is unbalanced,
with injection rates approximately 60% of the
extraction. Excess extracted water is either dis-
charged to the combined storm water/sanitary sys-
tem on-site after treatment or used for smear-zone
recirculation to further enhance source zone mass
reduction.
• Extracted groundwater is treated through an ex situ
treatment system, consisting of oil/water separators,
air stripping, and bag filters.
• The treated groundwater is dosed with oxygen to
increase the dissolved oxygen levels in the injected
water. The amended water is then reinjected upgra-
dient of the extraction well to allow for in situ treat-
ment of the dissolved-phase contaminants via the
injected amendment.
PMWs consisting of a shallow and deep interval well are
installed at the approximate midpoint of each recirculation
cell to monitor the effectiveness of the recirculation cell at
delivering and distributing oxygen and change in contami-
nant concentrations over time. The PMWs are screened at
the same intervals as their respective DGR cell injection and
extraction wells.
5.7.5  Groundwater Extraction and Reinjection
As stated earlier, the groundwater recirculation in each
cell is unbalanced, with an overall total injection rate for
all recirculation cells of approximately 60% of the total
extracted groundwater volume from all cells. These opera-
tional recirculation profiles were selected to limit drawdown
and expansion of the LNAPL smear zone during recircula-
tion, while allowing for hydraulic control of the plume and
delivery of oxygenated water to the subsurface. The total
operational extraction rate for groundwater treatment from
the expanded full-scale system is up to 83,520 gal/day (gpd),
with up to 50,400 gpd total to be oxygenated and reinjected
A΄
A
Monitoring well
LNAPL extent
0 250 Approximate regional
Scale (ft) groundwater flow direction
FIGURE 5.32  Extent of TVOC concentrations in groundwater after 18 months of DGR operation. Compare to Figure 5.30 for original
extent of TVOCs.
Remediation Engineering
upgradient. The resultant total recirculation profiles for
each cell are
• Approximately 21,600 gpd from three extraction
well clusters, with reinjection of approximately
15,840 gpd in three injection well clusters in Area A
• Approximately 36,000 gpd from five extraction
well clusters, with reinjection of approximately
24,480 gpd in three injection well clusters in Area B
• Approximately 25,920 gpd from two extraction well
clusters, with reinjection of up to 10,080 gpd in two
injection well clusters in Area C (the balance of
injection and extraction rates in Area C is less than
60% because of the hydraulic interaction with the
other recirculation cells)
5.7.6 DGR Performance and Results
The initial DGR systems (Areas A and B) became operational
in early 2014, and the expanded system began operation in late
2015. As of this writing, the expanded system has not been
fully evaluated for performance. Therefore, only Areas A and
B are discussed herein. Following a baseline monitoring event
in the DGR wells performed prior to operation, systems A and
B were monitored on a monthly basis through mid-2014 after
system start-up, and then quarterly after mid-2014.
As of mid-2015, the combined injection volume for DGR
Areas A and B was over 18,400,000 gal, resulting in a total
injected oxygen mass of almost 1700 lb. The oxygen mass
injected represents approximately 55% of the total expected
oxygen mass required to treat the initial estimated dissolved-
phase mass beneath the LNAPL source area, which was esti-
mated at approximately 3100 lb.
Total extraction for both DGR Areas A and B as of June
2015 is approximately 27,500,000 gal. Based on average esti-
mated VOC concentrations from the extraction well efflu-
ent, and the volume of water extracted, approximately 108
lb of dissolved-phase VOCs have been removed through
A A΄ Cross section
>10 µg/L TVOC
>100 µg/L TVOC
Dynamic Groundwater Recirculation 171

A A΄
West East
700 North ramp 700

680 680

660 660
Feet above mean sealevel (AMSL)

640 640
>100 µg/L
620 620
>10 μg/L
600 600

580 580

560 560

540 540

520 520

500 Well locations Geology Total VOCs in groundwater (2015) 500

Aircraft pad/apron/tarmac Monitoring Injection Extraction >10 μg/L
Medium to very fine sand
LNAPL
LNAPL smear zone Interbedded sand/clay/silt >100 μg/L
Well riser
Water table (dashed where inferred)
Silt and clay
0 50 100 200 300
Screen Boulders, gravel, and sand
interval
Approximate horizontal scale (ft)
Bedrock
Vertical scale 1'' = 30'

FIGURE 5.33  Cross section A–A′ showing extent of TVOC concentrations in groundwater after 18 months of dynamic groundwater recir-
culation (DGR) operation. Compare to Figure 5.31 for TVOC contours prior to DGR operation.

groundwater extraction. This represents approximately 7.5% edge of the source area plume, resulting in flow toward the
of the initial estimated dissolved-phase mass for the portion of Area B extraction wells from the stagnation point, and cutoff
the dissolved-phase plume beneath the LNAPL source area. of the dissolved-phase plume from areas further downgradient.
Based on the 18-month assessment, almost 95% of the
combined dissolved-phase mass of BTEX, naphthalene, and
5.7.7 Summary and Conclusions
acetone has been removed during the evaluation period. This
estimate is further supported by the plume-wide monitoring To date, the DGR system has been effective at meeting its
data in Figures 5.32 and 5.33, which indicates decreased VOC primary goals, arresting plume movement, and reducing
concentrations and a shrinking dissolved-phase plume both dissolved-phase concentrations. Dissolved-phase concentra-
beneath the LNAPL source area and in areas downgradient tions of VOCs beneath the LNAPL source area have sig-
of the source area. The largest reduction of dissolved-phase nificantly decreased (95%) in just 18  months of operation,
mass was from acetone, representing approximately 98% of and the DGR system has been further expanded to treat
the mass reduction in the dissolved phase. The reduction of additional areas of the dissolved-phase plume north of the
dissolved-phase contaminant mass appears to be primar- previous pilot areas. The DGR system has also cut off the
ily from degradation, as the DGR system is limiting further dissolved-phase plume from further downgradient migration
downgradient migration of the dissolved-phase plume. beyond the source area thereby supporting enhanced natural
Groundwater potentiometric contour maps show- attenuation of the greater plume. The next phase of work will
ing groundwater elevations in the DGR area were used to include evaluation of recalcitrant areas and stagnation points
assess hydraulic control of the LNAPL and dissolved-phase within the dissolved-phase plume as the basis for optimiz-
plumes. Typical heads during system operation are shown ing the direction and magnitude of the recirculation cells.
in Figure 5.34. Based on an analysis of flow direction from The DGR system was designed with operational flexibility
the potentiometric contours, the DGR system has maintained such that the recirculation cells can redirect flow in multiple
hydraulic control of the dissolved-phase plume beneath the directions to flush and oxygenate potential stagnation points
LNAPL source area. As shown in Figures 5.33 and 5.34, that may have developed beneath the source area.
plume-wide monitoring data supports this assessment. Figure The expanded system is expected to operate until reduc-
5.34 also shows a stagnation point along the downgradient tions of the LNAPL source area are such that continued flux
172
648
649
650
64
8
651 64
8
651
649
650
FIGURE 5.34  Typical groundwater elevations in the dynamic groundwater recirculation area during operation.
of contaminants off the LNAPL body will not result in further
downgradient expansion of the dissolved-phase plume. Once
active remediation has been discontinued, additional monitor-
ing will confirm the stability of the dissolved-phase plume. If
necessary, portions of the DGR system can be switched on
to provide additional treatment and hydraulic control, until
plume stability can be confirmed.
REFERENCES
1. National Research Council. 1994. Alternatives for Groundwater
Cleanup. Washington, DC: National Academy Press.
2. Kelly, M.M. February 1994. Applying innovative technologies
to site contamination: Historical trends and future demand.
Presented at Haz Mat South ‘94, Orlando, FL.
3. Hubbert, M.K. 1957. Darcy’s law and the field equa-
tions of the flow of underground fluids. Bulletin de
l’Associationd’Hydrologie Scientifique 5: 24–59.
4. Aris, R. 1956. On the dispersion of a solute in a fluid flowing
through a tube. Proceedings of the Royal Society A 235: 67–77.
5. Aris, R. and N.R. Amundson. 1957. Some remarks on longitudi-
nal mixing or diffusion in fixed beds. AIChE Journal 3: 280–282.
6. McHenry, K.W. and R.H. Wilhelm. 1957. Axial mixing of
binary gas mixtures flowing in a random bed of spheres.
AlChE Journal 3: 83–91.
7. Deans, H.A. 1963. A mathematical model for dispersion in
the direction of flow in porous media. Society of Petroleum
Engineers Journal 3(1): 49–52.
8. Coats, K.H. and B.D. Smith. 1964. Dead-end pore volume and
dispersion in porous media. Society of Petroleum Engineers
Journal 4(3): 73–84.
9. Guilbeault, M.A., B.L. Parker, and J.A. Cherry. 2005. Mass
flux distributions from DNAPL zones in sandy aquifers.
Groundwater 43(1): 70–86.
10. Payne, F.C., J.A. Quinnan, and S.T. Potter. 2008. Remediation
Hydraulics. Boca Raton, FL: CRC Press, 408 pp.
11. Potter, S.T., F. Payne, M. Schnobrich, and J. Quinnan. 2015.
Large plume remediation: Quantifying the effects of scale
on remedy design and operation. Remediation Technology
Summit (RemTEC15), Denver, CO, March 1–4, 2015.
Remediation Engineering
64
7
646
647 Groundwater monitoring well
DGR injection well
646
DGR extraction well
647
7
64
Performance monitoring well
648 Groundwater contour
Groundwater flow direction
Stagnation point
64
8
LNAPL extent
0 200
A A΄ Cross section
Scale (ft)
12. Zheng, C. 2010. MT3DMS v5.3 supplemental user’s guide.
Technical Report to the U.S. Army Engineer Research and
Development Center, Department of Geological Sciences,
University of Alabama, Tuscaloosa, AL, 51pp.
13. Bagtzoglou, A.C. and P.M. Oates. 2007. Chaotic advection
and enhanced groundwater remediation. Journal of Materials
in Civil Engineering 19(1): 75–83.
14. Mayes, D.C. and R.M. Neupauer. 2012. Plume spreading in
groundwater by stretching and folding. Water Resources
Research 48: 1–10.
15. Ottino, J.M. 1990. Mixing, chaotic advection, and turbulence.
Annual Review of Fluid Mechanics 22(1): 207–254.
16. Piscopo, A.N., R.M. Neupauer, and D.C. Mays. 2013. Engineered
injection and extraction to enhance reaction for improved in situ
remediation. Water Resources Research 49: 1–8.
17. USEPA. 1993. Administrative order of consent. Reese Air
Force Base, Docket No. VI-7003-93-1. July 23, 1993.
18. Potter, S.T., E. Moreno-Barbero, and C.E. Divine. 2008.
MODALL: A practical tool for designing and optimizing cap-
ture systems. Ground Water 46: 335–340.
19. Landers, J. 2011. Civil engineering news: Groundwater model
shortens remediation project by 20  years. Civil Engineering
Magazine, November 2011, pp. 26–27.
20. Schnobrich, M., D. Nelson, M. Logan, A. Auffermann, and
J. Martin. 2011. Optimized design of large plume enhanced
reductive dechlorination (ERD) systems: An analysis of 85
sites. RemTEC 2011. Platform Presentation. Chicago, IL.
21. Suthersan, S., S. Potter and M. Schnobrich 2013. Ground­
water restoration: Large-scale benefits of small-scale pro-
cesses. Groundwater Monitoring and Remediation 33:
31–37.
22. Zaney, R. 2013. Taming the “Tower Plume.” The Military
Engineer 105(681): 51–52.
23. Gelhar, L.W. and J.L. Wilson. 1974. Ground-water quality
modeling. Groundwater 12(6): 399–408.
24. USEPA. 1988. Interim final guidance on remedial actions or
contaminated ground water at Superfund sites. Washington,
DC: U.S. EPA, 100pp.
25. Zheng, C., G.D. Bennett, and C.B. Andrews 1991. Analysis
of ground water remedial alternatives at a Superfund site.
Groundwater 29(6): 838–848.
 6 Injected Reagent–Based Remedies
6.1 INTRODUCTION TO IN SITU
REACTIVE ZONES
Since the first edition of this book, no other class of remedial
technologies has evolved as significantly as injection-based
cleanup strategies. The combination of improved character-
ization techniques, a renaissance in our understanding of
groundwater contaminant transport, and expansion of our
knowledge base pertaining to microbial ecology and chemi-
cal transformation processes has enabled deployment and
completion of in  situ remedies with considerable control.
While it can be argued that the initial motive for applying
these technologies was one of saving money as an alternative
to many underwhelming groundwater extraction remedies,
continuous innovation has led to (1) faster, cheaper solutions,
(2) less-invasive technologies capable of achieving stringent
cleanup objectives, and (3) complementary technologies to
the natural environment that leverage nature’s capacity to
degrade pollutants.
Oxidation, reduction, and natural biogeochemical pro-
cesses play a major role in the mobility, transport, and fate of
inorganic and organic contaminants in the subsurface, specif-
ically in groundwater systems. The development of engineer-
ing applications to manipulate and enhance these conditions
was therefore a predictable extension of bench-scale and
site assessment observations. As most contaminants exhibit
unique transformation processes in the presence of other
naturally occurring and anthropogenic materials, these reac-
tions can be utilized to achieve various microbial reactions
or chemical reactions within in situ reactive zones (IRZs) to
remediate contaminated sites.
6.1.1  Background
The realization that mass removal efficiencies can be signifi-
cantly enhanced using air as a stand-alone extractive media
or in addition to water led to the development and application
of in situ extractive technologies such as soil vapor extraction
and in situ air sparging. While the shift towards these tech-
nologies was driven by reductions in overall remedial cost,
the end result has been much quicker cleanup times to more
acceptable cleanup levels. This win–win situation for the entire
remediation industry fostered development of a wide array of
alternative in situ technologies that represented environmen-
tally, economically, and sustainable treatment solutions.
The in situ extractive techniques subsequently gave way to
in situ nonextractive techniques such as funnel and gate sys-
tems. In situ mass destruction techniques such as IRZs are the
preferred remediation technologies today, due to their supe-
rior technical and cost efficiencies and the ease in which they
are deployed. Oxidation, reduction, and other biogeochemical
processes play a major role in the mobility, transport, and
fate of inorganic and organic contaminants in the subsurface,
specifically in groundwater systems. Hence, engineering and
manipulation of these conditions and processes to create dif-
ferent types of IRZs to remediate contaminated sites was a
predictable evolution. Different processes to achieve various
microbial reactions or chemical reactions can be designed to
be implemented within these IRZs.
6.1.1.1  IRZ Definition
The concept of an IRZ is based on the creation of a unique sub-
surface zone in which contaminants retained in saturated soil
media or migrating in groundwater are intercepted and per-
manently immobilized or degraded into inert or harmless end
products. Figure 6.1a and b depict the concept of IRZs. The
successful design of these reactive zones requires the ability to
engineer two sets of reactions: (1) between the injected reagents
and the contaminants; and (2) between the injected reagents and
the subsurface environment to manipulate the biogeochemistry
to optimize the required reactions. These two different sets of
reactions are often complementary and reagent selection con-
siderations include an accounting of both favorable geochemi-
cal indicators to the IRZ treatment process and potentially
detrimental site conditions that could limit overall treatment
effectiveness. As these conditions will be different at each con-
taminated site (or within a given plume), the biggest challenge
is designing an engineered system for the systematic control of
these reactions under the naturally variable or heterogeneous
conditions found in the field.
The fundamental requirements for developing effective
reactive zones can be generally consolidated into two over-
arching principles: (1) the kinetics of the target reactions
must occur at a rate equal to or greater than the mass flux of
contaminants and other competing reactants passing through
the IRZ with moving groundwater, and (2) injected reagents
must be successfully distributed and sustained at sufficient
concentration within the IRZ to promote the target reaction.
Successful execution is therefore reliant on the proper reagent
selection but also the receptivity of the reactive zone to uni-
form fluid introduction.
Many processes that take place in groundwater systems
influence contaminant transformation in the subsurface and
have to be taken into consideration when designing an IRZ.
Contaminants can sorb onto the soil, volatilize, react with
water and hydrolyze, undergo chemical precipitation, be sub-
jected to abiotic reactions and/or biodegradation, and be part
of oxidation–reduction sequences. The factors that are criti-
cal for successful engineering and implementation of in situ
remediation processes are chemical and physical character-
istics of the contaminants, which are influenced mostly by
their molecular structure; environmental conditions, which
173
174 Remediation Engineering

Individual reactive zones created by

individual injection points providing a
collective IRZ curtain
Source area
IRZ grid

Contaminant plume

(a)

Reagent Injection Reagent

O2 In situ
reactive zone
NO3–
SO42– Contaminant
plume
Continuous flux of
electron acceptors
(b)

FIGURE 6.1  (a) Plan view of creation of downgradient IRZ barrier transect and source area IRZ grid. (b) Cross-sectional view of IRZs
created by individual injection wells.

can be summarized as the biogeochemical conditions; and the
hydrogeologic conditions that control delivery and transport
of reagents for the target in situ reactions.
6.1.1.2  Types of IRZ Reactions
Contaminants within the subsurface environment are sub-
jected to various physical, chemical, and biological processes.
These processes act in an interconnected way in environ-
mental systems that determine the overall fate of these com-
pounds. Some of these processes leave the structure of the
chemical unaffected and are generally termed as transport
mechanisms. Other processes transform the chemical into one
or several other products of different environmental behav-
ior and effects. These types of processes alter the molecular
structure of a compound and may include chemical, biochem-
ical, and/or biological transformation reactions.
The types of reactions that can be designed and imple-
mented within an IRZ are many. Chemical, physical,
biochemical, and microbial reactions in water can be homo-
geneous, occurring entirely among dissolved species, or het-
erogeneous, occurring at the liquid–solid–gas interfaces. The
development of microbial communities within biofilms and
on soil surfaces and the presence of naturally occurring reac-
tive metals within the soil matrix result in most subsurface
reactions being heterogeneous, with purely homogeneous
reactions relatively rare in the groundwater environment. This
difference in reaction types is most apparent in discrepancies
between bench-scale reaction vessel observations and actual
achievable field treatment performance.
Reactions can be defined as processes in which chemical
bonds are broken, new bonds are formed, or one atom replaces
another in the molecular structure of a compound. Reactions
in general can be categorized as substitution, elimination, and
configuration reactions. Within the IRZs, the general expecta-
tion is for transformation to result in harmless end products or
products less harmful than their parent compounds—with the
ideal case being mineralization. Mineralization is defined as
the complete conversion of an organic chemical to stable inor-
ganic forms of natural C, H, N, O, P, and other elements (e.g.,
conversion to CO2, H2O, NO32−, NH4+, PO43−). As there are
examples of “incomplete” transformation daughter products
that are of greater environmental concern (e.g., vinyl chlo-
ride generated during chlorinated ethene or ethane degrada-
tion), appropriate reaction zone design is necessary to ensure
that the properties, reactivities, and toxicities of intermediate
products do not pose greater risk.
For our evaluation of the various transformation reac-
tions that contaminants undergo naturally or are engineered
in the subsurface environment, it is convenient and common
to divide these processes into two major categories: chemical
Injected Reagent–Based Remedies
and biological. These reactions can be subdivided into those
where there is no net electron transfer occurring between the
contaminant and a reactant in the environment and into oxi-
dation–reduction (redox) reactions where electrons are either
transferred from (oxidation) or to (reduction) the contaminant.
Historically, geochemical processes were thought to be
largely, if not entirely, driven by abiotic chemical reactions.
We now know that many important geochemical reactions are
driven by bacteria. Microorganisms have been found in even
the harshest of environments—deep-sea hydrothermal vents,
toxic abandoned mine sites, and even deep under the Earth’s
surface—so their ability to adapt to and utilize a variety of
toxic contaminants is not unexpected. Numerous studies have
documented that chemical reactions close to microbial sur-
faces or within networks of biofilm are very different from
those of the bulk solution. The chemistry of this “microbial
space” is complex and has a significant influence on the desir-
able reactions within an IRZ.
Reactions, chemical or biochemical, may be described
from the standpoint of either kinetics or equilibrium. Kinetics
describe the rate at which a reaction takes place and is sig-
nificant when comparing a particular reaction rate to the rate
at which a comparable process takes place. Equilibrium, by
contrast, describes the final expected chemical composition
in a control volume. A control volume with its biogeochemi-
cal components is often referred to as a system. Equilibrium
is relevant in the case of reactions that are rapid (e.g., during
chemical oxidation processes) and accounts for the particular
geochemical conditions within a reactive zone.
When reactants first come together—before any products
have been formed—their rate of reaction is determined in part
by their initial concentrations. As the reaction products accu-
mulate, the concentration of each reactant decreases and so
does the reaction rate. For reversible reactions, the accumu-
lation of the product molecules begins to participate in the
reverse reaction, which reforms the reactants. This reaction
is slow at first but speeds up as the concentration of products
increases. Eventually, the rates of the forward and reverse
reactions become equal, so that the concentrations of reac-
tants and products stop changing. The mixture of reactants
and products is then said to be in chemical equilibrium.
As most groundwater aquifers are “open systems” (i.e.,
no control volume) and continuously exposed to naturally
migrating organics and inorganics, equilibrium in these set-
tings is usually referred to as a “steady-state” condition—but
true equilibrium is not achieved. These steady-state condi-
tions can be easily perturbed based on changes in concentra-
tion of either the reactants or products of a given equilibrium
relationship, via the introduction of contaminants, which can
upset the existing geochemistry or be consumed by micro-
organisms, and by injection reagents designed to induce
target reactions to facilitate contaminant destruction or
transformation.
6.1.1.3  Contaminant Considerations
A contaminant’s physicochemical properties dictate its over-
all behavior within the subsurface and its accessibility for
175
injection-based treatment applications. A contaminant’s rela-
tive susceptibility to biological or chemical transformation
reactions, its tendency to sorb to soil matrices or form precipi-
tates, and its degree of volatility and solubility all control the
particular phase in which contaminants reside, how they par-
tition and migrate through the subsurface, and how they react
or are transformed. These nuances are highlighted throughout
this chapter, with specific attention paid to the development
of injection-based design applications that can be deployed as
part of biological, chemical, or abiotic IRZ applications.
Contaminants can be utilized by microorganisms as
electron donors (and are oxidized), electron acceptors (and
are reduced), or cations and anions in exchange reactions.
For biodegradation applications, depending on contaminant
behavior and the natural capabilities of a site-specific micro-
bial community, injection reagents often entail the limiting
species (either an electron donor or acceptor) to support utili-
zation by the microbial species. A variety of organic contami-
nants serve as electron donors and include benzene, toluene,
ketones, and single- or multiringed petroleum hydrocarbons
(PHCs). The corresponding injection reagents designed to
foster in situ biological treatment of these constituents there-
fore include a spectrum of natural electron acceptors includ-
ing oxygen, nitrate, or sulfate, which are then utilized by the
microbial community as the contaminant is transformed.
Conversely, electron donors are utilized as the primary
injection reagents for treatment of contaminants that serve
as electron acceptors—most notably chlorinated aliphatic
hydrocarbons, perchlorate, explosives, and other inorganics.
Contaminant metabolism by individual microbial species
or the broader microbial consortia varies based on a variety
of factors including a contaminant’s relative stability, degree
of substitution and steric availability to enzymatic attack, its
molecular similarity to other common organic compounds
involved in cellular metabolism, its relative toxicity, and the
overall time that a compound has existed within the environ-
ment. For classes of contaminants that have existed for millen-
nia (e.g., aromatic hydrocarbons), microbial species long ago
adapted the ability to utilize these compounds for both energy
and growth. For other contaminants of more recent anthro-
pogenic origin (e.g., 1,4-dioxane, polychlorinated biphenyls
[PCBs], poly- and perfluoroalkyl substances [PFAS]), consid-
erably fewer organisms are available that mediate transforma-
tion reactions—if at all.
Where microbial technologies are not applicable or require
too much time, chemical oxidation and reduction technolo-
gies are considered. Similar contaminant properties related to
bonding, ligand substitution, and structure also affect whether
specific oxidants are applicable or the kinetics by which these
contact reactions occur. For kinetic-based oxidation–reduction
remedies, where the mediating reactant has a defined or lim-
ited half-life, contaminant solubility is of high importance as
treatment occurs in the dissolved phase.
In  situ remedial strategies inherently leverage the natural
processes that contribute to contaminant decline and reagent-
related contaminant transformation. The process of performing
a detailed analysis of a contaminated site in order to assess the
176
potential of the site for the application of an IRZ has much in
common with the assessment performed for monitored natural
attenuation (MNA). Such an assessment bases decision making
on a review of data that includes the contaminants themselves,
electron donors, electron acceptors, partial-degradation by-
products, geochemical parameters, and hydrogeology. Trend
analyses can help determine whether an ongoing source exists
at the site that is still contributing dissolved-phase contaminants
at a rate that natural attenuation processes cannot overcome. In
such a situation, in situ treatment may accelerate contaminant
destruction significantly. In extreme cases, a more aggressive
source removal approach may need to be initiated first.
For contaminants known to be biodegradable, it is impor-
tant to stress that scientific documentation of the mechanism
claimed as responsible for contaminant destruction or con-
trol is scientifically feasible and that the proposed mecha-
nism is actually occurring at the site. Thus, in addition to
documenting contaminant removal in a pilot test or full-scale
treatment process, an IRZ system designer should also be
able to d­emonstrate the fingerprints of the contaminant(s)
transformation processes. For example, these would include
the appearance of intermediate degradation products
(e.g., cis-1,2-dichloroethene (cis-DCE), vinyl chloride, and
ethene during PCE or TCE dehalogenation), the appearance
of indicators that the desired alternate electron acceptor pro-
cesses have been achieved (e.g., reduced dissolved oxygen
(DO) and oxidation reduction potential (ORP), increased fer-
rous iron, sulfide or methane), and the utilization of appropri-
ate electron donors during the implementation of a microbial
IRZ system for enhanced reductive dechlorination (ERD).
6.1.2 Key Parameters for Design
From a classic hydrogeology standpoint, groundwater aqui-
fers are homogeneous and isotropic and could be interpreted
simply based on slug testing, groundwater potentiometric
gradients, and aquifer transmissivity. This approach was rea-
sonable for the design of groundwater supply wells, which
captured groundwater from broad areas with little concern
for its origin. It took decades of groundwater remediation
through the 1970s, 1980s, and 1990s to fully understand that
the application of classic hydrogeologic principles to contami-
nant cleanup was resulting in extended treatment time frames,
remedy failure, and extensive remedial cost overruns due to
inadequate subsurface characterization and an overall limited
awareness of contaminant transport. The emergence of injec-
tion-based remedial strategies and the accumulation of data
pertaining to subsurface reagent transport were a key driver
in prompting a reevaluation of hydrogeology as it pertains to
contaminant transport. The original assumption that contami-
nants moved via advection and dispersion has been entirely
replaced by the awareness that transport is controlled via
advection and diffusion. Further, application of historic site
depositional concepts has yielded the new assumptions that
aquifers are actually heterogeneous and anisotropic as a rule.
The understanding that contaminants migrate via advec-
tive pathways in more permeable soils and are stored or
Remediation Engineering
sequestered in finer-grained low-permeability matrices is a
key aspect for approaching IRZ designs. Ultimately, more
permeable soils control the advancement of injection fluids
both vertically and laterally from a delivery point and play
a significant role in the advective and diffusive distribution
of reagents following delivery. While classical hydrogeologic
interpretations remain important from a macroscopic site
assessment standpoint, a more microscopic view of specific
site heterogeneities is provided by injection tracer testing and
appropriate geologic interpretation to best guide injection
reagent selection, dosing considerations, injection point place-
ment, and fluid introduction strategies. The following sections
provide a detailed view of how each of these components is
integrated in IRZ delivery design.
6.1.2.1  Volume–Radius Relationship
Within the subsurface, we can envision a network of intercon-
nected pore spaces, the larger and better connected of which
provide less resistance to groundwater movement and serve
as the primary groundwater migration pathways. Figure 6.2
shows a pore-scale depiction of an aquifer matrix. Smaller and
more poorly connected pore spaces present greater resistance
to groundwater movement and harbor a static groundwater
mass that lies on the sideline of more migratory pathways.
A key concept in this construct is that a relatively small frac-
tion of the aquifer pore spaces is “migratory” and actually
participates in advective groundwater and contaminant flow.
This concept is especially important when we consider the
distribution of contaminants and design methods for distribu-
tion of reagents in aquifers.
In a homogeneous soil system, fluids injected into an aquifer
matrix through a vertical injection well travel outward radially
through the soil formation that intersects the depth interval of
the injection well. Differences between horizontal and vertical
FIGURE 6.2  Dual-domain transport in an aquifer; arrow size rep-
resents migratory pore fraction with size differences variable based
on differences in relative permeabilities.
Injected Reagent–Based Remedies 177

hydraulic conductivities determine the relative proportions of
horizontal and vertical injected fluid movement. In many aqui-
fers, the vertical hydraulic conductivity is significantly lower
than the horizontal hydraulic conductivity, effectively confin-
ing injected fluids to the injection screen interval. As discussed
in Section 6.1.2, injected fluids travel principally through the
migratory flow paths or the mobile fraction of the aquifer. Even
in homogeneous soil systems, the mobile fraction will repre-
sent some percentage of the total porosity and serve as the cor-
rection factor to determine how far injection fluids travel based
on the injection volume introduced. Equation 6.1 provides a
calculation of rinj, the radius occupied by the injected fluid
immediately after the injection process is completed:
Vinj
rinj = (6.1)
p ´ h ´ qm
where
h is the injection zone thickness (normally the length of the
injection well screen)
θm is the mobile fraction
Vinj is the injected volume
Equation 6.1 is only valid when the rate of fluid injection
temporarily overwhelms the natural groundwater movement
through the injection zone and is a reasonable assumption in
most slow to moderate flow groundwater systems where injec-
tions are completed over a matter of days to weeks.
The mobile fraction of an aquifer represents a certain
percentage of the overall aquifer porosity. A summary of
observed values of θm (as a percentage of total aquifer volume)
is provided in Table 6.1, with corresponding injection volumes
provided for variable target values of rinj in Figure 6.3. For a
given unit volume, the value of rinj will increase with decreas-
ing values of θm. As observed in Table 6.1, the values of θm
will always be less than the total drainable fraction (or total
porosity) of an aquifer and are most often lower than con-
ventional effective porosity assumptions for most soil types.
It is easy to understand that fluids will migrate more exten-
sively within gravels compared to clays (with the quantity of
gravel contributing to the value of θm), but differences in θm
are also encountered in sands and gravels of variable grain
size. The overall differences in values for mobile fraction,
effective porosity, and total porosity illuminate the role that
dual-domain transport plays in reagent, contaminant, and
groundwater transport. Reagents will migrate preferentially
within the mobile fraction, will move via slower advection
through permeable soils with lower hydraulic conductivity
values, and diffuse between these zones and into the surface
of low-permeability soils.
Intuitively, the introduction of fluids into the mobile frac-
tion of an aquifer will displace existing groundwater (and
contaminants) radially outward from the zone of injection or
vertical upward via groundwater mounding. This is a function
of the overall incompressibility of water and can represent a
potential concern, particularly in applications when injection
wells are positioned as part of a broad grid, the target injection
volumes are considerable (e.g., 1000s of gallons per point),
and injection activities are conducted as part of routine deliv-
ery events. Estimates for plume displacement can be deter-
mined for a given injection well by reorganizing Equation 6.1

TABLE 6.1
Summary of Mobile Porosity Estimates Determined by Tracer Tests
Location Aquifer Aquifer Material Mobile Porosity Notes
Quebec, Canada — Poorly sorted sand and gravel 8.5% 6.4 m3 injection in 7.25 h
Central Valley, California — Poorly sorted sand and gravel 4% to 7% 575 m3 injection over 30 days; arrival
monitored in 7 wells
Northern Texas Ogallala Poorly sorted sand and gravel 9% 1460 m3 injection over 28 days
New Jersey Passaic Formation Fractured sandstone 0.1% to 0.7% 24.6 m3 injection over 2 days
Los Angeles, California Gaspur Aquifer Alluvial formation 10.2% 17 m3 injection over 8 h
Northern New Jersey — Glacial outwash 14.5% 7.57 m3 in 3 days
Northern Missouri — Weathered mudstone regolith 7% to 10% 4.54 m3 in 9 days
Sao Paulo, Brazil — Alluvial formation 7% 18.9 m3 over 2.5 days
Phoenix, Arizona — Alluvial formation 7% 2.27 m3 in 8 h
Savannah River Site, South Atlantic Coastal Plain Silty sand 5% Model calibration
Carolina1
Kaiserslautern, Germany Trifels Formation Fractured sandstone 0.08% to 0.1% Multiple injections and volumes between
0.1 m3 and 5 m3
West Texas Rio Grande River Valley Alluvium, sand, and gravel 1.7% 18.9 m3
Northern Texas Ogallala Alluvium, poorly sorted sand, 0.3 to 1.7% Dipole test, 61.3 m3 in 22.8 h
and gravel
Central Colorado Cherry Creek Alluvium, sand, and gravel 11% to 18% Two injection tests, 4.9 m3 and 7.6 m3
Central Colorado Denver Formation Siltstone, sandstone, mudstone 1% to 5% Monopole—tracer injected in monitoring
well/pumping well
178
70,000
Typical fractured bedrock
60,000
Typical natural porous medium
Volume (gal) per 10 ft thick section
50,000
40,000
30,000
20,000
10,000
0
0 5
FIGURE 6.3  Relationship between aquifer mobile fraction, target radial distribution from an injection well, and injection volume for
porous media and fractured rock systems. (From Payne F.C. et al., Remediation Hydraulics, CRC Press, Boca Raton, FL, 2008.)
to solve for the injection radius based on a volume equiva-
lent to two-times that injected (i.e., the injection volume plus
the native groundwater displaced). This calculation assumes
that all groundwater travels horizontally (and negates mound-
ing), so represents a conservative estimate in unconfined
systems. As detailed as part of Section 6.1.3.2, the potential
for plume displacement can be managed as part of injection
layout design, is minimized in barrier-style applications ori-
ented perpendicular to groundwater flow, or can be irrelevant
when employing soluble substrates that will migrate within
advective groundwater flow following delivery (i.e., into the
displaced groundwater).
6.1.2.2  Injection Delivery Methods
Injection delivery methods include fixed injection wells,
temporary injection points, direct-push delivery techniques,
hydraulic fracturing, or pneumatic fracturing. The spe-
cific delivery methodology is generally selected based on
the desired injection reagent (i.e., whether it is soluble or
insoluble) and target soil formation in which the injection is
intended. Permanent well applications are constructed with
materials appropriate for the geologic formation, groundwa-
ter quality, and selected reagent. A typical injection well is
shown in Figure 6.4. Wells in an unconsolidated formation are
typically 2 to 4 in. in diameter and constructed using either
stainless steel or polyvinyl chloride (PVC) wire wrapped well
screens sized for the soil formation. Stainless steel screen
constructions, while more expensive, represent the gold stan-
dard for injection applications. Stainless steel provides for
improved hydraulic communication with the aquifer; can be
more aggressively redeveloped using jetting, surge block, and
well rehabilitation chemicals; and are wise investments for
Remediation Engineering
0.30
0.20
Mobile porosity
0.10
0.05
0.02
10 15 20 25 30
Radial distance (ft)
IRZ programs that require multiple or routine injection activi-
ties. In bedrock, an open borehole in the target-saturated zone
is acceptable, but conversion of existing bedrock open-hole
wells to screened wells is advantageous to focus delivery of
reagents into the specific fracture zones requiring treatment.
Wells constructed in this fashion provide a permanent and
repeatable means of delivering reagent to the subsurface.
IRZ wells must be screened to target the vertical impacts
in groundwater. Thus, the depth and screened interval will
be determined by the vertical delineation of the groundwa-
ter impacts—with all the limitations this implies. The lithol-
ogy will also have an impact on the well design and screened
interval since the injected reagent will flow with groundwater,
following the path of least resistance. Where the saturated
thickness of contamination exceeds 20 to 30 ft, multiple well
points are recommended to improve horizontal distribution
and circumvent the possibility of injection fluids being trans-
mitted through preferential flow intervals.
Hydraulic or pneumatic fracturing applications are both
viable techniques to engineer subsurface soil formation fail-
ure such that reagents can be propagated via the pressure-
induced fractures. Hydraulic injection applications utilize
direct-push tooling to advance injection rods to the target
delivery depth or utilize predrilled guide borings through
which the fracture tooling is extended to the desired depth of
injection (Figure 6.5a and b). As the name implies, hydraulic
fracturing relies on creating weaknesses and deformation in
the soil matrix through which small volumes of fluidized
reagent slurries (for semisoluble or nonsoluble reagents) or
dissolved reagents in water are introduced. Comparatively,
pneumatic fracturing employs similar delivery concepts but
relies on either gas, sand, or other propagants to establish
Injected Reagent–Based Remedies
¼'' pressure relief
valve
Land surface
4'–0''
6''
6''
10'–0''
FIGURE 6.4  Typical injection well design.
fractures through which the reagents are then advanced.
There are a variety of fracture techniques and injection tool-
ing available, each of which has specific nuances by which
fractures are established and fluids are delivered. These
vary in overall complexity from simple direct-push drive
rods with delivery equipment capable of achieving injection
pressures between 50 and 100 psi to more complex applica-
tions reliant on predrilled boreholes, injection nozzles that
extend deeper into the subsurface, and equipment feasible
of achieving injection pressures in excess of 1000 psi. Due
to limitations with advancing direct-push injection tooling,
this more simplistic delivery method is frequently limited to
shallow, unconsolidated formations at depths typically less
than 50 ft below grade.
There are considerable differences in overall injection vol-
umes between well-based delivery and fracture applications.
179
1'' ball valve
Concrete pad
4 '' boot seal well cap
8 '' casing
Hydrated bentonite
(from top of neat
cement to well vault)
4 '' SCH. 80 PVC
Neat cement grout
(double length of screen)
Fine choker sand
4'' stainless steel/SCH. 80 PVC
coupler
4'' stainless steel wire wrap screen
(≤15 ft. length)
Sand filter pack
Well-based injections typically entail significant volumes of
fluid (often 1000s of gallons) that consume the available pore
space over which the well screen is installed. Comparatively,
fractures developed via high-pressure applications are less
than one inch in vertical thickness and considerably smaller
reagent volumes (10s to 100s of gallons) are applied to move
horizontally through these narrow features. To compensate
for the narrow vertical delivery achieved, fracture injection
designs utilize multiple discrete intervals to allow vertical
coverage across the interval of contamination. These intervals
are often spaced between 1 to 5 ft apart. This approach results
in an overall reagent distribution that is highly stratified, with
concentrated reagents emplaced within thin fractures that are
interbedded with reagent deficient native soil materials that
also contain contaminants. As reagent transport and diffu-
sion are the primary mechanisms by which contaminants
180
Reagent delivery
Ground surface
(a) Media-filled fractures
FIGURE 6.5  Fracture-based injection tooling. (a) Direct-push delivery point. (b) Precased boring with downhole fracture injection tooling.
in reagent-deficient soil strata are treated following fracture
injections, adequate assessment of the site-specific geology
and the nature of contaminant distribution is imperative to
enable achievement of complete treatment and reduce the
required number of injection applications.
As fracture-based delivery methods require only tempo-
rary injection points and no permanent well network, these
can be more cost-effective when only one injection event is
required. When multiple events are expected, permanent well-
based strategies are more cost-effective due to the reduced
costs of completing subsequent injection events. Well-based
strategies can also be more cost-effective on a per-event
basis due to the ability to manifold multiple wells together
for simultaneous injection. Generally, well-based applications
provide more uniform reagent coverage, enable larger vol-
umes during delivery, and offer far greater fluid distribution
control during delivery. These are not appropriate, however,
(a)
FIGURE 6.6  Multiple wellhead connection fittings and injection setups to achieve either gravity feed delivery (a) or pressure-based appli-
cation (b).
Remediation Engineering
Reagent delivery
Ground surface
(b) Media-filled fractures
when the geology is less permeable or uninjectable via low-
pressure applications or in cases where solid-phase reagents
are desired and require fracture emplacement opposed to
standard well screens.
6.1.2.3  Injection Pressure Considerations
Reagent injection can be implemented in two ways: via grav-
ity feed delivery or via pressurized injection application
(Figure 6.6a and b). Fluid injection into a saturated soil media
must overcome resistive forces associated with groundwater
displacement from within the target radius of influence (ROI).
While general resistance to fluid displacement is tied to the
natural incompressibility of water, injection flow rates are fur-
ther limited by the natural soil permeability, the presence of
confined or semiconfined aquifer systems, or the buildup of
gases and precipitates from the target reactions. As discussed
in Section 6.1.2.1, the horizontal hydraulic conductivity is
(b)
Injected Reagent–Based Remedies
significantly greater than the vertical conductivity, which
results in the preferential transport of injection fluids laterally
away from the point of introduction. While lateral transport
predominates, vertical groundwater mounding does occur
and can act to limit injection flow rates in confined aquifer
systems where vertical transport is not available. In these
systems, which often exhibit naturally upward groundwater
gradients or are under natural pressure, fluid injection under
gravity feed or even via pressurized applications is often
limited.
As described in the preceding section, a variety of injec-
tion techniques are available to introduce fluid into the sub-
surface. With fixed injection well applications, gravity feed
(or low-pressure) delivery approaches are preferable to pres-
surized applications as they are most protective of the injec-
tion well integrity, require less above-grade infrastructure,
and rely on the natural distribution of reagents through the
primary aquifer transport pathways. Gravity feed delivery is
also the best means to ensure that the pressure applied to the
soil formation does not result in the failure of the soil matrix
and result in unintended hydraulic fracturing.
Hydraulic fracturing occurs when pore water is overpres-
surized to the point that it physically separates the soil matrix.
Safe injection pressures can be determined considering the
overburden stress of an aquifer at the top of an injection inter-
val assuming normally consolidated soils. The weight of over-
burden soils compresses the soil matrix, giving it strength to
resist shear deformation. This stress is transmitted as grain-
to-grain contact pressures that increase with depth and pro-
vide natural vertical and horizontal effective stresses that
resist shearing.1 Below the water table, groundwater in pore
spaces counteracts natural soil stiffening by exerting pressure
in all directions and reducing the grain-to-grain contact pres-
sures. Under normal subsurface conditions, changes in pore
pressure do not alter the soil architecture except for some
minor elastic strain. However, if the pore pressure increases
excessively, the contact pressure between the grains may drop
to zero, effectively separating the grains (i.e., fracturing the
soil). In noncohesive soils, fracturing will alter the soil struc-
ture and decrease the formation yield. In cohesive soils, these
fractures may then persist as new mobile pathways and may
permanently serve as preferential pathways that can short-
circuit future fluid introduction.
The weight of soils and groundwater above the injection
interval results in a vertical effective stress that is consider-
ably greater than the horizontal effective stress. Accordingly,
the horizontal effective stress is the determining factor for
formation failure. Applied injection pressure increases the
soil pore pressure and increases the ratio of the vertical to
horizontal effective stress. As this ratio increases (as horizon-
tal effective stress approaches zero), failure occurs.1 Applied
pressures used to engineer fractures leverage this relationship,
ultimately enabling the lateral transport of reagents from the
injection point. The lateral extent of fractures is limited, how-
ever, as fractures will naturally propagate upward toward the
vadose zone or ground surface. The angle at which the frac-
ture would propagate vertically is related to the friction angle,
181
which is a characteristic of a particular soil and describes the
resistance to shear.
While methods for determining safe injection pressures
are available for a given soil type, these empirical calcula-
tions can be further supported via laboratory geotechnical
analyses (soil cohesive strength, shear testing, compression
testing) or via data collected by cone penetrometer testing
to obtain shear strength estimates. A theoretical injection
pressure calculation does provide a reasonable starting
pressure for injection testing and is particularly relevant
to the preservation of permanent injection wells. Some
key concepts to keep in mind as designers are determin-
ing appropriate injection pressures are summarized in the
following:
• In a homogeneous soil, the likelihood of fracture at
a given injection pressure decreases with depth. The
top of an injection interval (top of screen) is most
vulnerable.
• In heterogeneous soils (essentially all natural soils),
the resistance to fracturing (the shear strength) of
soil is highly variable, depending on whether the soil
is cohesive and on the grain size and sorting.
• When injecting into the heterogeneous medium,
the weakest intervals will fracture first. Existing
planes of weakness or low-strength strata (such as
well-sorted fine sand) have the greatest tendency for
deformation.
• Fractures will typically not propagate across strata
of differing strengths or across existing planes of
weakness.
• Many unconsolidated formations are already frac-
tured naturally. This is particularly true of shallow
cohesive soils that may have been unsaturated at
some point in geologic history or undergone signifi-
cant stress and strain.
The theoretical injection pressure that would result in aquifer
deformation can be calculated based upon the position of the
injection interval in relation to the vadose and saturated zones
within an aquifer in both unconfined and confined settings.
The total vertical stress (σs) of the overburden soils is calcu-
lated by multiplying the thickness of the vadose zone (hvz) and
saturated zone (hsz) above the injection interval by their cor-
responding density (ρvz and ρvz, respectively) via the following
equation:
ss = (hvz ´ rvz ) + (hsz ´ rsz ) (6.2)
The saturated pore pressure (P) can be calculated by multi-
plying the height of the static water column above the injec-
tion interval (water table elevation to the top of the screened
interval) by the unit weight of water (ρH2O) as shown in the
following:
P = (hsz ´ rH2 O ) (6.3)
182
The initial vertical effective stress (σe) represents the differ-
ence between the total vertical stress and the pore pressure, as
shown in the following:
se = ss - P (6.4)
This method assumes normally consolidated soils and that the
horizontal effective stress represents the limiting constraint
with respect to fracturing. Under this assumption, vertical
fractures would be expected. If overly consolidated soils
exist, the vertical effective stress becomes the limiting con-
straint and horizontal fractures are of concern. Based on the
composition of the lithology (i.e., sand, fine sand, gravel), a
friction angle (φ) is assumed according to previous experience
at the site or based on representative literature values.1 The
friction angle is then used with the initial vertical effective
stress to determine the maximum allowable injection pressure
(Pmax), as shown in the following:
Pmax = (1 - sin q) ´ se ´ 0.5 (6.5)
Note the additional 0.5 coefficient in this calculation, which
is related to the assumption of normally consolidated soils. A
complete derivation of the method mentioned earlier and the
applicability to variation in differing soil types is detailed in
Remediation Hydraulics.1 The value of Pmax is presented in
units of pressure but can be also correlated with a correspond-
ing change in water elevation within the injection well via unit
conversion. As Pmax represents the allowable stress at the top of
the well screen (or injection tip depth), these values can all be
integrated with a safety factor (SF) to determine an allowable
gauge pressure observed at the wellhead via the following:
æ P - (hvz ´ rH2 O ) ö
Pg = ç max ÷ (6.6)
è 1 + SF ø new reagents are developed. A detailed discussion of many
Values for SF can be selected by the designer and used to eval-
uate a range of potential injection pressures that could result
in formation fracturing or well failure. As the aforementioned
methodology allows the determination of a starting safe injec-
tion pressure for use during injection, it is recommended that
this be evaluated once the well is constructed at the onset of
the injection program. Incremental additions of pressure can
be applied gradually upward from no pressure (gravity feed)
to the target safe injection pressure. Stepwise changes in pres-
sure can then be applied with corresponding measurements of
injection flow rate, and these observations can then be used to
establish a target injection pressure and flow rate for a given
well over the course of the injection program.
For a confined aquifer, a similar progression is followed
with the addition of compensating for unique specific weights
of the confining layer and the potential for pore pressure satu-
ration above the confining layer (represented as the height of
the observed static water column [hwc]), as corrected in the
following. Due to the negligible vertical displacement that can
Remediation Engineering
be achieved in confined aquifers, these systems support (and
generally require) larger injection pressures:
æ P - (hvz + hsz - hwc ) ´ rH2 O ) ö
Pg = ç max ÷ (6.7)
è 1 + SF ø
While gravity or low-pressure injections can be preferable for
a number of reasons, low-pressure application is not always
feasible based on the soil type, reagent selected, or aquifer
conditions. In these instances, applied pressure injections are
preferable to allow delivery. While fracture-based injection
applications can achieve higher flow rates and require shorter
durations to complete compared to low-pressure delivery,
engineered fracture formation is inherently hard to control.
As described earlier, fractures are established through less
cohesive soils, natural formation weakness, or toward points
of pressure relief. Pressure relief often occurs via monitoring
wells used to evaluate the treatment area, buried infrastruc-
ture, or upward toward the groundwater interface or vadose
zone (with decreased vertical pressure). These pathways can
be challenging to control in both homogeneous and heteroge-
neous soil systems and if not accounted for as part of injection
point orientation can result in reagent short circuiting and lim-
ited contact between the reagents and the target contaminants.
6.1.2.4  Reagent Types and Selection Considerations
Based on the preliminary evaluation of the existing subsur-
face environment, appropriate reagents have to be selected
that are tailored to a contaminant’s or group of contami-
nants’ concentration, distribution within the aquifer (e.g.,
within advective transport or diffuse storage zones), and
phase (nonaqueous-phase liquid [NAPL], sorbed, dissolved).
There are currently a wide variety of commodity and propri-
etary reagents available that can be effectively used in IRZ
applications—and this list will only continue to expand as
materials used in biological and chemical treatment remedies
is provided in Sections 6.2 and 6.3, respectively. In addition
to contaminant-specific considerations, the following are a
number of other key design factors that must be considered
during the IRZ design phase:
1.
Reagent solubility dictates the maximum dosing
concentration that can be mixed above grade and
applied into subsurface; dissolved reagents migrate
with advective groundwater flow beyond the area
of injection, while semisoluble or solid injectants
exhibit limited mobility.
2.
Reagent injectability is considered when selecting
the appropriate delivery methodology to achieve dis-
tribution; materials that are soluble in water or have
a small enough particle size (e.g., less than 1 micron)
can be delivered via a fixed well and advanced
through a soil matrix. Other solid materials will
require elevated injection pressures to induce soil
fractures for reagent emplacement.
Injected Reagent–Based Remedies
3.
Reagent longevity is the duration of time over which
the reagent remains present within the IRZ at suf-
ficient strength to promote the target reaction; these
durations can vary from hours to days (peroxides) to
years (emulsified vegetable oils [EVOs], zerovalent
iron [ZVI]).
4.
Reagent-related by-products are considered to
account for any potential chemical intermediates
generated during the target reactions; these can
include transient intermediates formed during con-
taminant transformation, redox-sensitive metals lib-
erated from native soils, or gaseous species that may
form associated with either biological or chemical
treatment.
5.
Reagent handling considerations include an over-
all awareness of a chemical’s reactivity, negative
exposure risks to personnel, negative ecological
interactions, or compatibility with above-grade or
subsurface materials to ensure that proper health
and safety precautions or engineering controls are
implemented to mitigate any adverse impacts during
remediation.
An overall assessment of these factors is necessary as part
of any IRZ design development. The solubility, injectability,
and longevity considerations are integral to achieving the nec-
essary subsurface delivery and duration of target treatment
reactions. As discussed earlier, injected reagents tend to flow
through the mobile fraction of an aquifer, which also serve as
contaminant migratory pathways. Contaminant mass that has
resided in an aquifer for extended periods of time will have
had sufficient time to diffuse into less permeable portions of
the aquifer matrix. This stored mass outside of the primary
injection intervals increases the overall difficulty of establish-
ing contact between injected reagent and contaminants. To
address diffuse or stored mass present in low ­permeability
or interbedded soil systems, IRZ design preferences often
­consider more persistent reagents that can diffuse into these
static pore spaces for treatment.
As nearly all reagents used in either biological or chemi-
cal IRZ applications will disrupt the natural steady-state
equilibrium conditions within a given soil and groundwater
system, it is important to have an awareness of specific non-
target by-products (a number of which are also regulated and
included as part of monitoring programs) that may be gener-
ated and their resultant behavior within or outside the IRZ. To
accommodate both nontarget by-product generation and man-
age bulk reagents above grade, appropriate health and safety
precautions must be taken by on-site personnel to eliminate
the potential exposure to potentially hazardous or nuisance
conditions. Most handling provisions are generally tied to the
behavior of the reagents themselves and are more rigorous
and explicit for chemical oxidation and generally less robust
(outside of secondary containment or incidental spill response
plans) for many food- or feed-grade reagents used in biologi-
cal treatment remedies.
183
6.1.2.5  Injection Frequency
The successful application of an IRZ system is first and fore-
most reliant on the timely, cost-effective, and consistent deliv-
ery of the reagent to the treatment zone in quantities carefully
tuned to produce the desired reactions in the subsurface.
Injection timing is based on two primary controlling factors:
(1) the duration over which a “working strength” concentra-
tion of reagent remains available and (2) the rate of which the
reagent migrates away from the injection zone via advective
groundwater transport. These two criteria can often be satis-
fied based on initial tracer or injection pilot testing (Section
5.1.3) and can be continuously evaluated over the course of
treatment to tailor the injection events to changes in contami-
nant concentrations and observed IRZ conditions.
As detailed in Section 6.1.2.1, injection fluids migrate
within the mobile fraction to a target ROI. As the mobile
fraction represents some portion of the overall soil porosity,
reagent dilution between the mobile and less mobile pore water
will occur and needs to be accounted for as part of dosing.
Theoretically, if the mobile fraction for a given soil formation
is 10% and the total porosity is 30%, reagent concentrations
would be expected to be diluted by two-thirds after the injec-
tion is completed. Once delivered, all reagents will have a
unique half-life based on their overall molecular constitution,
their reactivity with the soil and groundwater geochemistry,
or their rate of microbial utilization. The reagent-specific half-
life is utilized to determine the overall duration to exhaustion
based on the in situ starting concentration (C0; following dilu-
tion) and the minimum concentration that must be available to
promote the target reactions based on the half-life equations
provided in Chapter 2. Once obtained, this duration repre-
sents the minimum time between injection events.
For soluble substrates that migrate with natural groundwa-
ter flow, the second primary criterion for dosing frequency is
the overall rate of reagent washout from the injection area.
As highlighted in Figure 6.7, the overall distance a reagent is
expected to travel is determined based on the duration of time
calculated using the aforementioned half-life method divided
by the groundwater velocity. Complete washout is defined as
the duration of time required for groundwater advection to
carry the reagent beyond the diameter of the injection area
(Figure 6.7), following which subsequent injection applica-
tions are warranted to sustain the IRZ. By critically evaluat-
ing the rate of reagent consumption versus that of washout
as part of upfront IRZ designs, we can tailor which variable
represents the controlling parameter for design purposes and
modify the injection approach to achieve ideal scenarios that
balance reductions in field implementation time, injection
delivery infrastructure, and overall program cost.
Finally, as the half-lives for different reagents can change
over the course of injection programs and as treatment is
achieved within and downgradient of the IRZ, performance
monitoring activities are used to confirm the reagent longevity
and transport in order to adapt the injection strategy over the
course of the program. It is an expectation that modifications
to the injection frequency will be warranted over multievent
184
90
Time of groundwater travel (days)
60
30
FIGURE 6.7  Dynamics of soluble reagent transport in groundwater downgradient from injection points.
injection programs, and performance data are integral to tai-
loring the program based on IRZ development and observed
treatment of the target contaminant(s). As examples, chemi-
cal oxidants may react faster with natural soil organics or
labile metal species present at the onset of injection (and have
reduced longevity) or biological substrates may be consumed
faster as the target microbial community proliferates within
the IRZ over time.
6.1.3  Injection Tests and Tracer Studies
The most fundamental activity to determining the key design
parameters presented in Section 6.1.2 is via completion of
injection or tracer testing. An injection test may be com-
pleted at any stage in the design and/or implementation of a
full-scale in situ remedy; however, these tests are most com-
monly completed as part of pilot or predesign project phases.
While many tests follow a similar overall approach—inject
reagents and pay close attention—each is unique to the spe-
cific site conditions, contaminant types, and overall remedial
application.
The phrase “tracer test” is often used as reference to injec-
tion tests that include only an inert tracer (e.g., fluorescent dye,
salts, isotopes) for use in assessing reagent distribution from a
delivery point and the subsequent dissolved-phase transport.
The terms “pilot test” and “field demonstration” typically
entail both a tracer and the reagents anticipated as part of the
full-scale design. As many reagents in themselves serve as
tracers while they are present in the subsurface, they are often
employed to serve as both tracers and reactants for contami-
nant treatment. Reagent-based injection tests are expected to
vary significantly from conservative tracer test as the reagents
are reactive, may sorb to the geologic matrix, and are tran-
sient based on their utilization. When coupled together, how-
ever, the combination of tracer transport, reagent distribution
and consumption, and confirmation of contaminant treatment
performance provides a robust set of information for use in
demonstrating the efficacy of the target reactions, supporting
Remediation Engineering
Reactive zone length governed by:
Reagent longevity (days):
C
ln
C0
t=
–k
Groundwater velocity:
Distance = vt × t
full-scale IRZ implementation, and satisfying regulatory
agency questions regarding the applicability of the desired
IRZ technique.
These tests should always focus on a significant area of con-
cern within the plume and can vary in scale from single-well
injection tests to larger injection areas that can be applicable
as an interim remedial measure. The following feasibility and
selection criteria should be considered while evaluating the
design of an IRZ pilot test:
• Aquifer permeability and thickness in the targeted
test area
• Volume of fluid required to achieve a target horizon-
tal and vertical distribution
• Technical specifications and equipment require-
ments for reagent delivery
• Injection and monitoring well(s) position and their
anticipated hydraulic communication
• Reagent dosage, frequency, and subsurface dilution
• Reagent consumption, persistence, and potential
concerns with respect to the formation of any by-
products—even over short durations
• Pilot test groundwater monitoring protocol
• Implementation costs
Groundwater tracer tests entail two general components:
(1) the delivery of a tracer into the subsurface and (2) post-
delivery monitoring to assess changes in tracer concentration
within the subsurface. Tracer tests can be completed using
one individual well or multiple wells depending on the design
parameters sought. Single-well tests entail the delivery of a
tracer and then follow-on groundwater monitoring to assess
the rate of overall washout of the tracer from the specific well
location. As these tests are not capable of understanding the
overall horizontal or vertical distribution of the tracer, they are
only appropriate to assess the rate of groundwater transport
through the given well location. Comparatively, multiple well
tracer tests entail combinations of injection and monitoring
Injected Reagent–Based Remedies
wells, and offer a direct means to understand the nature of
hydraulic communication within a groundwater system, and
are the general standard for use in supporting IRZ designs.
Multiple well pilot tests must employ a minimum num-
ber of injection wells that can be used to properly deliver
the reagent to the target zone. The screened interval should
intercept the impacted zone, with consideration given to the
lithology and groundwater flow conditions. As one of the fun-
damental primary objectives of completing a tracer test is to
determine the mobile fraction of an aquifer, conservative esti-
mates should be made for this parameter and then confirmed
directly by the test. If there are little or poor quality geologic
data available, consideration should be given to the need to
gather supplemental geologic data using split spoon sampling
techniques during installation or via other appropriate means.
Detailed geologic information collected during installation
of the tracer well network should also be used to make any
final modifications to the spatial injection test well layout and
the vertical placement of well screen intervals in the field and
to revise planned injection volume assumptions. Following
installation, wells should be fully developed to remove fines
and soil particles within the injection and monitoring wells
to ensure hydraulic communication with the surrounding
aquifer.
The tracer test duration or frequency of injections (if mul-
tiple are planned) will vary with the geologic, biogeochemi-
cal, and hydrogeologic conditions of each site. As a result,
the injection duration can be highly variable dependent on
the ability of the aquifer formation to receive fluid and the
total volume planned. Careful injection test planning is there-
fore used to select the appropriate well network arrangement,
determine the delivery volume and types of tracers, and to
develop the associated monitoring program. These aspects
are then used to balance overall cost based on anticipated site
injectability. A summary of these injection test components is
discussed in the following sections.
6.1.3.1  Tracer Types
As described earlier, there are a wide variety of tracers that
can be used to acquire the necessary IRZ design parameters.
These include fluorescent dyes, soluble salts, isotopes, or the
injection reagents and associated biogeochemical indicators
linked to their chemical makeup or IRZ process. Selection
of a given tracer is determined by their overall compatibil-
ity with subsurface geochemistry, site geology, reagents used,
their detection limits relative to injection strength (the signal-
to-noise ratio), and overall cost of materials and analyses.
Fluorescent dyes are conservative tracers that are read-
ily available, nontoxic, relatively easy to use, practical, and
convenient. Commonly used dye tracers include fluorescein,
rhodamine WT (rhodamine), eosine, and sulforhodamine B
(SRB). While these dyes are widely applied, the site-specific
geology and geochemistry should be considered prior to use.
Fluorescent dyes are pH sensitive and will lose visual color
at low pH. While this reduces the ability to visually detect
dyes in the field, fixed-lab analytical accuracy is not affected.
Fluorescent dyes do not appreciably sorb or biodegrade;
185
however, there is potential for minimal sorption to soils with
high clay content2,3 or natural soil organics, which may drive
designers to consider nonretardative tracers in highly inter-
bedded systems. These dyes are also not applicable for chemi-
cal oxidation injection tests, as they are organic and will be
consumed by most oxidants.
A significant advantage to fluorescent dyes is the high
signal-to-noise ratio. Analytical detection limits are reported
to be as low as 0.0005 parts per billion (ppb) to 0.1 ppb in the
absence of interference, which compared to a typical injection
concentration of 25,000 to 50,000 ppb yields over five orders
of magnitude for dilution in the subsurface. The visual detec-
tion limit with the naked eye is also approximately 140 ppb,
which allows for qualitative comparisons to field-mixed dye
standards to guide real-time decision making in the field.
Soluble salts are conservative environmental tracers that
are low cost, are relatively easy to use, and are measurable
in real time. Typical salt tracers commonly use chloride and
bromide, which are readily soluble in water. Both of these
are readily available, are low cost, and can be monitored in
the field using a downhole conductivity probe or conductivity
logger to generate breakthrough curves. A vertical profile of
conductivity across monitoring well screened intervals can be
collected and used to generate high-resolution breakthrough
curves at multiple depth intervals within a well to understand
preferential conductive flow pathways. As both bromide and
chloride are present at some background concentration in
most groundwater systems, understanding the initial back-
ground concentration is important for determining the appro-
priate dosing strength.
There are some conditions where soluble salts may not be
the best choice for a tracer. The high detection limit (relative
to fluorescent dyes) of soluble salts requires a higher injec-
tion concentration for the tracer signal to be measurable at
extended distances. Injection solutions with elevated soluble
salt concentrations result in a significant contrast in density
between the tracer and ambient groundwater and can con-
tribute to density-driven transport (Figure 6.8). In permeable
systems where fluid density allows for downward vertical
transport, alternative tracers may be more applicable to assess
horizontal flow. Bromide should not be used at sites where
strong oxidizing chemicals are being used to minimize the
potential for generation of bromate, which is a suspected
human carcinogen. When deployed in the vicinity of surface
waters, bromide distribution and dilution in the subsurface
should also be considered as photolytic reactions can also
produce bromate.
Stable isotope tracers are isotopes that do not undergo
radioactive decay; the nuclei are stable and therefore masses
remain the same. In terms of the water molecule itself, oxy-
gen has three stable isotopes, 16O, 17O, and 18O; and hydro-
gen has two stable isotopes, 1H and 2H (deuterium), of which
16O and 2H are the most abundant. The stable isotopes 18O
(oxygen-18) and deuterium occur naturally in the environment
and are used routinely to provide information on hydrological
processes, including groundwater–surface water interactions.
Of these, deuterium is most frequently used as an applied
186 Remediation Engineering

Injection Monitoring Injection Monitoring

well well well well

(a) (b)

FIGURE 6.8  (a) Horizontal reagent transport and (b) reagent density-influenced transport.

tracer and consists of water with the heavier deuterium atom
at a higher overall percentage than that observed naturally.
Similar to salt tracers, the background deuterium concentra-
tions must be sampled to understand the appropriate dosing
strength, and the magnitude of overall isotope response is
determined relative to background concentrations. Deuterium
is the only perfectly conservative tracer and is chemically
inert, so is often used in conjunction with in  situ chemical
oxidation (ISCO) remedy designs.
The toxicity of deuterium water is low4 and does not pose
human health or ecotoxicological risks at typical injection
concentrations. The primary drawback of using deuterium is
that it cannot be measured via visual or geochemical indica-
tors real time in the field, but its high signal-to-noise ratio
and true representation of aqueous transport are considerable
advantages.
At the simplest level, a tracer is any parameter that when
injected into an aquifer demonstrates a deviation from the
preinjection steady-state condition. While the applied trac-
ers discussed earlier are the most effective for quantitative
assessment of injection response, considerable creativity
can be employed when selecting qualitative indicators of
to assess injection breakthrough. Individual reagents will
exhibit different geochemical signatures (e.g., specific con-
ductivity, pH, turbidity) unique to their molecular composi-
tion, which can be significantly different from the native
groundwater. These can serve as stand-alone indicators of
response or as supporting lines of assessment in conjunc-
tion with more quantitative tracers. Temperature is also an
inherent tracer that can also be used as a secondary indica-
tor of tracer arrival due to the relative difference between
injected water temperatures and that of the ambient ground-
water. Heat loss from the injection fluid to the groundwa-
ter and soil formation is relatively rapid, so temperature is
usually applicable at wells in close proximity to the injec-
tion well. Downhole data loggers that provide temperature,
water level, and conductivity response in injection response
monitoring wells can be good practice if significant devia-
tions in these parameters are expected.
6.1.3.2  Test Layout and Monitoring Programs
There are a variety of well orientations that can be utilized to
perform injection tests. Typical layouts include a minimum
number of injection wells that are surrounded by multiple
monitoring wells placed at strategic distances. Monitoring
wells positioned within the target injection ROI are com-
monly referred to as “dose-response” wells, and monitoring
wells positioned further away are referred to as “drift” wells
(Figure 6.9). Dose-response wells are frequently placed at dif-
ferent distances within the injection radius to allow assess-
ment of aquifer heterogeneities based on the timing of tracer
breakthrough. The functional objective of these wells is to
enable capture of periodic samples over the course of the
injection in order to develop an injection breakthrough curve
(Figure 6.10).
Drift monitoring wells are positioned in spatial locations
that align with the expected direction of groundwater flow. It
is preferable for injection test monitoring wells to be placed
at variable distances from the injection well(s) to correlate
with the predicted arrival of the tracer (e.g., one, two, or three
Flow direction variance
MW5 MW3 MW4
Drift
MW1 MW2
DR1
Approximate
GW flow
direction
Injection
DR3 IW DR2
Initial target tracer distribution
FIGURE 6.9  Conceptual pilot test well layout; well locations
reflect associated use for injection (IW), dose response (DR), and
downgradient drift monitoring wells (MW).
Injected Reagent–Based Remedies 187

0.40 Tracer response

C – Cbackground
NCR =
0.35 Cinj – Cbackground
Cmax

Normalized concentration response (NCR)

0.30

Cmax/2 indicates bulk Stabilized breakthrough

0.25
tracer response for use in
in situ concentration and mobile Cmax
0.20 fraction calculations.
2
0.15
Cumulative injected volume
corresponding to Cmax/2 is used
0.10 for predicting injection volume
estimates to achieve specified in situ
0.05 reagent concentrations.

C0
0.00

–0.05
0 2,000 4,000 6,000 8,000 10,000 12,000
Cumulative injected volume (gal)

FIGURE 6.10  Ideal tracer breakthrough at a monitoring well, representing the normalized change in tracer concentration response with
cumulative volume injected.

months postinjection) based on the expected groundwater Aside from injecting an insufficient volume of fluid to
velocity and desired pilot test duration. Reasonable ground- achieve tracer breakthrough, there are several common rea-
water velocity estimates can be estimated using a recent sons for tracer test failure. A primary reason is the placement
potentiometric surface map, the estimated mobile porosity, of an inadequate, or inappropriately screened, monitoring
and an applicable hydraulic conductivity (K) to the geologic network. Achieving direct hydraulic communication between
material within the injection interval using Darcy’s law—but the injection and monitoring wells is the fundamental aim
these estimates will then be confirmed by actual postinjection of tracer testing, so geologic information should be obtained
field data. This method of well orientation allows the reactive during well installation to screen wells within the apparent
zone to be defined both parallel and perpendicular to ground- permeability zones. Another common cause for tracer test
water flow. Once again, consideration should be given to the failure is an inappropriate monitoring frequency. Upfront
variability of the site geology in locating screened intervals. It estimation of the anticipated groundwater velocity is a key
may be necessary to monitor multiple intervals if the geology component for timing tracer sampling events for a specific
dictates. Heterogeneity can also lead to channeling into pref- well network. An adaptive monitoring plan should always be
erential flow pathways, thus requiring more pilot test wells employed to allow changes in monitoring frequency based
to ensure adequate evaluation. When possible, existing moni- on real-time observations. Finally, erroneous assumptions of
toring wells may be used as injection or observation wells in groundwater flow direction prior to the tracer test can also
order to control costs. lead to the migration of tracers away from the monitoring
Tracer monitoring activities are typically completed as network. Although flow direction is typically assumed from
part of two different phases: the injection phase and the drift various lines of evidence (e.g., developed contaminant plume
phase. Injection phase monitoring includes frequent (one to shape or hydraulic gradient), subsurface heterogeneities can
several times per day) monitoring at dose-response wells dur- result in actual flow directions different from those originally
ing the active injection. Information collected at this stage assumed. The placement of dose-response and drift monitor-
will be used to determine the mobile fraction and injected ing at a variety of locations offset from the injection well is
volume to distribution ratio. Drift phase monitoring is com- advantageous to capture localized differences in groundwater
pleted following the active injection and includes periodic flow direction (Figure 6.9).
monitoring at the injection well(s), dose-response wells,
and downgradient drift wells following injection activities. 6.1.3.3  Mobile Porosity and Velocity Interpretation
Data are used to assess the decline in tracer concentrations Once the well network is installed, the injection is imple-
within the injection area (i.e., tracer washout) and the arrival mented. The injection is conducted while continuous moni-
of tracer within the drift network. These data support deter- toring is performed at the dose-response wells. Careful
mination of groundwater flow direction and average ground- observation is used to track increases in tracer breakthrough
water velocity, and in tests where reagents are applied, the response over the duration of the test, and the completion of the
data can also support assessment of reagent persistence and tracer injection is identified once a stable and consistent tracer
reaction rate. concentration is observed at the target dose-response well(s).
188 Remediation Engineering

This determination is supported by field assessment of real- velocity identifies the average rate at which the center of the
time sampling parameters (e.g., visual dye response, changes injected tracer radius will pass through downgradient moni-
in specific conductivity), which are then coupled with sam- toring points. The transport velocity can be determined based
ples collected for quantitative lab analysis. To achieve a on the following equation:
breakthrough curve similar to Figure 6.10, at least five dose-
response samples are typically required. After the injection, d
vt = (6.10)
normalized tracer responses (the observed sample concentra- t C peak
tion divided by the concentration injected) are determined 2

based on the following equation:

where
Cobserved - Cbackground vt is the transport velocity
Cnormalized = (6.8) d is the distance from the leading edge of the injected
Cinjected
tracer ROI to the drift monitoring well
tCpeak/2 is the time to observe a tracer response equivalent
The normalized concentration is then plotted as a percent-
to one-half of the maximum tracer response during the
age versus cumulative volume injected to develop the break-
postinjection monitoring period
through curve. The appropriate injected volume to achieve
the desired percentage response is selected from the break-
The bulk velocity is more complicated and requires
through curve and Equation 6.1 is rearranged to solve for a
more specific attention to the concepts of groundwater flow
corresponding mobile porosity as shown in Equation 6.9:
through a porous media. The tracer arrival curve at an obser-
Vinj vation well during the drift monitoring period represents a
qm = (6.9) finite data distribution, and as such statistical moments exist
p ´ rinj ´ h ´ 7.48
2

to describe the size and shape of distribution (Figure 6.11).

The calculated mobile pore space and selected injection vol-
ume are referred to as the volume to distribution ratio. While
the theoretical volume for a specific concentration dose
response can be obtained based on the corresponding volume
required to achieve a specific normalized response, geologic
heterogeneities often result in variable values of θm when
comparing multiple dose-response wells. For this reason, it is
common to select one value of θm that corresponds to 50% of
the maximum tracer response observed.
Temporal moments can provide information on transport in
an aquifer. The first temporal moment of a tracer distribution
represents the mean tracer travel time (T) and when corre-
lated with distance d provides a bulk groundwater velocity.
The first temporal moment (zeroth absolute) (M0) is defined
in Equation 6.11 as
ò
M 0 = C dt (6.11)

Following the injection portion of the tracer test, down- Equation 6.11 can then be rewritten in Equation 6.12 as
gradient drift wells are monitored over the course of several
weeks to months to support development of ambient trans- n

å
Ck + Ck -1
port breakthrough curves. Immediately after the injection, M0 = (t k - t k -1 ) (6.12)
the center of the injected ROI is assumed to be at the injec- 2
k =1
tion well and represents the center of mass. While the 50%
breakthrough concentration is typically used to identify a where
representative value of θ m , the nature of the breakthrough C is the normalized tracer concentration
curve is a true reflection of the variance in permeabilities t is the elapsed time
within the injection area. The first breakthrough arrival rep-
resents tracers migrating through the most permeable strata, The normalized concentration is given by Equation 6.13:
and tracer concentrations increase as it moves through
the less permeable strata. Similar behavior is anticipated c - cbg
C= (6.13)
as tracer migrates downgradient toward the drift wells. cs - cbg
Accordingly, it is expected that low concentrations will be
initially observed, will increase over time to a peak, and will where
then subsequently decline. The center of mass concept can C is the analytical concentration of the tracer response at
still be applied to these locations and is used as the preferred time t
method to determining groundwater velocity. cbg is the background concentration
To optimize the value of groundwater velocity data cs is the concentration of the injected tracer, all in units of
gleaned from a tracer test, it is necessary to separate seep- mass per volume
age or “transport” velocity from the effective or “bulk” veloc-
ity. In the absence of applied pressure or active injection, the The second temporal moment expresses a degree of spread-
transport velocity identifies the rate at which injected reagent ing and asymmetry about the mean tracer travel time and is
will first reach downgradient monitoring points and bulk a reflection of heterogeneities and anisotropy of the aquifer.
Injected Reagent–Based Remedies 189

Elapsed time (days)

0 200 400 600 800
1 100%

First arrival 90%

80%

Normalized tracer concentration

0.1
70%

Cumulative tracer arrival

60%

0.01 50%
Mean arrival 40%

30%
0.001
20%

10%

0.0001 0%

FIGURE 6.11  Method of moments washout curve for a normalized tracer injection test. Curves represent observed washout of tracer con-
centration versus that calculated and mean arrival time determined based on 50% cumulative tracer breakthrough.

In order to accurately determine the mean tracer travel time
following a normalized tracer input of time duration Ts, it is
necessary to relate the first and second moments to account
for retarding effects of porous media on transport. The
second temporal moment (first absolute) (M1) is defined by
Equation 6.14 as
n times T and Tcorrected with a simple percent difference equa-
å
Ck + Ck -1 æt +t ö
ò
M1 = TC dt =
k =1
2
(t k - t k -1 ) ç k k -1 ÷ (6.14)
è 2 ø
The mean tracer travel time, T, can be used in conjunction
with d to determine an approximate bulk groundwater veloc-
ity and is calculated according to Equation 6.15 as
M1
T= - 0.5 * Ts (6.15)
M0
The distribution of postinjection tracer responses at down-
gradient drift wells is heavily influenced by the early arrival
and tailing regions of the breakthrough curve. For this rea-
son, practical implementation of tracer tests must balance
the cost of prolonged monitoring with the value of fully
developing the asymptotic tail. Experience with tracer test-
ing data sets indicating the tail portion of the breakthrough
curve closely follows first-order rate kinetics in agree-
ment with a site-specific half-life of the observed tracer.
Therefore, the tail portion of the curve can be projected
using the half-life calculation below to avoid extended mon-
itoring durations:
C = Coe - kt (6.16)
The projected tail moments can then be used to determine
a corrected T by summing the predicted moments (M0Model
and M1Model) over a specified model duration and the observed
moments from analytical data (M0 and M1) in Equation 6.17:
M1Model + M1
Tcorrected = + 0.5 * Ts (6.17)
M 0 Model + M 0
A certain extent of field monitoring during tracer washout
is essential to validate the model. Relating the mean travel
tion indicates the agreement between the two measurements.
A percent difference less than 20% indicates that additional
monitoring is not required.
Comparing the bulk and transport velocities provides infor-
mation about the transport efficiency of an aquifer. The bulk
velocity divided by the transport velocity is defined here as
the degree of transport. Note that the degree of transport can-
not be greater than 1 as it is a proportion of the bulk ground-
water velocity (slower) to the transport velocity (faster). For
the purpose of this discussion, aquifer transport is discussed
in three main categories: significant, moderate, and minimal
nonideal transport (Figure 6.12). Nonideal transport refers to
the expected dual-domain effects of porous media, specifi-
cally the mobile to immobile fractions of an aquifer:
• Significant nonideal transport is approximated by a
degree of transport less than 0.25 and implies poor
hydraulic connectivity of immobile and mobile pore
space. This type of transport is usually associated
with impermeable materials that exhibit unfavorable
injection hydraulics (clays and silts). Aquifers classi-
fied as exhibiting significant nonideal transport typi-
cally demonstrate multiple peaks of tracer response
and indicate major retardation of tracer during ambi-
ent migration. Prolonged postinjection field moni-
toring is often necessary to obtain representative
velocity information.
190 Remediation Engineering

Elapsed time (days) Elapsed time (days)

0 50 100 150 200 250 300 0 50 100 150 200 250 300
0.01 100% 0.01 100%
Significant nonideal transport Moderate nonideal transport
90% 90%

80% 80%

Normalized tracer concentration

Normalized tracer concentration

0.001 0.001

Cumulative tracer arrival

Cumulative tracer arrival
70% 70%

60% 60%

0.0001 50% 0.0001 Mean arrival 50%

Mean arrival time
40% 40%
time
30% 30%
0.00001 0.00001
20% 20%

10% 10%

0.000001 0% 0.000001 0%
(a) (b)

Elapsed time (days)

0 50 100 150 200 250 300
0.01 100%
Minimal nonideal transport
90%

80%
Normalized tracer concentration

0.001

Cumulative tracer arrival

70%

60%

0.0001 50%
Mean arrival
time 40%

30%
0.00001
20%

10%

0.000001 0%
(c)

FIGURE 6.12  Tracer data representing (a) significant nonideal, (b) moderate nonideal, and (c) minimal nonideal transport.

• Moderate nonideal transport is approximated by 6.1.4  Injection Configurations

a degree of transport between 0.25 and 0.75 and
implies average dual-domain influence. Moderate Reactive zones can be implemented in a number of differ-
nonideal transport distributions are Gaussian, sug- ent configurations and approaches, which is consistent with
gest modest retardation, and indicate equal influence the fact that no two source areas or groundwater plumes are
of immobile and mobile porosity on transport. The exactly the same. Whether biological or chemical, the cre-
duration of postinjection field monitoring in these ation of a coherent injection zone requires uniform reagent
instances can be dictated by the data set and confir- distribution within the target IRZ. There are a variety of
mation of tailing tracer concentrations. reagent distribution orientations used in IRZ implementa-
• Minimal nonideal transport is approximated by a tion including injection wells, direct-push points, polar injec-
degree of transport between 0.75 and 1. Minimal tion and extraction wells used for recirculation, infiltration
nonideal transport suggests excellent communica- galleries, or via injection-based permeable reactive zones.
tion between immobile and mobile aquifer fractions Several example injection-based applications are highlighted
and is usually associated with permeable materials in Figure 6.13. While these strategies reflect an injection and
that exhibit favorable injection hydraulics (sands, drift delivery approach, these applications can also be cou-
coarse sands, gravels). Distributions of this type of pled with groundwater recirculation to enhance reagent deliv-
transport are Gaussian and indicate little retardation ery as detailed in Chapter 5 and in Section 6.1.4.1. Selection of
of tracer during ambient migration. The duration of the appropriate delivery strategy is driven by multiple techni-
postinjection field monitoring in these instances can cal factors including groundwater velocity, reagent solubility,
be dictated by the data set and confirmation of tail- geologic conditions, and injectability, which are then gener-
ing tracer concentrations. ally balanced by cost-driving decisions associated with the
Injected Reagent–Based Remedies
(a) (b)
FIGURE 6.13  Conceptual IRZ injection configurations. (a) Plume-wide treatment. (b) Focused source zone and downgradient cutoff IRZ
placement. (c) Multiple barrier injection transects along plume length. (d) Downgradient cutoff injection transect.
necessary infrastructure, field execution time, and reagent
demands. For the purposes of this discussion, there are three
basic layouts that can be used: source area treatment, barrier
transects, and plume-wide applications. Each of these can be
modified based on given site conditions and can be integrated
with or enhanced by other remedial technologies or treatment
strategies.
Source area reactive zones are specifically designed to
target localized areas that contribute dissolved contami-
nant concentrations to a downgradient groundwater plume
(see conceptual plume in Figure 6.13a through d). Source
area layouts are often employed in situations where natural
attenuation processes or downgradient capture strategies (via
injection barriers or other plume cutoff/containment strategy)
are successfully controlling the movement of the contaminant
plume. Achieving source treatment has become a fundamental
aspect (and in many cases a regulatory requirement) of most
remediation applications, and IRZ approaches are designed to
eliminate the source of contaminant mass quickly. Once the
IRZ has brought down concentrations in the source area to
target concentrations, injections in the source area can cease.
Depending on the volume of contaminant source mass, IRZ
source treatment may result in the transient increase in daugh-
ter compounds and facilitate contaminant desorption from
the soil matrix. In these cases, it may be important to initiate
treatment downgradient of the source zone prior to or concur-
rent with source treatment to eliminate any transient loss of
contaminant beyond the IRZ.
Plume cutoff barrier transects consist of a series of reagent
injection wells or points typically established in a row per-
pendicular to the groundwater flow direction along a line that
191
(c) (d)
represents a critical boundary for remediation (Figure 6.13b,
c and d). This layout is commonly employed along or near a
property line or in the vicinity of other boundaries established
for the purpose of containment or closure. The location of this
layout can also be selected based on practical means (e.g.,
located near a road for drilling and injection access) or in an
available open area in developed settings. In most cases, from
a capital cost perspective, cutoff or transect-based layouts are
less expensive to deploy relative to plume-wide remediation
due to the reduced well installation costs and decrease in total
reagent required. Barrier operational objectives are focused
on establishing strategic plume control points by which the
plume can be segmented and managed based on predeter-
mined operational durations.
Plume-wide reactive zones target a large portion of the
impacted groundwater in order to achieve more aggressive,
short-term treatment. Typically, the injection points will be
spaced throughout the target-impacted groundwater (Figure
6.13a). By applying the reactive zone across the entire plume,
reagents can be distributed across a broad area enabling expe-
dited treatment in less time. There are obvious cost and imple-
mentability implications with such an application: higher
capital costs are traded for shorter remedial time frames and
commensurate reduction in total life-cycle operational costs.
In many cases where stand-alone IRZ remedies are deployed
for plume treatment, a combination of source area and barrier
transect layouts is employed (Figure 6.13b and c). The number
of injection points and the spatial distribution of these points
are a function of the contaminant distribution, the hydrogeol-
ogy of the impacted zone, the type of injection delivery, and
the nature of the reagent being used. The injection wells need
192
to achieve reagent distribution within the entire area targeted
by the reactive zone. The geology and groundwater transport
velocity will control how wide an area a single point can impact
and how far the reagents will migrate. In less permeable geolo-
gies, groundwater is likely to move relatively slowly and may
limit the overall injectability of the formation. The resulting
reactive zone developed from a single point will have a lim-
ited impact laterally from the injection point and reagents will
move shorter distances in the direction of groundwater flow.
Therefore, more points will be needed on a closer spacing.
The type of reagent used has a large bearing on the spa-
tial distribution of the injection points. Water-soluble reagents
will have flow characteristics similar to that of groundwater,
will move readily with ambient advective transport, and can
support development of elongated IRZs. Semisoluble or spar-
ingly soluble reagents (e.g., EVO, ZVI, oxygen-releasing slur-
ries) will be retained within the soil matrix as groundwater
migrates through the IRZ. The design of these systems is dis-
cussed in further detail in Sections 6.2 and 6.3.
Depending on the overall scale of injection and number of
points, a decision can be made as to whether manual batch
mixing (Figure 6.14a) or a fully automated injection sys-
tem (Figure 6.14b) is required. This decision is made based
on costs (injection labor vs. equipment), site conditions that
warrant either above- or below-grade infrastructure, or the
expected duration of the overall injection program. For exam-
ple, where injection wells are positioned in a high-traffic area
(e.g., in a parking lot, at an active facility) and ongoing injec-
tions are required over an elongated duration, a centralized
(a)
FIGURE 6.14  (a) Batch mixing injection setup. (b) Fully automated mixing system.
Remediation Engineering
distribution system with permanent subsurface delivery infra-
structure may be desirable even though it adds to the cost of
the remediation program.
6.1.4.1  Pulse and Drift versus Recirculation
This section and Section 6.1.4.2 detail available methods by
which to construct IRZ injection delivery networks to achieve
source and plume-wide cleanup objectives. Once injected
into the subsurface, the reagent-specific longevity, the reagent
solubility, and the advective groundwater velocity will dictate
where the IRZ develops and how far it extends in the sub-
surface. For assumption purposes, completely soluble (and
nonsorptive) reagents will advance at rates equivalent to the
groundwater transport velocity. Depending on the reagent
characteristics, the overall transport will be affected by nat-
ural sorption mechanisms (for organic substrates), soil ion
exchange processes (for inorganic reagents), and dual-domain
processes. As the overall rate of cleanup achieved within an
IRZ and a given groundwater plume is related to how far
the reagents advance in the subsurface, the identification of
design groundwater velocities via available site information or
the methodology discussed in Section 6.1.3.3 is paramount to
developing an overall IRZ well network. This is also used to
develop the capital and operational costs for the injection pro-
gram and to establish the well network based on site cleanup
objectives or necessary remedial time frames.
Pulse and drift generally refers to injection programs that
rely solely on natural groundwater transport for postinjection
reagent distribution. Injection events are completed, reagent
(b)
Injected Reagent–Based Remedies
90
Time of groundwater travel (days)
60
30
0
r = 5 days
r = 15 days
FIGURE 6.15  Conceptual superposition of injection events to
form a coherent reactive zone at a site with a groundwater velocity
of 1 foot per day. Injection volumes on the left are sufficient to cover
a 30-day diameter and are repeated at a 30-day interval. Injection
volumes on the right are sufficient to cover a 10-day radius and must
be repeated every 10 days to maintain steady reagent concentrations.
Reactive zone tracer tests show very little longitudinal or transverse
dispersion, and designed overlap of injection fields is required to
avoid gaps in reagent coverage.
distribution is achieved perpendicular and parallel to ground-
water flow corresponding to the volume to radial distribution
ratio, and the reagent subsequently migrates downgradient
of the injection zone (Figure 6.15). As discussed previously,
the timing of injection events is then balanced by the overall
reagent longevity (how long it exists at a working strength
concentration) and the degree of washout, whichever is short-
est. For groundwater systems with moderate or faster transport
velocities (e.g., greater than 0.5 ft per day) and reagents with
longer overall half-lives (i.e., weeks to months), a considerable
area of influence can be achieved using pulse and drift strate-
gies. These systems ultimately enable fewer injection wells or
barriers of injection wells to achieve broad treatment coverage
within the injection area. Accordingly, where groundwater
velocities are slower (e.g., less than 0.1 ft per day), the area of
the IRZ is likely to remain limited in the vicinity of the injec-
tion wells and would require more closely spaced injection
transects to ensure IRZ coverage (Figure 6.16).
As discussed in Chapter 5, groundwater recirculation can
be highly advantageous in overcoming the extended remedial
time frames of conventional groundwater extraction remedies
by enhancing the transport of groundwater and contaminants
through the subsurface. This concept can be similarly applied
for IRZ applications, with the added benefit that the applied
transport gradients within injection/extraction well dipoles
enhance the subsurface transport of injected reagents. These
applications can have a variety of orientations depending on
a site’s specific geologic conditions, but in general, most uti-
lize groundwater extraction, above-grade treatment to remove
contaminants, above-grade dosing to achieve a target reagent
193
100%
Residual reagent concentration
90% 0.1 ft/day
0.5 ft/day
80%
1 ft/day
70% 2 ft/day
60%
50%
40%
30%
20%
10%
0%
0 50 100 150 200
Travel distance (ft)
FIGURE 6.16  Normalized reagent concentration at variable dis-
tances for systems of variable groundwater velocities; injection
reagent assumed to have a 20-day half-life.
concentration, and then strategic reinjection to deliver the
reagent into the subsurface. In some instances, the reagent
applied to the extraction stream also serves as the treatment
remedy and eliminates the need for additional ex  situ treat-
ment infrastructure.
From a construction standpoint, pulse and drift designs
require less overall infrastructure and equipment to operate.
These injections are completed periodically (e.g., monthly,
quarterly, annually) and usually only require operational
oversight while injections are being completed. Injections are
completed using mixing tanks, injection and mixing pumps,
and conveyance lines to facilitate reagent preparation and
wellhead delivery. Depending on site complexity, these sys-
tems can comprise temporary equipment that is staged for
each event and then demobilized following completion, dedi-
cated trailer-based setups with some degree of automation, or
fully automated systems that run with limited oversight. For
recirculation setups, the need for ex  situ treatment prior to
reagent dosing and reinjection will require a dedicated treat-
ment train. While these can be developed to be somewhat
mobile, these injection setups are commonly positioned in
one location for the duration of the remedy.
6.1.4.2 Large Plume Treatment: Barrier
Spacing Design Considerations
While plume-wide treatment can be conducted using injec-
tion configurations similar to that shown in Figure 6.13a,
these strategies are not economical for the vast majority of
groundwater plumes larger than several hundred feet in
length. Instead, plume treatment applications typically entail
combinations of both source zone IRZ and injection transects
that are positioned strategically along the length of the plume
(Figure 6.13c). These transects are used to support IRZ estab-
lishment, establish treated fronts of groundwater as contam-
inants decline within the IRZ, and segment the plume into
reasonable distances by which contaminant attenuation can be
achieved between barriers. The overall operational duration
of any injection barrier is driven by the duration of time over
which untreated contaminants migrate toward it. Therefore,
when installed in series, the total injection program dura-
tion is driven by the rate of contaminant flushing and treated
194 Remediation Engineering

4
1 Reactive barriers
Groundwater
2 Source treatment
flow 2 1 3 1 3 4
3 Flushing zones
4 MNA zones
4

FIGURE 6.17  Conceptual large plume injection approach reflecting multiple reactive zones.

groundwater from one barrier to the next. As a result, identi- 2 1 1

fying the appropriate barrier spacing is one of the most criti-
cal elements to achieve the ideal balance between operational 3

Aqueous-phase concentration (mg/L)

duration (i.e., treatment time) and overall remedial cost.
Plume-wide barrier designs rely on three primary com- 1
1
ponents: the IRZ, the flushing zone (or redox recovery zone),
and the MNA zone (Figure 6.17). Within the IRZ, injection
activities are completed on a periodic basis to sustain suffi-
cient reagent strength in the subsurface. Contaminant declines
2
within this zone are the fastest observed and the residence time
within the IRZ must be sufficient to enable complete treatment
1 Reactive barriers
prior to reagent exhaustion. The overall IRZ residence time is
2 Source treatment
determined based on the groundwater velocity and reagent half- 3 3
3 Flushing zones
life and will be different for completely soluble reagents (which
move with advective groundwater flow) versus semisoluble or
nonsoluble reagents (which remain relatively stationary). For FIGURE 6.18  Contaminant treatment and desorption patterns in a
reactive zone sequence and source treatment strategy. Contaminant
semisoluble or nonsoluble reagents, the IRZ barrier residence
desorption occurs within flushing zones where contamination is
time will be similar to that of a permeable reactive wall, in that delivered to downgradient barrier where it is treated. Downgradient
the diameter of the injection zone parallel to groundwater flow barrier placed in strategic location such that distal plume toe can be
is divided by the site-specific groundwater velocity. managed via natural attenuation (or treated via barrier).
For soluble reagents that migrate with both contaminants
and groundwater, the residence time accounts for both the
injection program (Figure 6.18). The exhaustion of reagent
duration of groundwater flow through the injection barrier
at the downgradient edge of the IRZ means that the primary
and the time over which working strength reagent concentra-
treatment mechanisms within the flushing zone are primar-
tions remain. The longevity of the reagent can be determined
ily due to dilution. If the IRZ achieves its design intent, con-
by solving for t in the half-life equation based on the in situ
taminant flux will be eliminated and multiple passes of clean
starting concentration (C0) following injection (accounting for
groundwater through the permeable soil strata will serve to
dilution in groundwater between the aquifer mobile fraction
dilute contaminant concentrations via groundwater flushing.
and total pore water), the minimum reagent concentration
The total number of pore flushes required (NPV) to achieve suf-
necessary to promote treatment (C), and the reagent-specific
ficient dilution from a starting concentration within the plume
half-life (used to develop a decay rate). The overall length of
(C0) to the target cleanup objective (C) can be estimated via
the IRZ (residence time) is then determined by multiplying
the following equation:
the reagent longevity and the groundwater velocity to iden-
tify a total transport distance. This residence time can then
be compared to the necessary time needed to achieve con- æC ö
N PV = - R ´ ln ç ÷ (6.18)
taminant treatment objectives within the IRZ. As appropri- è C0 ø
ate, designers can increase the dosing strength to extend the
overall residence time (and allow greater transport) or reduce In this equation, R represents the contaminant retardation
the dosing strength to limit and control reagent distribution (if factor obtained by first determining the contaminant sorp-
downgradient receptors are a potential concern). In addition to tion coefficient (Kd). This is calculated based on the fraction
allowing prediction of overall reagent distribution, residence of organic carbon in soil (foc) and the contaminant-specific
time estimates are also highly useful in identifying locations organic carbon partitioning coefficient (Koc) as shown in
for IRZ monitoring well placement. Equation 6.19. R is then determined using Kd in conjunction
Treated groundwater exiting the downgradient end of the with the bulk density of soil (ρs) and the total aquifer porosity
IRZ is referred to as, the clean water front. Over the course (θt), as shown in Equation 6.20:
of operation, this front will advance downgradient toward
the subsequent barrier (or the distal plume toe) during the K d = foc ´ K oc (6.19)
Injected Reagent–Based Remedies
rs
R = 1 + Kd ´ (6.20)
qt
The total NPV required to achieve cleanup objectives is used
to determine the total flushing time (tF) using the groundwater
velocity (vgw) and the overall flushing distance (dF) between
the downgradient edge of the IRZ (the point of reagent exhaus-
tion) and the subsequent treatment barrier (Equation 6.21):
dF
t F = N PV ´ (6.21)
vgw
Once the flushing duration is determined, designers should
use an iterative approach to identify the ideal barrier spacing
that balances the overall capital costs for injection infrastruc-
ture (i.e., number of injection wells and injection barriers),
the operational expense associated with running the injection
program, and the duration of time required to achieve treat-
ment within both the IRZ and the flushing zones. This pro-
cess can be used to avoid installing barriers that are too far
apart to achieve treatment objectives within a reasonable time
period and can guide regulatory and stakeholder expectations
pertaining to treatment progress over the course of operation.
This evaluation also provides a reasonable assessment of life-
cycle IRZ treatment costs for comparison to other potential
remedial strategies.
The utilization of flushing zones allows designers to limit
the overall footprint in which IRZ treatment is applied and
to significantly leverage dilution as a natural attenuation pro-
cess. Flushing zones provide an added advantage in that sec-
ondary by-products generated within the IRZ (e.g., reduced
metal species, pH change, soluble inorganics, dissolved meth-
ane) can precipitate, attenuate, or repartition via ambient
reactions within native soils and groundwater. To reflect this
benefit, the term flushing zone is often referred to as the redox
recovery zone.
The expected rates of treatment within both IRZ and flush-
ing zones can be used to develop an overall management
strategy for the plume. It is common for these two zones to
be focused on the primary plume core where contaminant
concentrations exist at one to several orders of magnitude
above the treatment goals. In these instances, contaminant
concentrations outside of the IRZ and flushing zones would
be expected to attenuate via a combination of natural attenua-
tion mechanisms (e.g., dilution, sorption, biotic/abiotic trans-
formation) while active treatment is ongoing. If the objective
is to achieve complete treatment over a period of five years, a
minimum target concentration expected to attenuate over the
same duration can be determined based on site-specific data
and used to establish an MNA zone.
6.1.5 Performance Monitoring
Sections 6.1.1 through 6.1.4 provide a broad overview of how
to carefully select, design, and implement an IRZ treatment
strategy. Compared to other treatment strategies that allow
direct confirmation that contaminant mass is being excavated,
195
volatilized, or captured, IRZ treatment strategies rely on care-
ful inferences of overall treatment progress based on changes
observed in groundwater. The expectation that all IRZ appli-
cations will be modified or adapted over the course of opera-
tion implies that the performance monitoring program should
include the appropriate data that can guide overall remedial
decision making and serve as a constant feedback loop to
tailor treatment activities and determine when they can be
discontinued.
To properly evaluate the IRZ technology in the field,
a network of monitoring wells is required. The monitoring
wells need to be located within the IRZ treatment zone and
downgradient of the injection network in the direction of
groundwater flow to confirm reagent distribution, validate
design parameters (e.g., groundwater velocity), evaluate the
rate of reactant utilization, assess contaminant transforma-
tion rates and treatment extent, and evaluate heterogeneities
within the treatment area. This is typically accomplished by
spacing individual wells or sets of wells at different transport
distances from the IRZ treatment area or within a downgradi-
ent flushing zone, and different configurations of wells can
be used based on the IRZ well network orientation, site-spe-
cific conditions, and regulatory requirements. It is preferable
to have at least one monitoring well with sufficient histori-
cal contaminant data that can be used to correlate treatment
observations. All new wells installed to assess IRZ treatment
performance should be sampled at least once prior to start-up
to obtain a representative baseline pretreatment value.
Ongoing monitoring of IRZ system implementation is
done for two purposes: to help control the system (process
monitoring) and to evaluate its performance (performance
monitoring). Groundwater sampling for process monitoring
purposes should be performed using select injection wells
and closely-associated monitoring wells. The intent is to pro-
vide almost real-time feedback that can be used to adapt and
control the selected IRZ reactive processes and maintain it
to optimize the treatment efficiency. The frequency for these
sampling events should be selected and fine-tuned as the pro-
cess is ongoing. However, it is likely that these events will be
more frequent near the beginning of the injection program,
when the optimum reagent-dosing plan for each site is being
established. A typical frequency is weekly to biweekly during
the first month of injections, biweekly or monthly during the
next 2 to 3 months of implementation, and bimonthly to quar-
terly for the remainder of the active implementation period.
The parameter list for these sampling events will vary based
on the target contaminants and reagents selected, and detailed
lists of these parameters are discussed pertaining to specific
biological and chemical strategies presented in Sections 6.2
and 6.3, respectively.
Performance monitoring should be initiated after process
monitoring has demonstrated that the target reactions within
the IRZ have been initiated. The list of parameters measured
during performance monitoring will likely include the concen-
tration of contaminants, their intermediate by-products, and
complete transformation end products. The frequency of moni-
toring will vary between the monitoring wells immediately
196
associated with the reactive zones and other monitoring wells
located within the plume. Generally, the monitoring wells asso-
ciated with the reactive zones will be measured more frequently
than the site-wide monitoring wells that are monitored as part
of the required compliance monitoring.
Data collected over the course of the monitoring program
is used to confirm declines in contaminant concentration
trends. For IRZ programs that facilitate contaminant transfor-
mation or destruction, the contribution of destructive degra-
dation processes should be discerned from nondestructive or
physical attenuation that will also be ongoing. As an example,
the observed increase in contaminant daughter products cis-
1,2-DCE and vinyl chloride during TCE solvent biodegrada-
tion provides real-time indication that the targeted treatment
mechanisms are being achieved. Comparatively, correlated
declines in all of these constituents demonstrate that physical
attenuation may predominate. Data review will also support
qualitative and quantitative trend analyses that can be used to
assess changes in contaminant concentrations, confirm that
treatment is progressing according to the design objectives, or
identify areas for optimization.
Many of the same tools that are used for data evaluation
and interpretation prior to and during IRZ system design can
be used during IRZ implementation as well. However, some
additional tools become valuable during and after imple-
mentation. For example, comparison of rate(s) of change of
contaminant(s) concentration before and after treatment from
time series curves is often helpful in clearly demonstrating the
effectiveness of the remedy. However, since the reaction pro-
cesses that take place within a microbial IRZ proceed through
several mechanisms and are controlled by microbial population
dynamics and desorption processes, the changes in contami-
nant concentration(s) will not necessarily fit a simple kinetic
model. Where applicable to capture changes in parent contami-
nants and their respective daughter products (e.g., chlorinated
ethenes and ethanes), time series concentration curves should
be done on a molar rather than mass basis so that the effects of
sequential degradation processes can be more clearly perceived.
Monitoring frequency should always remain flexible dur-
ing the life cycle of the reactive zone. This allows modifi-
cation of sample timing based on earlier observations and
fine-tunes future data collection to site-specific nuances and
the process being implemented. Acceptance of the need to be
flexible is critical to the regulatory agency’s perceptions of the
monitoring effort and the client’s understanding of the budget
and schedule.
6.1.6 Enhanced NAPL Dissolution
NAPL treatment has been and remains one of the primary
challenges of remediation. Historically a challenge requiring
more presumptive recovery remedies opposed to in situ treat-
ment, increased confidence in injection-based remedies for
NAPL treatment has been directly correlated with refinement
of our site characterization techniques, increased awareness
of injection hydraulics, and our overall familiarity with the
treatment mechanisms and deployment requirements.
Remediation Engineering
Early NAPL remedies applied combinations of prod-
uct recovery and vacuum-enhanced physical techniques or
looked to enhanced oil recovery options that used surfactants,
polymers, steam, or increased temperatures.5 Application of
the patented Suntech method6 during the mid-1970s was the
first time a remedy akin to in situ bioremediation was applied
commercially as a stand-alone measure to restore impacted
soils and aqueous solutions. This method entailed delivery of
both oxygen and nutrients to promote the aerobic bioremedia-
tion of PHCs and light nonaqueous-phase liquids (LNAPLs),
and this concept provided the foundation on which much of
the design applications discussed in Section 6.2 have been
built. Still, while the successes with LNAPL treatment were
building, hydraulic containment was viewed as the only
“practical contaminant management option”5 and biodegra-
dation or in situ concepts were thought to be “generally inef-
fective for DNAPL sites.”7 This [well-placed] pessimism is
reflected in regulatory and industry-consortium guidance
documents, where biological DNAPL treatment programs
were designated as “unlikely” or only “possible” in 2003,8
and then cautiously identified in 2005 as a potential DNAPL
strategy when applied correctly or when implemented at sim-
ple sites.9 Finally, in 2007, the ITRC expert panel concluded
with a “unanimous ‘Yes’” that bioremediation is a viable
DNAPL source zone remedial option.10 While the industry
has reached broad consensus that injection strategies are via-
ble for DNAPL source zones, this optimism is still tempered
when measureable thicknesses of separate-phase DNAPL (or
LNAPL) exist and may likely be more efficiently addressed
via other technologies found in this book.
While injection-based remedies are applicable for source
zone treatment, these techniques (biological or chemical) are
inherently dissolved-phase treatment remedies. In order to
achieve NAPL treatment, contaminants must partition from the
NAPL phase into the aqueous phase. Design of any injection-
based remedy for source areas containing free-phase or resid-
ual DNAPL or LNAPL must therefore be done with a sober
understanding of the volume and distribution of contaminants
within the soil architecture. These factors relate to the degree
of source mass accessibility to injection techniques and have a
significant bearing on the overall remedial duration.
Remedial design oriented toward enhancing removal of
sorbed, residual phase, and separate phase NAPL mass within
source areas is desired as it is strongly linked to reductions in
the overall remediation time frame (Figure 6.19). NAPL dis-
solution is controlled by two primary factors: the mass trans-
fer coefficient and the concentration gradient, as described by
Equation 6.22:
dC
= K L (Cs - Ceq ) (6.22)
dt
where
dC/dt is the rate of change of NAPL dissolution (mg ft−1 t−1)
Cs is the relative solubility of a contaminant (mg/L)
Ceq is the interfacial equilibrium concentration (mg/L)
KL is the mass transfer coefficient (t−1)
Injected Reagent–Based Remedies 197

Hydrophobic organic contaminant mass distribution 0.07

0.06
NAPL mass

Solubility concentration (mol/L)

Drainable
Residual 0.05
Aquifer mass (g /m3)

Total
nonaqueous-phase mass 0.04

Sorbed mass 0.03

0.02
Migrating aqueous-phase mass
Static aqueous-phase mass
0.01

Total aqueous-phase mass, g/m3
Total aquifer mass, g/m3
FIGURE 6.19  Conceptual distribution of hydrophobic organics
along the core of a plume that has complete saturation of aque-
ous and sorbent compartments in the source zone, with formation
of residual and drainable nonaqueous-phase liquids. Steady-state
concentrations in downgradient areas are determined by combined
effects of dilution and degradation.
The mass transfer coefficient is a function of several param-
eters, including NAPL surface area, groundwater velocity,
and physical properties such as molecular diffusion, dynamic
viscosity, and density.11 In reviewing Equation 6.22, there are
four general mechanisms by which dissolution is enhanced by
injection-based techniques:
1. Depress Ceq —perhaps the most intuitive mechanism,
achieving treatment in the dissolved phase increases
the overall value of Cs − Ceq, thereby promoting addi-
tional mass transfer from the NAPL to the aqueous
phase.
2. Increase Cs —similar to historical enhanced oil
recovery techniques, surfactants or cosolvents both
affect the overall magnitude of Cs.12–14 This is a pri-
mary advantage of in  situ biological treatment, as
biosurfactants, such as glycolipids and lipoproteins,
are all exuded by the microbial community, and fer-
mentable carbon substrates will generate alcohols
and ketone intermediates that also increase the value
of Cs —in some cases up to threefold.15,16
3. Transform the parent contaminant into lighter,
higher-solubility daughter products—particular
to chlorinated ethene and ethane transformation,
the relative solubility of key transformation daugh-
ter products (e.g., cis-DCE and VC) is higher than
the parent species and allows for increased overall
mass transfer of the parent compound to the aqueous
phase as dechlorination occurs (Figure 6.20).
4. Increase the overall NAPL surface area to mass
ratio—modification of K L through the interaction of
0
PCE TCE cis-DCE trans-DCE VC
Cl Cl Cl H H H H Cl H H
C C C C C C C C C C
Cl Cl Cl Cl Cl Cl Cl H Cl H
FIGURE 6.20  Relative solubilities of PCE, TCE, and their daugh-
ter products cis-DCE and VC.
biosurfactants, and NAPL can increase NAPL sur-
face area,16 which thereby contributes to the overall
enhancement of NAPL dissolution.
Mechanism 1 is achievable via a variety of different IRZ strat-
egies, as the majority of injectants are specifically targeted to
achieve contaminant degradation or destruction. In addition
to Mechanism 1, Mechanisms 2 through 4 are all achievable
via biological remedies. In addition to NAPLs, sorbed mass
also contributes significantly to lingering soil and dissolved-
phase concentrations in source areas. Sorption of hydrophobic
compounds is based on the soil partitioning coefficient (Kd),
which represents the extent that the hydrophobic compound
partitions between aqueous and soil systems.17 Kd has been
shown to decrease during fermentation of carbon substrates,16
confirming that desorption of sorbed mass occurs in the pres-
ence of fermented fluid.
The collective benefit of these processes in biological IRZs
is regarded as the primary advantage of in  situ biological
treatment strategies for source zone treatment when compared
to other injection-based remedies (e.g., chemical oxidation).
A review of chlorinated solvent source zone applications has
demonstrated that biological IRZs can be near equivalent to
thermal remedies for total reduction in DNAPL parent spe-
cies concentration and exhibited twofold less rebound that
comparable chemical oxidation strategies.18 An example of
this collective benefit is highlighted in Figure 6.21, in which
the total molar mass of observed chlorinated ethenes follow-
ing treatment increased fivefold within six months following
initiation of the carbon-based injection program.
The aforementioned parameters (concentration gradient,
NAPL surface area, and soil partitioning coefficient) all con-
tribute to the overall dissolution of NAPL and desorption of
198 Remediation Engineering

450

PCE, TCE, c-DCE, VC, and ethene (µmol/L)

Ethene
400 VC
5× increase in molarity from baseline TOC
DCE
350 Methane
TCE 100,000
300 PCE 10,000

TOC and methane (mg/L)

250 1,000
100
200
10
150 1

100 0.1
0.01
50
0.001
0 0.0001
–49 112 174 232 312 357 425 553 663 819 959 1022 1113 1208 1323
Time (days)

FIGURE 6.21  Field data set from source zone monitoring well influenced by organic carbon injections. Following initiation of treatment,
total chlorinated ethene molarity increased by fivefold reflecting a combination of DNAPL source removal mechanisms related to increased
daughter product solubility, enhanced dissolution of residual source mass, and enhanced dissolved-phase treatment rates.

sorbed mass within a source zone. Understanding how these the water surface and through the saturated zone allows for
can be manipulated can lead to optimized source mass removal. more effective treatment using injection-based techniques. As
As all are dependent on saturating the mobile aquifer fraction discussed in Chapter 2, physical DNAPL transport also allows
with reagent to reduce dissolved-phase concentrations, injec- for its distribution as smaller globules or ganglia that diminish
tion wells or delivery points must be installed to achieve this its tendency to accumulate in pools and result in greater over-
reagent distribution objective. As detailed in Chapter 4, many all NAPL surface areas. These two factors can allow greater
high-resolution sampling techniques can provide a robust data in situ treatment success for DNAPL source zones when com-
set to understand the vertical stratification of source mass and pared to LNAPL. LNAPL exhibits a generally opposite behav-
its residence in either high- or low-permeability intervals. ior trend based on its relative density to water, with free-phase
These techniques can inform design decision making and materials predestined to accumulate at the groundwater sur-
ensure that the NAPL is both accessible to in situ techniques face (decreasing overall NAPL body surface area) where it is
and can be addressed within a reasonable time. This infor- less accessible to dissolved-phase reagents. While the solubil-
mation can also provide early warning indications to support ity and degradability of many regulated LNAPL contaminants
evaluation of alternative short-term physical removal tech- (e.g., benzene, toluene, ethylbenzene and xylenes (BTEX),
niques intended to capture bulk phase mass prior to deploy- and, ketones) are relatively significant, these materials must
ment of an injection-based polishing strategy. Due to its higher partition across the LNAPL-water interface in order to be
density relative to water, downward DNAPL transport toward accessible to injection-based techniques. Figure 6.22 presents

30,000
10,000
Persulfate concentration (mg/L)

25,000
Benzene concentration (µg/L)

1,000 20,000

15,000
100
10,000
10
Benzene 5,000
Persulfate
1 0
–30 10 50 90 130 170 210 250 290 330 370 410 450 490
Elapsed time relative to injection (days)

FIGURE 6.22  Observed benzene concentrations at a monitoring well within an area containing residual petroleum LNAPL. Persulfate
injection from adjacent injection well results in significant persulfate anion (and associated sulfate radical) breakthrough achieving treat-
ment of dissolved-phase benzene. Following persulfate oxidant consumption, additional benzene dissolution from residual LNAPL at the
groundwater interface results in restoration of preinjection concentrations.
Injected Reagent–Based Remedies
a data set collected at a monitoring well containing LNAPL
in a source area where a persulfate oxidation injection was
completed. While significant benzene treatment was achieved
while free persulfate was present, complete benzene rebound
to levels above the baseline concentration was observed as the
oxidant was consumed. This example highlights the potential
value in addressing sideline NAPL material (in this case at or
above the groundwater interface) via alternative physical tech-
niques (e.g., soil vapor extraction [SVE], vacuum extraction,
LNAPL skimming) prior to implementing an in situ dissolved-
phase remedy.
6.2  IN SITU BIOREMEDIATION
In  situ bioremediation is a technology that utilizes biologi-
cal processes to remove a contaminant through metabolic or
cometabolic processes, resulting in either lesser toxic com-
pounds or innocuous end products such as carbon dioxide
and water. The type of microbial community present, its rela-
tive stability, and how the community might be “engineered”
differ for each contaminant and each individual site. Within
every ecosystem, there is a network of interacting organisms
competing for limited resources. Each of these organisms
must have the following four basic needs fulfilled:
1. An energy source to support the endergonic reac-
tions that are entailed in the building of proteins
and other molecules. Organisms capture energy
from reduction–oxidation reactions they organize
between electron donors and electron acceptors and
store that energy in molecules such as adenosine-5′-
triphosphate (ATP).
2. A carbon source to build proteins and other mol-
ecules. In many cases, the electron donor and car-
bon source are the same. However, chemotrophic
species gain energy from reduction–oxidation reac-
tions arranged between inorganic compounds, so
they must gather carbon to build biomass from other
sources.
3. Mineral nutrients such as nitrogen and phosphorus
are required in the formation of many biochemical
compounds critical to life. ATP, DNA, and RNA are
a few examples.
4. Many organisms require organic nutrients that they
cannot synthesize, but which are essential to their
metabolism. Vitamins such as B12 and other cofac-
tors are examples of organic nutrients.
These four components, combined with variables such as tem-
perature, pH, and redox potential, comprise the backbone of
the aquifer habitat.
The composition of aquifer microbial communities shifts
continuously in response to changes in the physical and chem-
ical habitat. Ecologists use the term succession to describe
a predictable progression in the species composition of plant
and animal communities in response to major habitat distur-
bances. Species early in the succession prepare the habitat for
199
species that appear later. For terrestrial ecosystems, the suc-
cession occurs over time, on a particular piece of real estate.
Over many generations, a dynamic equilibrium is achieved.
In an aquifer, groundwater flow is a dominant feature of the
habitat, and the concept of succession needs to be adjusted
somewhat to support analysis of typical aquifer microbial
ecology. To make those adjustments, we borrow from con-
cepts of stream ecology.
In 1980, Robin Vannote and his coworkers published
a benchmark study on aquatic ecology titled “The River
Continuum Concept.”19 They provided a framework for
understanding how communities of organisms are structured
in flowing ecosystems. From their analysis, it became clear
that stream communities form a continuum of species associ-
ations that are structured in response to the carbon and energy
sources arriving at any point in the continuum. In the upper-
most reaches of a stream, carbon arrives largely unprocessed,
as particulate organic matter (e.g., in the form of leaves and
twigs). Here, the stream communities are dominated by spe-
cies that perform the first stages of carbon decomposition. In
the lower reaches, carbon is highly processed, arriving mostly
in the form of dissolved organic matter. At any point in the
continuum, the composition of species is determined by the
quality and quantity of arriving carbon and energy.
It is very useful to borrow from “The River Continuum
Concept” in building an understanding of the aquifer ecosys-
tem, because the structure and dynamics of an aquifer resem-
ble those of a surface stream ecosystem in many ways: there is
a unidirectional flow of water through the system; the biomass
is predominantly affixed to solid surfaces and the organisms
survive by processing organic matter that arrives in the passing
water; organisms are adapted to remain attached to the solid
medium as long as the habitat is suitable but may detach and
drift in the flowing water when conditions become adverse;
the products of organic carbon processing by organisms at any
point in the continuum comprise the carbon source (input) to
the organisms occupying a position immediately downstream;
availability of oxygen, nitrates, and other electron acceptors
at any point in the continuum is determined by the amount
passed along from upstream communities and by the rate of
recharge from above; the biomass and its composition at any
point in the continuum are determined by the rate and nature
of the carbon supply, by the rate and nature of electron accep-
tor supply, and by the rate and composition of mineral nutrient
supplies, all arriving from upstream (upgradient).
An aquifer microbial continuum is a succession of micro-
bial community structure, aligned along the groundwater flow
path in any aquifer. This succession constitutes a continuum of
habitat conditions and species composition. The steady-state
microbial community structure at any point in the continuum
is a reflection of the inputs received from upgradient commu-
nities and through recharge from above (or below). When the
inputs remain approximately constant, the microbial commu-
nity structure will maintain an approximate steady state. This
continuum can be disrupted by a change in the inputs at any
point—and that is our objective in deploying in situ biologi-
cal treatment remedies. The microbial community structure
200
downgradient from the point of disruption will restructure
in response to the changing habitat, and a succession of spe-
cies occurs in response to these changes as a new steady-state
structure develops.
The dearth of information about soil microbial commu-
nities is a consequence of their enormous complexity and
genetic diversity, and the fact that the microorganisms that
can be isolated from soil and studied in isolation represent
only a small portion of the microbial groups present in situ.
Soil microorganisms do not behave as a homogeneous trophic
level and the species composition of a soil microbial com-
munity can influence microbial processes in the soil both
qualitatively and quantitatively. As a result, it is important to
examine the internal dynamics of soil microbial communities
not simply for the sake of characterizing these fascinatingly
complex biotic systems but also to understand how bacterial
populations evolve based on changes in the biogeochemical
environment.
The great diversity of microorganisms and their versatile
metabolism mirrors the wide range of substrates that are used
for microbial growth and the natural environments in which
they are found. Many types of microorganisms are able to
adapt and metabolize different and often relatively new indus-
trial compounds, which are often considered to be recalcitrant
and persistent in the environment.
Metabolic processes involve the use of the contaminant by
the organisms as a source of energy or as a carbon source for
growth. Cometabolic processes involve the degradation of the
contaminant by an enzyme produced by the microorganism
for another reason, resulting in fortuitous degradation of the
contaminant with no direct benefit to the organism respon-
sible for enzyme synthesis. In the case of cometabolism,
contaminant degradation occurs in the presence of an alter-
native growth substrate used as the predominant energy and
carbon source.20 These processes can be enhanced through
the addition of a growth stimulant, which is something that
is currently limiting or missing from the natural environ-
ment. Bioremediation can be achieved either ex situ, such as
within an aboveground bioreactor, or in  situ, by emplacing
the microbial stimulant into the targeted treatment zone in the
natural environment. The type of stimulant added to the treat-
ment zone depends on the contaminant type, the site-specific
geochemistry, and the targeted biodegradation mechanism. It
is critical to understand what primary degradation pathway
is being targeted and the underlying science behind why the
stimulant will work in order to be successful in field applica-
tion of in situ bioremediation methods.
Microorganisms, just as humans, obtain energy for growth
and energy from physiologically coupling oxidation and
reduction reactions. During these growth-promoting reac-
tions, electrons are transferred from one group of compounds
called electron donors to another group called electron accep-
tors, and energy is released. Electron donors are compounds
that occur in relatively reduced states and include a variety
of natural organic materials, sugars, and organic acids that
can be either directly utilized or fermented to yield dissolved
hydrogen electron donor (Figure 6.23). Many contaminant
Remediation Engineering
Electron acceptors Electron donors
(O2, NO3–, SO42–, etc.) (C6H12O6, etc.)
Microbial reactions on
e– e–
Contaminant Contaminant
as as
electron donor electron acceptor
Oxidation Reduction
FIGURE 6.23  Depiction of contaminant(s) participating in micro-
bial oxidation or reduction reactions.
compounds such as PHCs, ketones, alcohols, lightly chlo-
rinated (less oxidized) ethenes, ethanes, and methanes also
can act as electron donors. Electron acceptors are elements or
compounds that occur in relatively oxidized states and include
dissolved oxygen, NO32−, Fe3+, SO42−, CO2, and several highly
chlorinated solvents.
A reaction is considered to be biotic if it directly involves
the participation of metabolically active microorganisms.
The consumption of naturally occurring electron donors and
acceptors will result in an overall change in aquifer geo-
chemical composition, which can in turn influence second-
ary reactions and support abiotic reactions with the target
contaminants of interest. Many important pathways by which
contaminant molecules are microbially transformed within
the reactive zones involve oxidative and reductive steps. The
easiest way to recognize whether a contaminant has been oxi-
dized or reduced during a reaction is to check whether there
has been a net change in the oxidation state(s) of atoms like C,
N, or S involved in the reaction.
Since most subsurface redox reactions are microbially
mediated, the evaluation of how much energy an organism
may derive from a given reaction may provide very useful
insight into the sequences of these reactions and the kinds of
organisms expected under given conditions.
In general, the more easily biotransformable contaminants
have simple molecular structures (which are often similar to
the structures of naturally occurring organic compounds), are
water soluble and nontoxic, and can be transformed by aero-
bic metabolism. In contrast, contaminants that resist biotrans-
formation may have complex molecular structures (especially
structures not found in nature or of recent anthropogenic
origin) and low water solubility, or they may be toxic to the
microorganisms. As microbial communities reside in ground-
water and soils with sufficient moisture content, microbial
contaminant transformation via biochemical reactions can
only take place when the contaminants are present and avail-
able in the dissolved phase.
It has been conventional to categorize all microbially
catalyzed reactions as either aerobic or anaerobic reactions.
Under aerobic conditions (in the presence of oxygen), bacte-
ria couple the oxidation of contaminants (electron donors) to
the reduction of oxygen (electron acceptors). Under anaerobic
conditions, most organic compounds are degraded by groups
of interacting microorganisms referred to as a consortium.
Injected Reagent–Based Remedies
Electron acceptors Microorganisms Change Aqueous chemistry
(oxidants) in ΔH + reduced species
O2 Aerobic respiration +ve CO2, H2O
NO3– Nitrate reduction +ve N2
Mn4+ Manganese reduction –ve Mn2+
Fe3+ Iron reduction –ve Fe2+
SO42– Sulfate reduction +ve S2–, HS–
CO2 Methanogenesis +ve CH4
FIGURE 6.24  Primary microbial oxidation processes.
While the terms aerobic and anaerobic are commonly used,
it is important to note that within the same system subsurface
groundwater system, different microenvironments may exist
that exhibit oxygen-rich and oxygen-poor conditions and con-
tain other electron donors and acceptors that can be utilized
by the microbial community. Accordingly, referring to the
collective microbial processes more generally as either oxida-
tion or reduction reactions better describes the occurrence of
microbial electron transfer from electron donors to electron
acceptors based on their relative availability. Several typical
examples of microbial reactions that are leveraged within IRZ
systems are highlighted in Figure 6.24. During these reac-
tions, the electron donors and electron acceptors are both
considered primary growth substrates because they promote
microbial growth.
6.2.1 Microbiology
An aquifer is a very complex and dynamic system, teeming
with life. The number of microbial species populating an
aquifer ecosystem is typically very high. Studies have shown
up to 4000 distinct genomes in soil samples analyzed for
DNA content.21,22 This was more than 200-fold higher than
results or enumeration of phenotypes in isolation plate counts.
Bacterial populations in aquifer ecosystems are numerically
immense. Groundwater samples often contain 109 or more
colony-forming units (CFUs) per milliliter, and soil samples
may contain more than 106 CFUs per gram. CFUs are spores
and viable bacterial cells that form colonies when placed in
favorable laboratory culture conditions. Most of the bacterial
biomass in an aquifer is firmly attached to the soil particles,
and the groundwater fraction of the population is quite small
in comparison. Generation times for bacteria can be very
short, ranging from tens of minutes to tens of hours. This
makes the aquifer ecosystem very responsive to changes in
habitat conditions.
Every cubic meter of an aquifer formation is composed of
intermingled solids and liquids, populated by a diverse array
of flora and, in some cases, fauna. In an unconsolidated aqui-
fer formation, the habitable surface area of particles that com-
prise the porous medium may reach 1 million square meters
for every cubic meter of aquifer. The specific surface of non-
swelling clays such as kaolinite ranges from 10 to 30 m2 g–1,
while the specific surface of swelling clays such as montmoril-
lonite and vermiculite may reach 800 m2 g–1.23 These surfaces
201
are populated by organisms that make a living from organic
matter flowing past in the groundwater, by consuming organic
matter trapped among the mineral particles, or by the oxida-
tion and reduction of inorganic matter that may include the
mineral particles themselves. The soil, the groundwater, and
the organisms populating that physical structure comprise the
aquifer ecosystem.
Aquifer microbial populations may include representatives
from all three of the biological domains: Bacteria, Archaea,
and Eukarya. Bacteria include genera such as Bacillus,
Clostridium, and Pseudomonas, while Archaea include the
methanogens such as those in the genus Methanosarcina.
Aquifer communities are dominated both in biomass and in
numbers by members of the Bacteria and the Archaea, but
Eukarya (which include all of the higher plants and animals)
may be represented in aquifer communities by members of
the fungi, the ciliates, and the flagellates.
The primary microbes targeted in bioremediation appli-
cations include those found on the Bacteria and Archaea
branches of the tree of life (Figure 6.25). Both Bacteria
and Archaea are prokaryotic organisms, meaning that they
are single-celled organisms that lack a membrane-enclosed
nucleus and other organelles. The use of the terms “microbe”
and “microorganism” to collectively refer to both types of
organisms is intentional rather than lumping both groups
into the category “bacteria” as there are key differences in
the membrane structure between these two groups. The four
fundamental differences between the archaeal membrane and
those of all other cells (both Bacteria and Eukaryotes) are
as follows: (1) chirality of glycerol, (2) ether linkages (ester
bonds are present in bacterial and eukaryotic cells), (3) iso-
prenoid chains, and (4) branching of side chains. The side
chains in the phospholipids of bacteria and eukaryotes are
fatty acids, chains of usually 16 to 18 carbon atoms. Archaea
do not use fatty acids to build their membrane phospholipids.
Instead, they have side chains of 20 carbon atoms built from
isoprene. These differences are important to understand as
they factor into some of the molecular techniques described
in Section 6.2.1.3, which can be used as part of a bioremedia-
tion monitoring program.
Most biodegradation in nature occurs via consortial
metabolism (or syntrophy), that is, by sequential metabolism
in which part of the pathway is found in one microorganism
and part in others. This conjecture is often applied to sys-
tems where the enzymological details of the biodegradation
step(s) are unknown, are inadequate, or cannot be derived
from studies conducted with pure cultures. While many
in  situ systems observed in a field setting are challenging
to reproduce in a lab, numerous microorganisms have been
identified that carry out specific chemical transformation
steps for a variety of target contaminants. As we attempt
to target these existing organisms (or augment them with
pure cultures) as part of injection programs, we must keep
in mind the vast diversity of biological IRZs that results
in an environment that metabolizes collectively, shares
biodegradative genes, and evolves collectively to biode-
grade new compounds that enter an environmental niche.24
202 Remediation Engineering

Eukarya
Archaea
Methanogens Animals Green plants

Extreme Fungi
Extreme
Bacteria halophiles Protozoa
thermophiles
Aerobic
heterotrophs
Dehalococcoides
Gram-positive
bacteria
Cyanobacteria

Protobacteria

FIGURE 6.25  Evolutionary relationships between the three major domains of life on Earth: the Bacteria, the Archaea, and the Eukarya.
The number of groups within each domain has been simplified, and spatial relationships on the graphs are not meant to imply evolutionary
relationships within the domains. All three domains are represented in aquifer biota.

While select microbial species may be largely responsible for
the specific transformation processes, we still must consider
the aggregate potential of the entire microbial community
and its bearing on treatment rates, geochemical conditions,
and reagent-dosing considerations.
6.2.1.1  Types of Microbial Reactions
As described in Section 2.6.2, microbial transformation
processes can be classified under several primary mecha-
nisms: (1) microbial oxidation, (2) microbial reduction, and
(3) cometabolic transformation. As described in Section
6.2.1, select contaminants are degraded via combinations of
these mechanisms via syntrophic processes. While there are
obvious differences in organism physiologies between these
groups, the manner in which they metabolize food and gener-
ate energy for growth and movement is the same. There are
two key elements to microbial metabolism: catabolism, by
which organisms generate energy (specifically generation of
ATP), and anabolism, where energy is used to build cellu-
lar components and additional biomass (Figure 6.26). Three
things are required for metabolism: an electron acceptor, an
electron donor, and a carbon source. Microorganisms, same as
humans, obtain energy for growth by coupling together oxida-
tion and reduction reactions, where electrons are transferred
from one group or compounds (electron donors) to another
group (electron acceptors), thereby releasing energy. Carbon
Energy Small Energy Large
Large
molecules molecules
molecules
Catabolism Anabolism
may not be part of the electron donor/acceptor process but
is required for anabolic reactions. In the oxidation–reduction
process, two compounds are transformed simultaneously—
one is reduced (gains electrons) and the other is oxidized
(loses electrons). The compound that is reduced is called the
electron acceptor (or oxidant) and the compound that is oxi-
dized is termed the electron donor (or reductant). The intent
of bioremediation is to add a key component missing from the
microbial environment that either limits or prevents the target
contaminant transformation reaction from occurring. In many
cases, this is either an electron donor or an electron acceptor,
which may be either naturally limited within a given ground-
water system or have already been depleted in the presence of
the contaminant.
Microbial metabolisms can be classified based on the fol-
lowing key principles: (1) how they obtain carbon for anabo-
lism, (2) how they obtain electron donors, and (3) what they
use as an energy source (Table 6.2). The naming conventions
reflected in Table 6.2 are often combined into descriptors
for specific groups of organisms. For example, a chemo-
lithoautotroph is an organism that obtains energy from the
TABLE 6.2
Microbial Naming Conventions Based on Primary
Metabolic Functions
Metabolism Principle Name Description
Method for obtaining carbon Autotrophic Carbon from CO2
Heterotrophic Carbon from organic
compounds
Method for obtaining Lithotrophic Electrons from
electron donor inorganic compounds
Organotrophic Electrons from organic
compounds

FIGURE 6.26  Simplified microbial metabolism. Catabolism Method for obtaining energy Chemotrophic Energy from external
entails the breakdown of larger molecules and food substrates yield- chemical compounds
ing smaller by-products and energy; anabolism requires energy and Phototrophic Energy from light
yields additional cell mass and cellular constituents.
Injected Reagent–Based Remedies
oxidation of an inorganic compound and carbon from the fix-
ation of carbon dioxide. Nitrifying bacteria, sulfur-oxidizing
bacteria, and iron-oxidizing bacteria are all examples of
chemolithoautotrophs.
Aerobic respiration, anaerobic respiration, and fermenta-
tion are the three types of metabolisms in which these pro-
cesses occur. In aerobic processes, oxygen is used as the
electron acceptor. Anaerobic reactions use something other
than oxygen as an electron acceptor such as nitrate, iron,
manganese, and sulfate, among other compounds. In many
cases, electron acceptors can be a contaminant targeted for
destruction (perchlorate, nitrate, chlorinated compounds).
Fermentation processes occur under anaerobic conditions and
use the same organic compound as an electron donor and an
electron acceptor. The end products of these reactions can
vary widely, dependent both on the contaminant undergoing
biodegradation processes and the type of metabolism process.
When organic compounds are completely oxidized to inor-
ganic end products such as carbon dioxide and water, the pro-
cess is referred to as mineralization.
6.2.1.2  Microbial Energetics
Microorganisms can cause major changes in the biogeochem-
istry of a groundwater system. Their small size and adaptabil-
ity, as well as the diversity of nutritional preferences, enable
them to catalyze a wide range of biotransformation reactions.
Microorganisms use enzymes to accelerate the rates of bio-
chemical reactions, which in turn help them to reproduce by
creating daughter cells composed of various cellular compo-
nents (Figure 6.27). The production of energy, its storage, and
its use are central to the economy of the bacterial cell in a
biogeochemical system.
There are two principal forms of energy: kinetic and poten-
tial. Kinetic energy is the energy of movement—the motion of
molecules, for example. The second form of energy, potential
energy, or stored energy, is more important in the function of
biological or chemical systems.
Several forms of potential energy are biologically signifi-
cant.25 Central to biology is the potential energy stored in the
bonds connecting atoms in molecules. Indeed, most of the
biochemical reactions involve the making or breaking of at
least one covalent chemical bond. This energy is recognized
New
n d
sa
t r on n cells
c o
Ele carb
Organic + Energy
contaminant
Micro-
organism Ele
ctr
Electron
on acceptors
s
(e.g., O2)
FIGURE 6.27  Conceptual description of microorganisms gaining
energy and utilizing contaminants as an electron donor for growth.
203
when chemicals undergo energy-releasing reactions. Glucose,
present in sugar, for example, is high in potential energy.
Microbial cells degrade glucose continuously, and the energy
released when glucose is metabolized is harnessed to do many
kinds of “microbial” work.
Another biologically important form of potential energy,
to which we shall refer often, is the energy in a concen-
tration gradient.25 When the concentration of a substance
on one side of a permeable barrier, such as a membrane,
is different from that on the other side, the result is a con-
centration gradient. Microbes form concentration gradients
between their interior and the external fluids by selectively
exchanging substrate, nutrients, waste products, and ions
with their surroundings. Also, compartments within bacte-
rial cells frequently contain different concentrations of ions
and other molecules.
Two important questions can be asked about any prospec-
tive biochemical reaction: (1) does the reaction yield energy
or consume energy? and (2) how fast does the reaction pro-
ceed? The first question is one of chemical thermodynamics,
and calculations can be performed to determine whether a
particular reaction will be profitable (by yielding energy) for
an organism. Organisms gaining the most energy from the
available electron donors and electron acceptors will tend to
dominate the microbial community for as long as that par-
ticular set of donors/acceptors are present. For example, when
oxygen is available, aerobic bacteria will be present in highest
quantities, and when oxygen becomes unavailable, opportuni-
ties arise for anaerobic bacteria that survive on less energy-
effective reduction–oxidation reactions to gain a foothold in
the community. With respect to the second question, enzymes
facilitate metabolic reactions by lowering energy thresholds
for reactions to occur. These enzymes determine how fast a
reaction proceeds.
According to the first law of thermodynamics, energy
is neither created nor destroyed, but it can be converted
from one form to another (conversion of mass to energy in
nuclear reactions is an exception to this rule). In all cells,
chemical potential energy, released by breakage of certain
chemical bonds, is used to generate potential energy in
the form of concentration and electric potential gradients.
Similarly, energy stored in chemical concentration gradi-
ents or electric potential gradients is used to synthesize
chemical bonds or to transport other molecules “uphill”
against a concentration gradient. This latter process occurs
during the transport of nutrients such as glucose into
microbial cells and transport of many waste products out
of cells. Because all forms of energy are interconvertible,
they can be expressed in the same units of measurement,
such as the calorie or joule.25
The maintenance and growth of any bacterial popula-
tion are founded on its ability to extract energy from the
chemical reaction of electron donors and acceptors. These
reactions can be described in terms of the enthalpy (H) or
heat consumed or released and the change in entropy (S)
entailed in the conversion of reactants to products. This
total energy change is termed the Gibbs free energy (G).
204
Reactions that lead to a net release of energy are termed
exergonic, while reactions that require a net input of
energy are termed endergonic. The products and reactants
involved in a reaction can be used to predict the direction
in which their reaction will proceed. Each can be used to
determine the relative values of free energy (∆G), as shown
in the following:
DG = G products - Greactants (6.23)
In mathematical terms, Gibbs law can be described by the fol-
lowing set of statements about ∆G:
• If ∆G is negative for a biochemical reaction, the for-
ward reaction or process (from left to right as writ-
ten) will tend to occur spontaneously.
• If ∆G is positive, the reverse reaction (from right to
left as written) will tend to occur.
• If ∆G is zero, both forward and reverse reactions
occur at equal rates; the reaction is at equilibrium.
For example, if one mole of glucose is completely oxidized,
686 kcal of energy is produced along with carbon dioxide and
water:
C6H12O6 + 8O2 ® 6CO2 + 12H 2O + 686 kcal
Thus, microbial cells using one mole of glucose as the energy
source cannot obtain more than 686 kcal of energy. This does
not mean, however, that all of that 686 kcal of energy is avail-
able to the cells. The second law of thermodynamics states
that some portion of the energy, the free energy, will be avail-
able to do work, whereas another portion, called entropy, will
be unavailable to do work. Studies of energy utilization in liv-
ing cells show that, of the 686 kcal released, a maximum of
only about 280 kcal is actually available as free energy (∆G)
and can be utilized by the microbial cells. The rest (60%) of
the energy released by glucose oxidation goes toward increas-
ing entropy and is lost as heat.26 The aforementioned example
reflects an aerobic microbial process, where glucose is used
as an electron donor in the presence of oxygen as an electron
acceptor, which yields a substantial energy gain. Anaerobic
organisms also may utilize glucose as a food source, but the
electron acceptors that are available (e.g., sulfate, nitrate, iron)
do not provide the same high energy yield obtained in aerobic
metabolism.
The value of ∆G, like an equilibrium constant, is inde-
pendent of the reaction mechanism and rate. Reactions with
negative values that have very slow rate constants may not
occur, unless a catalyst is present—but the catalyst presence
does not affect the value of ∆G. At constant temperature (T)
and pressure (consistent with most biological systems), the
change in bond energy between reactants and products (H)
and the change in the randomness of the system (S) can be
determined via the following:
G = H - TS (6.24)
Remediation Engineering
If T (expressed in units Kelvin (K)) remains constant, a
reaction will proceed spontaneously only if the free energy
change ∆G in the following van’t Hoff equation is negative:
DG = DH - TDS (6.25)
In Equation 6.25, the enthalpy H of reactants and products
is equal to their total bond energies, and ∆H represents the
overall change in bond energies.
Entropy S is a measure of the degree of randomness or
disorder of a system. Entropy increases as a system becomes
more disordered and decreases as it becomes more structured.
Consider, for example, the diffusion of solutes and nutrients
from one solution into another one in which their concentra-
tion is lower. This important biological reaction is driven only
by an increase in entropy; in such a process, ∆H is near zero.
The negative free energy of the reaction in which nutrient
molecules are liberated to diffuse over a larger volume will be
due solely to the positive value of ∆S in Equation 6.25.
Another example is when the formation of hydrophobic
bonds is driven primarily by a change in entropy. When a long
hydrophobic molecule is dissolved in water, the water mole-
cules are forced to form a cage around it, restricting their free
motion. This imposes a high degree of order on their arrange-
ment and lowers the entropy of the system (∆S < 0). Because
the entropy change is negative, hydrophobic molecules do not
dissolve well in aqueous solutions and tend to stay associated
with one another.
We can summarize the relationships between free energy,
enthalpy, and entropy as follows:
• An exothermic reaction (∆H < 0) that increases
entropy (∆S > 0) occurs spontaneously (∆G < 0).
• An endothermic reaction (∆H < 0) will occur spon-
taneously if ∆S increases enough so that the T∆S
term can overcome the positive ∆H.
• If the conversion of reactants into products results in
no change in free energy (∆G < 0), then the system is
at equilibrium, that is, any conversion of reactants to
products is balanced by an equal conversion of prod-
ucts to reactants.
The change in Gibbs energy for a reaction is calculated by
the difference between the Gibbs energy of products and
reactants:
DG = åG 0
products - åG 0
reactants (6.26)
where G 0 are values for the free energy of formation for indi-
vidual compounds, referenced to a standard physical–chemical
state. Values of ∆G for a reaction can be classified as either
exothermic, endothermic, or energy-conserving reactions. In
an exothermic reaction, the products contain less bond energy
than the reactants, the liberated energy is usually converted
to heat (the energy of molecular motion), and ∆H is nega-
tive. In an endothermic reaction, the products contain more
Injected Reagent–Based Remedies 205

bond energy than the reactants, heat is absorbed, and ∆H is
positive. Reactions tend to proceed if they liberate energy (if
∆H, 0), but this is only one of two important parameters of
free energy to consider; the other is entropy.
The metabolic energy yield of glucose consumption can
be calculated under aerobic and anaerobic conditions using
Equations 6.25 and 6.26 and values for Gibbs free energy of
formation from Table 6.3:
Aerobic
has limited energy gain potential, as shown in the compari-
son earlier, and the use of Gibbs free energy in determining
whether any reaction system supports growth in chemotrophic
anaerobes can be outlined.27 Researchers have recognized the
energy required for the formation of ATP as a threshold value,
below which energy released from metabolic reactions cannot
be captured by an organism:
ADP + Pi ® ATP DG = +60 kJ/mol (6.29)

C6H12O6 (s) + O2 (g) ® 6CO2 (g) + 6H 2O(g) where ADP is adenosine diphosphate and Pi is inorganic
phosphate.
DG = -2879 kJ/mol (6.27) All organisms utilize ATP to store and transfer energy
captured in metabolic reactions. Bacteria consume 20 mmol
Anaerobic of ATP in the production of 1 g of biomass.27 They also esti-
mated that the formation of ATP from ADP and inorganic
C6H12O6 (s) ® 3CO2 (g) + 3CH 4 (g) DG = -425 kJ/mol phosphate consumes between 42 and 50 kJ mol21 when the
(6.28) ATP-generating process is fully reversible. The ATP forma-
tion energy sets a threshold energy yield for a metabolic reac-
This comparison shows the limited energy available to anaer- tion to be energy conserving.
obes and explains the typically lower biomass observed in Adding a 20 kJ/mol heat loss estimate to the energy
anaerobic systems when electron donors are abundant. demand of ATP formation, it was estimated that 70 kJ/mol is
For an organism to survive on the metabolism of any required for ATP formation, 60 kJ/mol under the best circum-
electron donor–electron acceptor pair, the organism must be stances.28 The author also updated the notion of the minimal
capable of conducting its reduction and oxidation reactions energy gain to support growth: ATP synthesis is driven by
in an energy-conserving manner. Anaerobic metabolism active (energy-demanding) transport of protons across cells or
mitochondrial membranes. Because three protons must pass
the membrane for every ATP formed, the minimum energy
TABLE 6.3 gain from catabolic metabolism is 20 kJ/mol. Smaller free
Values for Gibbs Free Energy of Formation energy changes cannot be “captured” in support of bacterial
for Selected Compounds growth.
The standard free energy change of a reaction ∆G° is the
Compound DGf0 (kJ/mol) value of the change in free energy under the conditions of
O2 (g) 0 25°C (298 K), 1 atm pressure, pH 7.0 (as in pure water), and
CH4 (g) −50.53 initial concentrations of 1 M for all reactants and products
CO2 (g) −394.36 except protons, which are kept at pH 7.0. The sign of ∆G°
H2 (g) 0 depends on the direction in which the reaction is written. If
N2 (g) 0 the reaction A → B has a ∆G° of –x kcal/mol, then the reverse
H+ (at pH 0) 0 reaction B → A will have a ∆G° value of +x kcal/mol.
H+ (at pH 7) −40.01 Most biological reactions differ from standard conditions,
OH− (aq) −157.2 particularly in the concentrations of reactants. The change in
H2O (aq) −237.14 free energy of a reaction (∆G) is influenced by temperature,
HCO3− (aq) −586.8 pressure, and the initial concentrations of reactants and products.
NO3− (aq) −111.3
Most biological reactions—like others that take place in aqueous
NO22− (aq) −32.2
solutions—also are affected by the pH of the solution. The Gibbs
SO42− −744.5
free energy for a reaction at nonstandard conditions is described
H2S (g) −33.4
by Equation 6.30, where A and B are reactants and C and D are
HS− (aq) 12.1
products. The free energy change is determined by the standard
Fe3+ (aq) −4.7
Fe2+ (aq) −78.9
free energy of the reaction (calculated using Equation 6.30), the
CI− (aq) −131.2
reaction temperature, reaction stoichiometries, and the concen-
CH2CH2 (aq) 81.43 trations of the products and reactants as shown in the following:
CHClCH2 (aq) 59.65
DG = DG° + RT lnQ
CHClCHCl (aq) 27.8
CCl2CHCl (aq) 25.41 é [C ]c [ D]d ù
[ products]
CCl2CCl2 27.59 = DG° + RT ln = DG° + RT ln ê a b ú
C6H12O6 (s) −910.6  [reactants ] ë [ A] [ B] û
(6.30)
206
where R is the gas constant of 1.987 cal K–1 mol–1, T is the
temperature (Kelvin), and Q is the initial ratio of products to
reactants.
Thermodynamics determines which reactions are energeti-
cally favorable and which are not. However, the rate at which
the reactions are actually carried out does not depend on free
energy change but rather on the reaction mechanism itself.
If one were to mix glucose with oxygenated water in a bea-
ker, glucose and O2 will react only at an immeasurable rate to
form CO2 and water, even though that reaction is energetically
favorable. At ambient temperatures (25°C), collisions of oxy-
gen and glucose molecules occur too infrequently and without
enough force for the reaction to proceed. This reaction can
only take place at extremely high temperatures, say, 500°C or
higher, without the presence of a catalyst.
Microbial organisms, which depend on thousands of bio-
chemical reactions like the uptake of glucose in order to
sustain life and grow, solve this problem through the use of
enzymes. Enzymes are proteins that catalyze chemical reac-
tions in living cells. In the previous example, if glucose oxi-
dase, an enzyme that brings glucose and oxygen together, is
added to the solution in the beaker, the reaction will be com-
pleted to CO2 and water with some intermediate steps. During
the biochemical reactions of microbial metabolism, glucose
oxidase is produced by the bacteria.
Enzymatically catalyzed reactions can be summarized as
E + S « ES (6.31)
ES « E + P (6.32)
where
E is the enzyme
S is the substrate
ES is the enzyme–substrate complex
P is products
Field-scale and enrichment culture degradation behav-
ior represents the superposition of several variables, includ-
ing (1) bacterial biomass and nutritional status, (2) available
enzyme mass, (3) available coenzyme mass, (4) rate of coen-
zyme replenishment, and (5) enzyme kinetics. It is important
to keep in mind that fast kinetics are not usable from an engi-
neering point of view if the bacteria cannot generate signifi-
cant biomass in the field. Conversely, cometabolic processes
with low per-unit-biomass degradation rates may provide
substantial dechlorination in the field, if the species involved
reach high biomass levels.
6.2.1.3  Microbial Analysis/Molecular Techniques
Microbial communities differ in both qualitative and quan-
titative compositions. The relative proportion of their com-
munity members is subject to biogeochemical changes of the
environment as well as changes caused by the physiological
and metabolic changes caused by the organisms. Organisms
that are abundant and culturable under some conditions may
develop into dormant and possibly uncultured forms under
Remediation Engineering
other conditions. What has been learned from recent studies
on microbiological analyses of environmental samples can be
summarized as follows: (1) the cultured microorganisms rep-
resent only a small fraction of natural microbial communities
and hence the microbial diversity in terms of species richness
and species abundance is grossly underestimated, and (2) our
understanding of microbial diversity is not represented by the
cultured fraction of the diversity.
A 2002 report published by the American Society of
Microbiology points to two critical concerns regarding stud-
ies on microbial diversity. First, those few microbial spe-
cies that are grown and studied in culture poorly represent
the diversity of physiology, biochemistry, and morphologies
that can be found in nature. “Although the general patterns
of macroorganismal diversity are relatively well known, spa-
tial patterns of microorganismal diversity are completely
unknown.”29 Constraints on knowledge are caused largely
by methodologies that do not contend well with the complex-
ity of field sites and the scale differential between field habi-
tats and laboratory microorganisms. It is easy to understand
this difficulty when we realize how small a sample we take
to represent a typical field site. A contaminated aquifer that
measures 500 ft in length, 100 ft in average width, and 20 ft
in thickness has a total volume of 1,000,000 ft3. Each split
spoon sample we collect has a volume of 0.025 ft3, so there are
more than 40,000,000 possible split spoons in the aquifer soil
population. Similarly, assuming a 30% aqueous porosity, this
same aquifer contains approximately 8,500,000 L of water,
which equates to 170,000,000 individual 50 mL groundwater
samples. While the number of available molecular diagnos-
tic tools has grown considerably over the course of the past
decade and provide a number of methods by which to assess
microbial communities, it is important to understand that the
results of lab assays on a few split spoons or groundwater
samples cannot be representative of an entire field site.
As a result of our inability to cope with microbial diversity,
efforts have been spent to develop methodologies that are con-
sidered to be a quantum leap from the previous ones. These
methodologies are referred to as environmental molecular
diagnostics (EMDs) and include two primary categories of
analysis: (1) compound-specific isotope analysis (CSIA) and
(2) molecular biological techniques (MBTs).30 These tools
have been developed as an additional line of evidence for use
in conjunction with hydrogeologic and biogeochemical data
to assess relative differences in contaminant origins, evaluate
whether contaminant transformation is occurring, and iden-
tify the mechanisms and microorganisms responsible. A sum-
mary of the commonly applied bench-scale tests or EMDs is
provided in Table 6.4, with a discussion pertaining to each of
the specific methods in the following.
Microcosm tests are the most traditional method of assess-
ing contaminant transformation under various conditions.
These bench-scale tests are usually developed with soil and
groundwater samples from a given site, with individual ves-
sels sampled or sacrificed over the duration of the study to
assess relative changes in contaminant concentrations, trans-
formation by-products, or other geochemical parameters.

TABLE 6.4
Commonly Used Microbial and Molecular Analytical Tools
Test Method Description
Microcosm testing Bench-scale testing using site soil
and groundwater containing target
contaminants and reagent(s)
considered for field deployment
CSIA Laboratory quantification method to
evaluate changes in contaminant
composition as a result of biotic and
abiotic transformation
PCR Provides definitive evidence of the
presence of a particular microbial
species
qPCR Provides definitive evidence of the
presence of a particular microbial
species and their relative abundance;
quantifies microbial activity
associated with mediating enzymes
responsible for target reactions
Microbial fingerprinting Provides overview of total viable
(PLFA, DGGE, etc.) biomass, the types of organisms
present, and their general
physiological characteristics
SIP Use of isotope-labeled contaminants
to assess degree of microbial
transformation or incorporation as
microbial biomass
Data Required
• Laboratory data associated with
liquid and headspace samples
• Reagent and geochemical parameters
• Microbial sampling
• Groundwater samples from locations
where target contaminant and
associated by-products are present
• Geochemical and microbial
sampling
• Soil samples or groundwater
samples from wells
• Microbial biomass extraction from
in-well sampling devices
• Soil samples or groundwater
samples from wells
• Microbial biomass extraction from
in-well sampling devices
• Soil or groundwater samples
• Microbial extraction from in-well
sampling device
• Groundwater samples from target
well location
Pros
• Detailed, definitive information on
contaminant removal
• Provides proof of concept with select substrate
and nutrient selection
• Provides relative assessment of contaminant
transformation via fate and transport processes
• Demonstrates presence of target
microorganism(s) responsible for target
treatment or attenuation process
• DNA data demonstrate presence of target
microorganism(s) responsible for target
treatment or attenuation process and their
relative abundance
• RNA data provide evidence of ongoing
microbial activity and synthesis of key
enzymes for treatment process
• Provides detailed information on microbial
community and can identify known organisms
responsible for target treatment mechanisms
• Low cost per sample
• Provides detailed information pertaining to the
utilization of a target contaminant based on
changes in seeded contaminant isotope
composition
Injected Reagent–Based Remedies
Cons
• Elevated cost, extended time
• Does not eliminate need for pilot
testing to confirm design parameters
• Data interpretation limited to known
transformation behaviors and
available benchmarks for isotopic
shifts
• Does not provide relative abundance
of target microbial population
• Potential for false negatives when
target microorganisms are present
but at low overall population density
• Sampling limited to identified
primers and target gene sequences
• Specific only to known groups of
organisms, does not quantify
specific target organisms
• Extended deployment time for
sample collection
• Limited to contaminants with
available isotope-enriched solution
207
208
Individual vessels can be augmented with potential substrates
considered for use in the field, which allows tailored experi-
ment setup to best reflect future IRZ performance.
CSIA is a laboratory forensic method used to understand
the relative change in element isotopic ratios within the
environment. Each element that comprises a contaminant
molecule has a known isotopic ratio, which when affected
by biological or abiotic degradation can preferentially shift
toward the heavier end isotopes remaining in the compound.
The isotope signature of a given contaminant will be unique
to its origin and specific method of manufacturing, so CSIA
allows comparison of a given contaminant molecule (or ele-
ments therein) to the original material in order to determine
whether transformation processes have occurred. A repository
of information has been completed (and continues to expand)
that provides benchmark shifts in isotopic ratios under differ-
ent biodegradation scenarios, and these expected shifts are
then used to assess whether transformation has occurred.
Polymerase chain reaction (PCR) amplifies the genes of
a particular microorganism, a family of microorganisms, or
genes present in a given media.31 The PCR sampling process
entails an initial cell lysis step to release the genetic mate-
rial (e.g., DNA), which is then followed by an initial high-
temperature (94°C–97°C) denaturation step during which
DNA within the sample is unzipped into two separate strands.
Once unzipped, the temperature is reduced to between 47°C
and 60°C and primers are added to initiate DNA replication.
These primers are unique to the specific organism targeted
that serve to initiate replication of target gene sequence(s) dur-
ing the elongation process. During elongation, the tempera-
ture is increased to 72°C, and in the presence of nucleotides
that serve as the building blocks for replication, DNA reduc-
tase facilitates gene replication. This process is then repeated
multiple times to amplify the individual target genes within
the sample to achieve a sufficient number of gene copies. The
DNA sequences identified in PCR results are then compared
to known DNA sequences of organisms responsible for bio-
degradation and are reported as either present/absent for a
specific DNA target.31
Quantitative PCR (qPCR) expands on the PCR method-
ology to provide information regarding the abundance and
activity of microorganisms in a given sample. The process-
ing methodology is similar to that of PCR with the exception
that fluorescent dye markers are added to the DNA amplifica-
tion mixture and are then replicated over the course of the
amplification process to achieve a threshold level. The num-
ber of amplification cycles required to achieve the threshold
cycle can be calibrated with known standards and can then
be used to quantify the abundance of specific genetic targets
in the original sample.31 Where qPCR can be used to identify
whether and how much of a specific organism’s DNA is pres-
ent, reverse transcriptase (RT)-qPCR can be used to quan-
tify whether that particular organism is actively producing
the target enzymes responsible for a known degradation step.
This process is similar to that of qPCR but instead entails
the extraction of RNA, which is then reverse transcribed back
into the complementary DNA strand.
Remediation Engineering
Microbial fingerprinting techniques are broad-brush
assays for use in quantifying particular groups of microorgan-
isms based on shared microbial characteristics or structure.
There are several different analyses including phospholipid
fatty acid (PLFA) analysis, denaturing gradient gel electro-
phoresis (DGGE), or terminal restriction fragment length
polymorphism (T-RFLP). Of these, PLFA is the most gen-
eral and provides an overall assessment of the presence and
viability of broad classes of organisms (e.g., proteobacteria,
firmicutes, anaerobes) under native conditions or in response
to remediation activities. While DGGE and T-RFLP do not
provide the degree of organism specificity of qPCR analyses,
the outputs of these are based on a DNA-based assessment of
the predominant groups of organisms (e.g., sulfate-reducing
bacteria, iron-reducing bacteria), which are collectively active
or responded similarly to treatment activities.31
Stable isotope probing (SIP) is used to assess whether a
specific contaminant is being actively degraded at a given
site. SIP techniques have been developed for a variety of con-
taminants and typically entail the seeding of an in situ sam-
pling device with a known volume of enriched contaminant
with a specific ratio of carbon 12 (12C) and carbon 13 (13C).
Degradation is demonstrated by analyzing the parent com-
pound within the sampling device or carbon dioxide dissolved
in the surrounding water to assess the relative quantity of 13C
and its enrichment in the parent compound, cellular biomass,
or as a degradation end product. These analyses can be cou-
pled with other microbial analyses to test for known microor-
ganisms or families of organisms responsible for the specific
degradation pattern.
There are other EMD tools that can be used to assess either
specific microbial enzyme activity or population variability
that are either not widespread or not commercially available.
Several of these include enzyme activity probes, which can be
used to detect for the presence of select enzymes with identi-
fied relevance to biodegradation; microarray sampling, which
enables comparison of DNA PCR signatures from indepen-
dent samples; or fluorescence in  situ hybridization, which
entails the fluorescent labeling of target microorganisms for
use in assessing the relative organism abundance and their
spatial distribution, as the method leaves the cells intact.
How each of these tools is applied can be highly variable
depending on the particular site conditions and the particular
question being asked. Due to the higher relative cost of these
analyses compared to other conventional fixed-lab analysis,
it is important to understand what questions the diagnostic
tools or bench studies are being used to answer and how this
information is to be integrated into the available site informa-
tion. Many of these tools can be used as part of site charac-
terization activities to provide a more robust understanding of
contaminant fate and transport and to support remedial deci-
sion making, or as part of remedial troubleshooting to support
assessment of IRZ treatment already underway. Deployment
of these sampling techniques is not a requirement to develop
an IRZ design, as the hydrogeologic and biogeochemical
information can be sufficient. If field-scale pilot testing is
planned to develop useful predesign information (volume to
Injected Reagent–Based Remedies
radial distribution ratios, reagent dosing, injectability, etc.),
extensive EMD sampling or completion of laboratory bench-
scale testing may be overly redundant.
6.2.1.4  Biostimulation versus Bioaugmentation
After studying and cataloging halophilic microorganisms in
salt lakes across the globe, the Dutch botanist and microbiolo-
gist Lourens Baas Becking hypothesized that “everything is
everywhere, but the environment selects.”32 This hypothesis
reflected his observation that consistent groups of organisms
were encountered in widely dispersed salt lakes with similar
properties and that a unique environment’s geochemistry and
condition would stack the deck for different groups of organ-
isms to proliferate and thrive. As we have steadily identified
the organisms responsible for many contaminant transfor-
mation mechanisms, Baas Becking’s hypothesis has gener-
ally held true. Dehalococcoides mccartyi is active at many
sites where PCE and TCE have been released, regardless of
whether the site is in North America, Europe, or Australia.
Assuming an ideal geochemistry for a particular process,
there are two primary means by which designers can control
the overall rate of treatment in biological IRZs. The first is to
achieve a sufficient quantity of the limiting growth substrate
for a sustained period of time to allow treatment. So long as
growth substrate is available, the target microorganism will
perform the target transformation process as fast as the cells
allow. In these cases, simply enhancing the activity of these
organisms is sufficient to expedite contaminant cleanup. This
process, biostimulation, entails the addition of the limiting
growth substrate to foster development of naturally occur-
ring aquifer bacteria within an engineered IRZ. In the case
of PCE or TCE, which serve as electron acceptors, this is
accomplished through the injection of electron donors at rates
that exceed the recharge of electron acceptors. The increased
availability of electron donor drives the aquifer microbial
communities into sulfate reduction, acetogenesis, and metha-
nogenesis. The generation of enzymes for these activities can
foster broad-spectrum cometabolic dechlorination, and other
microorganisms including Desulfuromonas, Dehalospirillum,
Dehalococcoides, Dehalobacter, and Desulfomonile may also
directly utilize PCE and TCE as alternative electron acceptors.
In the aforementioned example, while one species rep-
resents the primary target of the IRZ, the combined benefit
of stimulating the broader microbial consortia generates a
robust approach reliant on coarse adjustments of the micro-
bial ecology to induce the desired dechlorinating behaviors.
In biostimulation-based programs, if the target microbial
species is not significantly active—or at reduced population
size—there may be an observed lag phase as the microbial
community responds to disruption of the native aquifer equi-
librium and specific organisms proliferate according to sub-
strate availability.
The second method by which we can control biological
IRZ treatment rates is to enhance the overall population of
the target microorganism by essentially increasing the target
or organism population to perform more of the target trans-
formation step. This is referred to as bioaugmentation and
209
is the process of supplementing the native aquifer microbial
community through the injection of large quantities of com-
mercially grown bacteria intended to overwhelm the native
communities. In laboratory microcosms, these bacteria can
achieve degradation rates that exceed those achieved through
biostimulation of native communities at the field scale. This is
expected in that the conditions in laboratory reaction vessels
can be maintained within an ideal range for degradation. The
challenge in utilizing bioaugmentation is therefore maintain-
ing reasonable control over key microbial habitat variables
required to increase overall performance.
As bacteria prefer to adhere to soil surfaces, their injection
in the subsurface is not anticipated to mimic that of a soluble
tracer. While bacteria are expected to migrate some distance
with advective groundwater flow (adhering to and colonizing
soil surfaces as they go), adhesion behavior will tend to limit
their migration to zones surrounding the injection points. In
many cases, these are also the zones in which the IRZ is being
performed, which allows additional control over the reactant
injection and subsurface delivery.
There has been a significant level of debate among the
designers of microbial IRZs with respect to the efficacy of
biostimulation and bioaugmentation. The debate has centered
on whether all biological IRZs should be bioaugmented at the
outset or whether the first level of the treatment should be
completed via biostimulation only. In practice, the subsur-
face conditions must be appropriate prior to bioaugmenta-
tion such that the introduced cultures are not eradicated or
outcompeted immediately following introduction. This need
often requires initiating treatment using biostimulation alone,
where the limiting growth substrates are delivered into the
subsurface to foster the desired IRZ conditions. Following
start-up, performance monitoring can then be used to evaluate
whether the native community is capable of achieving treat-
ment rates consistent with cleanup objectives. While Baas
Becking’s hypothesis has generally held true, there are select
conditions in which the native microbial community does not
contain the target species at the necessary abundance (or at
all) or it is desirable to expedite treatment and introduction
of supplemental microorganisms is warranted. Thus, we’ve
learned that Diego Fontaneto’s revised hypothesis is likely
more appropriate in that: “everything is not everywhere, but
most things are pretty widespread.”33
For IRZ systems with available bioaugmentation options, a
discussion is included to outline the overall design or optimi-
zation thought process later in this chapter.
6.2.1.5  Biofilms and Biofouling
As discussed earlier, the injection of growth substrates or
nutrients into the subsurface will result in the proliferation
of the microbial community. The growth of microbial aggre-
gates is a natural behavior of microbial communities, and they
are typically encountered as suspended flocs or as surface bio-
films. Biofilms are large aggregations of bacteria and other
microorganisms bound together in a mass of extracellular
polymeric structures (EPS) that connect cells together and tie
them to a surface. EPS is generated by bacteria to provide
210
Attachment Maturation
FIGURE 6.28  Agglomeration of microorganisms and EPS materials during biofilm growth phases. (From Burnell, S. et al., Remediation,
23(1) 85, 2013.)
biofilm stability and enable mixed microbial communities to
exist in close proximity, thereby promoting cooperation and
communication between cells.34 EPS typically comprises
polysaccharides, nucleic acids, and proteins, with the fraction
of each varying under different biogeochemical environments.
It is classified as both bound EPS in the form of solid-phase
material present as sheaths, and capsular polymers, form-
ing attached organic material and soluble EPS in the form of
soluble macromolecules, colloids, and slimes. Soluble EPS
develops through the slow but steady dissolution of solid EPS
via enzymes excreted for the purpose of digesting and hydro-
lyzing food substrates.34 As EPS develops, the biofilm colony
expands and is generally represented in Figure 6.28 through
the attachment, maturation, and dispersal stages.
Similar to EPS, soluble microbial products (SMPs) are
biodegradable compounds that are released during either cell
growth or cell lysis and are composed of moderately sized
organic carbon molecules.34 These products typically com-
prised proteins, polysaccharides, and some humic-like mate-
rials.35 SMPs can be categorized either as those compounds
released during substrate metabolism (substrate-utilization-
associated products) or those released during biomass decay,
following cell lysis (biomass-associated products). Both EPS
and SMP compounds are microbially produced and will
be present during biomass growth. While the terms EPS
and SMP were coined during different areas of wastewater
treatment research, both these terms are commonly used to
describe the form of carbon exuded as part of biofilms and
microbial communities.
Aerobic and anaerobic bacteria not only can thrive side by
side within biofilms when biogeochemical conditions permit,
but species also collaborate to share metabolic by-products,
exchange genetic capabilities, or reinforce their polysaccha-
ride protection. The polysaccharide structure in which these
colonies reside acts as a form of armor, prevents sloughing
within passing groundwater, insulates against impacts of sig-
nificant geochemical change, and gives the microorganisms
protection beyond their usual defense mechanisms.
While the typical average diameter of a bacterium in estab-
lished biofilms is about 0.5–1  mm, biofilm bacteria rarely
adhere directly to solid surfaces. Instead, at distances shorter
than 1 nm, short-range forces such as hydrogen bonding and
dipole formation tend to be the dominant adhesion effects. As
bacteria are held in place and fed by the organic and inor-
ganic molecules trapped by these short-range forces, they
form slime that anchors them to solid surfaces and serves as a
home for additional bacterial growth. As the biofilm increases
Remediation Engineering
Biofilm
Maturation and dispersal
in overall thickness, the penetration of nutrients present in soil
pore water to the soil surface declines and results in concen-
tration gradients that have a bearing on the development of the
colony. In general, biofilm growth is more significant under
aerobic conditions but can be self-limiting due to the more sig-
nificant concentration gradients that develop. Increased aero-
bic biofilm thickness prevents oxygen penetration through the
biofilm, and anaerobic growth closer to the soil surface can
result in biofilm shearing. The thickness of the biofilm under
anaerobic conditions is significantly smaller due to the afore-
mentioned shearing effects and the fact that the rate of biomass
growth is substantially lower under anaerobic conditions.
The introduction of nutrients and substrates as part of any
biological treatment remedy is intended to enhance the target
microbial activity and will therefore promote the proliferation
of the native microbial consortia. As a result, biofouling chal-
lenges related to biological growth and subsurface geochemi-
cal modification should be expected as part of any biological
treatment strategy (Figure 6.29a through d). Biofouling chal-
lenges can be generally bucketed in three primary categories:
(1) biofilm growth and expansion, (2) metal precipitation reac-
tions, and (3) microbial gas generation. Biofilm development
can temporarily or permanently reduce injection or extrac-
tion well performance, can reduce the effective pipe diameter
for above-grade infrastructure, and can reduce aquifer soil
matrix conductivity and permeability. Similarly, labile metals
(e.g., Fe2+, Mn2+) released from native soils under reducing
conditions will precipitate on well and piping infrastructure
when brought in contact with oxygen or will form precipitates
in the subsurface during target or secondary treatment reac-
tions, which can also influence soil permeability.
Gas generation can be a significant challenge in organic
carbon delivery programs, where CO2 released during fermen-
tation consumes large portions of the available soil porosity
and limits fluid delivery. Gas buildup within a soil formation
has a marked influence on permeability reduction and can be
determined based on the Kozeny–Carman equation shown in
the following:
3 2
é n - Dn ù é 1 - n0 + Dn ù
K = K0 ê 0 ú ê 1- n ú (6.33)
ë n0 û ë 0 û
where
K0 is the initial hydraulic conductivity
K is the final hydraulic conductivity
n 0 is the initial porosity
∆ is the relative change (decrease) in porosity
Injected Reagent–Based Remedies 211

(a) (b)

(c) (d)

FIGURE 6.29  (a–d) Various forms of biofouling encountered during in situ biological treatment strategies.

The relationship between reductions in permeability and
porosity using this equation is shown in Figure 6.30. It should
be noted that this formula generally oversimplifies the aquifer
conditions,36 but it does demonstrate that minor declines in
the available porosity can have a significant bearing on the
associated hydraulic conductivity.
The biofouling categories identified earlier are relevant for
both aerobic and anaerobic treatment systems. Oxygen deliv-
ery applications leverage aerobic communities that readily
100
90
Permeability reduction (%)
proliferate and generate both more biomass and more exten-
sive biofilms as compared to anaerobic microorganisms. But
comparatively, anaerobic systems often utilize large volumes
of organic carbon that must be delivered via piping and well
infrastructure. In the case of carbon delivery injection wells,
robust and focused biological growth will occur around the
injection points and contributes to the deterioration in well
performance over extended injection programs. To enable
effective management of biofouling challenges associated
with all of these mechanisms, system design specifications,
routine rehabilitation, and substrate dosing strategies should
all be considered prior to remedy deployment and then adap-

80 tively managed based on field observations during operation.

70 Examples of each of these considerations are highlighted
60
as part of Table 6.5. While these challenges are a necessary
50
evil for biological treatment strategies, system downtime and
40
30 operational and maintenance challenges can be minimized by
20 adequate planning and proactive management.
10
0
0 10 20 30 40 50 60 70 80 90 100 6.2.2 Aerobic Processes
Porosity reduction (%)
Given the ubiquitous nature of aerobic microorganisms, the
FIGURE 6.30  Relationship between porosity reduction and per- widespread use of gasoline, and the susceptibility of petro-
meability reduction as defined by the Kozeny–Carman equation. leum compounds to biodegradation, it is not surprising that
212 Remediation Engineering

TABLE 6.5
Primary Biofouling Mechanisms and Associated Design and Operational Management Strategies
Mechanism Associated Challenges
Biofilm growth • Reductions in aquifer hydraulic
and conductivity
agglomeration • Decreased injection/extraction
well performance (well screen
fouling)
• Agglomeration within and
clogging of system conveyance
infrastructure and treatment
train
Precipitate • Oxidation of reduced metals and
formation precipitation of target metal
contaminants
• Reductions in aquifer hydraulic
conductivity
• Scaling in above-grade
conveyance infrastructure or
treatment train
• Reductions in injection/
extraction well performance
Biogenic gas • The generation of supersaturated
generation carbon dioxide concentrations
results in gas bubble occupation
of pore space and reduces soil
permeability
• Significant pressure buildup
within injection wells between
delivery events
• Sustained reductions in
injectability and well
performance
Design Considerations
• Install wells with sufficient access and
size to accommodate redevelopment
tooling
• Select well and system materials
compatible with chemical treatments to
prevent/eliminate fouling
• Limit oxygen infiltration in all system
components (wells, above-grade
treatment train)—particularly for reduced
groundwater systems
• Minimize residence time of substrates or
treatment fluids in piping infrastructure
• Limiting oxygen infiltration in all system
components (wells, above-grade
treatment train) is the most important
provision for limiting long-term
inorganic precipitation within system
components
• Install wells that fully penetrate the
groundwater table to eliminate oxygen
entry into wells (and extracted fluids)
• Install wells with sufficient access and
size to accommodate redevelopment
tooling
• Select well and system materials
compatible with chemical treatments
used for inorganic rehabilitation
• Install wellhead pressure relief valves on
injection wells to evacuate fermentation
gases during access
• Adopt clean water injection practices
following reagent addition to push
fermentable substrates from the well
column into the soil formation
Operational Considerations
• Adoption of routine maintenance
activities to preempt biofouling
concerns—flushing reagents from wells
and conveyance infrastructure following
delivery, routine housekeeping, and
cleaning
• Completion of periodic rehabilitation
techniques to restore performance
• Routine physical well redevelopment
techniques (surge block, jetting, air lift)
• Well cleaning agents (acids, peroxide,
biocides, chlorine)
• Utilization of acids with minimal health
and safety concerns (phosphoric acid,
hydroxyacetic acid, citric acid) to
solubilize iron precipitates for removal
• Use of metal chelating agents for
recirculation programs to prevent
precipitation of reduced metals in
above-grade infrastructure
• For organic carbon delivery programs,
reduce dosing concentrations to limit
fermentation gas accumulation
• Use groundwater surging techniques to
evacuate accumulating soil gas
• Perform upward pH titration of
injection solution to limit robust
short-term fermentation during injection
• Adopt pulsed carbon delivery programs
(carbon dosing with clean water cycles)
to alleviate localized gas generation

the foundation of bioremediation was laid with petroleum
cleanup. Aerobic bioremediation was first developed in the
early 1970s in response to observations made after marine
petroleum spills.37 Subsequent studies demonstrated that
organisms capable of degrading petroleum materials could be
further enhanced by adding oxygen, nitrogen, and phosphate,38
and the concepts for in situ remediation were conceived.
Petroleum contaminants, like several other contami-
nants, can serve as carbon substrate and/or an electron donor
(e.g., PHCs), and nearly all are biodegradable under aerobic
conditions.39 Aerobic biodegradation is also applicable for
contaminants susceptible to cometabolic degradation (chlori-
nated ethenes), and in general the stimulation of aerobic bio-
degradation can be a robust and rapid remedial strategy. As
discussed previously, oxygen is the most thermodynamically
favorable electron acceptor for microbial degradation and
organisms capable of aerobically degrading contaminants
do so through the production of dioxygenase or monooxy-
genase enzymes that are responsible for transforming these
compounds into food sources such as phenols, alcohols, or
epoxides. The intent of aerobic bioremediation is therefore
to provide a sustained source of oxygen to maintain aerobic
conditions in the aquifer. In many cases, there will be a lag
time associated with establishing sustained oxygen concen-
trations as compounds that can serve as an electron donor will
have consumed available dissolved oxygen and can also be
degraded under anaerobic conditions. If sufficient time has
elapsed from the time of release, utilization of these contami-
nants can foster development of moderately (iron-reducing to
sulfate-reducing) to very reducing (methanogenic) conditions.
Injected Reagent–Based Remedies 213

In addition to the organic oxygen demand, reduced metals lib- Methane oxidation
erated during these reduction processes will consume deliv- H H O
MMO H
ered oxygen and will require a sustained period of operation H C H H C O H C O H C O H CO2
H
to transition the system back to aerobic conditions in order to H H
2H
2H, O2 2H
capitalize on the rapid biodegradation processes.
The key considerations for successful implementation of TCE epoxidation (cometabolic oxidation)
aerobic biodegradation include (1) the susceptibility of the Cl Cl MMO Cl O Cl
–
contaminant to aerobic biodegradation, (2) the presence or C C C C ? CO2, Cl , H2O
Cl Cl Cl H
absence of NAPL, and (3) the current status of the oxidation–
2H, O2
reduction potential of the aquifer (geochemistry). Aerobic (a)
organisms capable of degrading petroleum and other con-
CH3
taminant compounds are generally ubiquitous and are present
H3C O C CH3
at the vast majority of sites, so the primary goal for overall
success entails efficient, sustained delivery of oxygen delivery CH3
to the subsurface. Methyl-tert-butyl ether
(b)
6.2.2.1  Contaminant Types
In addition to the PHCs discussed earlier, other compounds FIGURE 6.31  (a) Cometabolic oxidation of TCE. (b) Methyl tert-
that are more conducive for aerobic biodegradation are non- butyl ether.
chlorinated phenolic compounds, alcohols, ketones, carbox-
ylic acids, amides, amines, esters, aldehydes, and aliphatic of MTBE, as the effective half saturation constant (Ks) for
and aromatic hydrocarbons with a single chlorine atom or oxygen during MTBE degradation is significantly higher
two chlorine atoms. Among the chlorinated compounds, than general oxidative respiration.40 In addition, inhibition of
chlorobenzene, methylene chloride (MC), chloromethane, MTBE degradation has been reported at oxygen concentra-
chloroethane, and vinyl chloride are among the commonly tions less than 1 mg/L.41
encountered contaminants that are biodegradable faster under
aerobic conditions. 6.2.2.2 Microorganisms
The most significant biological mechanism for the aerobic There are a wide array of microbial species capable of degrad-
degradation of chlorinated solvents is when they are used as ing organic compounds in the presence of oxygen. While the
a primary substrate (electron donor). In these direct oxidation known species can be grouped into a range of different micro-
reactions, the chlorinated compound acts as an electron donor bial genera (Table 6.6), this list is abbreviated based on our
and the microorganism uses molecular oxygen as an electron limited capability to culture and catalog only select organisms
acceptor. The microorganism obtains energy and organic in a laboratory. Most species do not have the enzymatic capac-
carbon from the degraded chlorinated compound. The more ity to completely oxidize all or even most contaminants in the
chlorinated compounds, PCE, carbon tetrachloride (CT), and subsurface20 and as described previously behave instead as a
hexachloroethane (HCA), due to their highly oxidized char- broad cooperative consortium that metabolizes contaminants
acter, are neither susceptible to aerobic oxidation nor are they as a collective. This behavior is well suited to the degradation
degraded under anaerobic oxidizing conditions when used as of petroleum contamination, as these materials contain a vari-
a primary substrate. TCE undergoes very slow aerobic deg- able range of straight-chain, cyclic, or aromatic hydrocarbons
radation to trichloroethanol and then to acetic acid, but the that must be collectively consumed. This is advantageous
reaction is not thermodynamically favorable. The tendency from a treatment design standpoint, as broad enrichment of
of chloroethene compounds to undergo oxidation increases subsurface oxygen concentrations will promote the activity of
with decreasing number of chlorine substituents. Therefore, a wide range of organisms that contribute to cleanup.
discussion of aerobic oxidation and mineralization has always While no species serves as a universal hydrocarbon
been focused on DCE and VC. degrader, some are pretty proficient. Pseudomonads are aero-
The capacity to degrade methyl tert-butyl ether (MTBE) bic gram-negative species that never exhibit fermentation
(Figure 6.31) is also found in a wide variety of microorgan- reactions, are ubiquitous to most soil systems, and exhibit
isms. Some organisms can use MTBE as their sole substrate the strongest degradation potential.20 Several Pseudomonas
for growth, and others need another substrate for cometab- strains have demonstrated the capacity to metabolize over
olism. The prospects for aerobic biodegradation by native 100 different types of organic compounds.20 Other organisms
microorganisms may be related to the age of the spill and are uniquely qualified to degrade organic pollutants, such as
the time that has been available for acclimation of the native the Rhodococcus genus (aerobic actinomycetes) that contain
microorganisms to MTBE. Under aerobic conditions, MTBE long-chain mycolic fatty acids as part of the cell wall that act
is mineralized directly to CO2. MTBE-degrading organisms as biosurfactants and increase their overall affinity for lipo-
require higher concentrations of oxygen than the usual aerobic philic nutrients20,42—like petroleum compounds. As described
bacteria. Maintaining adequate concentrations of oxygen is in Section 6.1.6, these surfactants act as emulsifying agents
an important design concentration for aerobic biodegradation for NAPL materials and increase contaminant solubilization.
214 Remediation Engineering

Some Rhodococcus species and others belonging to the

TABLE 6.6 Arthrobacter and Mycobacterium genera are known hydro-
Some Isolated Bacterial Genera with One or More carbon degraders that can also metabolize MTBE and tert-
Species Capable of Degrading Aromatic Compounds butyl alcohol (TBA) as a primary growth substrate.43
An individual organism’s unique genetic makeup affects
Gram-Negative Bacteria Gram-Positive Bacteria
how and which organic compounds they metabolize. Organic
Achromobacter Arthrobacter compounds are used as the sole substrate for both carbon
Acinetobacter Bacillus
and energy, during which the contaminant is mineralized.
Acidovorax Brevibacterium
This process can also occur cometabolically, during which
Alcaligenes Corynebacterium
an alternative growth substrate is used, but the organic com-
Burkholderia Janibacter
pound is metabolized in the presence of exuded microbial
Chryseobacterium Mycobacterium
enzymes. Petroleum materials contain a broad range of aro-
Cycloclasticus Nocardioides
Cytophaga Staphylococcus
matics, straight chain, and cyclic alkanes that are susceptible
Flavobacterium Terrabacter
to different enzymatic pathways. For n-alkanes, oxidation
Marinobacter is typically initiated on either end of the carbon chain to
Pasteurella form an alcohol (Figure 6.32), aldehyde, or fatty acid, which
Polaromonas then proceeds through β-oxidation to yield acetyl-CoA or
Pseudomonas propionyl-CoA, depending on the number of carbon atoms.
Ralstonia Cyclic alkanes, while relatively resistant to degradation, are
Rhodanobacter degraded cometabolically by the broad aerobic consortium,
Rhodococcus and several species have been identified that metabolize these
Stenotrophomonas compounds.20
Sphingomonas Aromatic organic compounds are of particular relevance
Xanthomonas as the BTEX constituents present in gasoline are widespread
in contaminated retail service stations and fuel terminals
Sources: Fritsche, W. and Hofrichter, M., Aerobic degradation by microor-
and in the case of benzene have very low regulatory cleanup
ganisms, in Biotechnology: Environmental Processes II, Volume
11b, Section Edition; Seo, J.S. et  al., Int. J. Environ. Res. Publ.
criteria (1 µg/L in New Jersey). Aromatics can be degraded
Health, 6, 278, 2009. by both monooxygenase and dioxygenase (Figure 6.32), with
dioxygenase interactions being most prevalent. Oxidation of
the aromatic ring occurs via hydroxylation in the presence of

Monooxygenase reactions
O2 H2O

CH3 - (CH2)n - CH3 CH3 - (CH2)n - CH3OH

n-Alkane Primary alcohol

Rubredoxin Rubredoxin
Fe2+ Fe3+

NADH NAD+

O2 H2O H H2O OH
H
O OH
H
H OH OH
NADH NAD+ NAD+ NADH
Benzene Arene oxide trans-Dihydrodiol Catechol
(a)
Dioxygenase reaction
O2 H OH
OH
OH
H OH
NADH NAD+ NAD+ NADH
Benzene cis-Dihydrodiol Catechol
(b)

FIGURE 6.32  (a) Initial oxygenase and (b) dioxygenase enzymatic pathways for hydrocarbon transformation into associated alcohols.
(Adapted from Seo, J.S. et al., Int. J. Environ. Res. Publi.Health, 6, 278, 2009.)
Injected Reagent–Based Remedies 215

CH3
NH2
OH

Toluene
Phenol Aniline

Benzene Phenanthrene
OH
OH

Catechol

COOH

OH
OH
Protocatechuate

COOH
COOH

COOH COOH
COOH
Benzoate (CH2)n-CH3
Phthalate

NO2
OH m-Nitrobenzoate
p-Hydroxy-
benzoate OH
Alkylphenol

FIGURE 6.33  Primary catechol and protocatechuate degradation intermediates of a variety of different aromatic hydrocarbons. (Adapted
from Seo, J.S. et al., Int. J. Environ. Res. Publ. Health, 6, 278, 2009.)

a dioxygenase that is then transformed to catechol via a dehy-
drogenase. As shown in Figure 6.33, this two-step pathway
is common for a variety of one-ring aromatic compounds of
variable substitution. Similar mechanisms are observed for
multiringed PAH compounds, wherein dioxygenase attack on
one of the aromatic rings yields a diol prior to a sequence
of dehydrogenation steps to yield salicylate. As shown for
naphthalene in Figure 6.34, salicylate is then decarboxylated
to form catechol prior to ring fission via meta- and ortho-
pathways.44 While larger PAH compounds (fluorene, phen-
anthrene, pyrene, etc.) proceed through unique metabolic
intermediates depending on the number of aromatic rings
and their relative substitution, the dioxygenase and dehydro-
genase enzymatic series highlighted earlier for both benzene
and naphthalene are consistent for a wide range of petroleum
compounds.20,44
Chlorinated aliphatic compounds with one or two carbons
per molecule can be transformed under aerobic conditions by
three types of microbial enzymes45,46: dehalogenases, hydro-
lytic dehalogenases, and oxygenases. Dehalogenases, which
require reduced glutathione as a cofactor, dehalogenate the
substrates by means of nucleophilic substitution. The first
product of this degradation pathway is an S-chloroalkyl-
glutathione, which is probably nonenzymatically converted
to glutathione and an aldehyde. Hydrolytic dehalogenases
hydrolyze their substrates, yielding alcohols. Oxygenases use
molecular oxygen as a reactant for the attack on the haloge-
nated compounds; the products could be alcohols, aldehydes,
or epoxides, depending on the structure of the compound.
Numerous chlorinated short-chain aliphatic hydrocar-
bons have been demonstrated to undergo aerobic transfor-
mation. Compounds that have all the available valences on
their carbon atoms substituted by chlorine, such as PCE or
CT, have never been shown to transform through any other
but reductive pathways. Generally, as the degree of chlori-
nation increases, the likelihood of aerobic transformation
decreases (Figure 6.35); the opposite is true for anaerobic
(reductive) transformations. Rates of aerobic oxidation are
more rapid for the less chlorinated organics, such as VC,
when compared to their reductive dechlorination rates; it
216 Remediation Engineering

Naphthalene

H OH
OH
cis-1,2-Dihydroxy-
H
1,2-dihydronaphthalene

OH
O
O OH
1,2-Dihydroxynaphthalene

1,2-Naphthoquinone

O O O COOH
2-Hydroxy-2H-chromene-
OH 2-carboxylic acid

Coumarin

OH
cis-o-Hydroxybenzalpyruvate
COOH

OH
2-Hydroxybenzaldehyde
CHO

OH OH OH
Catechol Gentisate
OH COOH HO COOH
Salicylate

Ring fission Further degradation

Acetaldehyde Succinate
+ +
Pyruvate Acetyl CoA

FIGURE 6.34  Proposed catabolic pathway for naphthalene degradation. (Adapted from Seo, J.S. et al., Int. J. Environ. Res. Publ. Health,
6, 278, 2009.)

has been well documented in the literature that VC is oxi-
dized directly to carbon dioxide and water.46 Aerobic oxi-
dation of cis-DCE has been proven, with some discrepancy
as to whether cis-DCE reduction occurs to VC and is then
followed by direct oxidation of VC to carbon dioxide, or
whether direct oxidation of cis-DCE occurred to produce
carbon dioxide. Other reports suggest that cis-DCE can be
degraded with cis-DCE acting as the primary substrate in
aerobic microbial reactions.
Among the methane compounds, MC and chlorometh-
ane have been found to be amenable to aerobic microbial
transformation. Pure cultures of the genera Pseudomonas
and Hyphomicrobium have been isolated, which can
grow on MC as the sole carbon and energy source.45–47
Alkylhalides (haloalkanes), such as 1,2-dichloroethane
(1,2-DCA), are frequently hydrolytically dehalogenated.
Xanthobacter autotrophicus utilizes 1,2-DCA as the sole
carbon source. Complex communities consisting of meth-
anotrophs and heterotrophs, which inhabit groundwater
aquifers, mineralize 1,2-DCA. A Pseudomonas fluorescens
strain isolated from water and soil contaminated by chlo-
rinated aliphatic hydrocarbons was shown to utilize 1,2-
DCA, 1,1,2-trichloroethane (1,2,1-TCA), and TCE, but not
PCE or 1,1,1-TCA.45–47
Injected Reagent–Based Remedies 217

and delivery infrastructure, the total cost of a pound of dis-

solved O2 delivered into the subsurface could range from
Re $33 to $488 depending on the method selected. The cheapest
re duc e
tiv s
method of delivering dissolved O2, if hydrogeologic condi-
ac t
tio i v e da tions are conducive, is by injecting compressed air into the
ns xi tion
O ac
re contaminated plume. Other options include induced airflow
through the vadose zone to enhance oxygen transfer through
areas of petroleum impact, via direct injection of dilute hydro-
Reactivity

gen peroxide or oxygen-enriched water into the contaminated

zone, or by emplacing solid or slurried oxygen-releasing
materials (ORMs) via fracture-based injection strategies.
Ultimately, site-specific parameters are going to control what
form of O2 delivery is most appropriate, as permanent deliv-
ery ­systems—while inexpensive to operate—are not always
deployable at a given location.

6.2.2.3.1 Biosparging
Poly Mono Originally developed in Europe, air sparging is a conventional
Degree of chlorination
means of engineered in  situ bioremediation via aerobic bio-
degradation. Injection of either compressed air or pure oxy-
FIGURE 6.35  Relative trends of oxidative versus reductive micro-
bial reactions as a function of chlorination. (Adapted from Loeffler,
gen directly into the contaminated zone is an efficient way to
F.E. et al., Diversity of dechlorinating bacteria, in Dechlorination: deliver oxygen to achieve the target reactions and can also be
Microbial Processes and Environmental Applications, M.M. used to strip volatile contaminants from the saturated zone. The
Haggblom and I.D. Bossert, Eds., Kluwer Academic Publishers, primary difference between biosparging and air sparging (see
Boston, MA, 2003.) Chapter 8) is the overall delivery rate of air to groundwater.
The purpose of a biosparge system is to deliver sustained, ele-
6.2.2.3  Oxygen Delivery Mechanisms vated concentrations of oxygen to the groundwater for use as an
The primary design challenge of any aerobic treatment remedy electron acceptor while minimizing volatilization of the con-
is determining the most technically effective and economical taminants. This is typically achieved by injecting compressed
method by which to deliver oxygen to the contaminants. Due oxygen or air to the groundwater at low pressure and low flow
to oxygen’s low solubility (approximately 9 mg/L at 20°C) and (typically 0.5–4 standard cubic feet per minute (SCFM)).
rapid rate of utilization by a variety of different microorgan- Biosparge systems are typically used to treat shallow,
isms, delivery applications require either automated delivery dissolved-phase groundwater impacts but can be applied to
systems or solid-phase materials to provide a sustained oxy- address deeper impacts or shallow LNAPL impacts. In order
gen supply while degradation is ongoing. To illustrate this, the for biosparging to be successfully implemented, the aquifer
amount of oxygen required for complete aerobic mineraliza- must be permeable enough to inject oxygen or air at pressures
tion of 1 g of hydrocarbon ranges from 3 to 3.5 g. In simple low enough to avoid damage to the soil formation and to sus-
volumetric terms, 300,000 kg of oxygen-saturated water must tain flow rates sufficient to maintain aerobic conditions. In
be delivered and mixed in order to ­mineralize 1 kg of PHCs. addition, permeable soil matrices allow greater oxygen dis-
As shown in Table 6.7, accounting for standard equipment tribution from the sparge wells and limit channeling effects
that can be observed in heterogeneous or less permeable
soil strata. The sparging of gases in aquifers with horizontal
TABLE 6.7 stratification or low-permeability strata below the water table
Comparative Costs for Oxygen Delivery may also result in the uncontrolled lateral migration of sparge
gases that can limit distribution within the target treatment
Cost to Deliver 5,000 Pounds
interval or potentially mobilize volatile constituents beyond
Technology of Dissolved Oxygena
the treatment zone. Therefore, biosparging should be care-
Air sparging $164,000 fully evaluated for aquifers with horizontal stratification or
Oxygenated water injection $173,000 confining units below the water table.
Oxygen diffusion $368,000 In a biosparge system, pure oxygen or atmospheric air is
Dilute peroxide injection $1,071,000 injected into the subsurface through sparge wells screened
Electrolytic oxygen generation $1,140,000
within the saturated zone (Figure 6.36). The rate of oxygen
Pure oxygen sparging $1,436,000
transfer into the bulk water is a diffusion-limited process,
Oxygen-releasing materials $2,438,000
and oxygen transfer occurs as the compressed oxygen or air
a Based on standard aboveground equipment and conveyance infrastructure, injected within the saturated soil matrix migrates upward
standardized for a defined area. and partitions into groundwater based on the Henry’s law
constant, vapor pressure, and groundwater temperature
218
Air
compressor
Low airflow
rates
FIGURE 6.36  Conceptual design of a biosparging system.
Stagnant
water zone Diffusion
zone
el
nn
ha
rc
Ai
FIGURE 6.37  Representation of upward oxygen transport from a
biosparge well. Air channels develop during periods of supplied air
and bubble transport through porous media. Dissolved oxygen from
the air channel dissolves into surrounding groundwater (diffusion
zone) for consumption by native microbial consortia. Outside of air
channels and associated diffusion zones, dissolved oxygen concen-
trations are depleted.
(Figure  6.37). The diffusion path lengths for transport of
oxygen through groundwater are defined by the distances
between air channels. Where channel spacing is large, diffu-
sion alone is not sufficient to transport adequate oxygen into
all areas of the aquifer. To overcome these limitations, many
biosparge systems are cycled on a consistent basis to induce
mixing between oxygen-rich air channels and the oxygen-
poor groundwater to enhance oxygen distribution and the rate
of oxygen transfer.
Biosparge well networks can exhibit a variety of con-
figurations, with grid-style networks applied for source area
application or as barrier systems to eliminate degradable
Remediation Engineering
contaminants migrating with advective groundwater flow.
For  shallow groundwater systems, the radial influence from
a given sparge point has conventionally been assumed to be
a maximum of one foot horizontal for each one foot of depth
below the water table, but the achievable radial distribution
declines with increased overall soil permeability as air has
greater ability to migrate vertically toward the groundwater
surface. Accordingly, radial distributions equivalent to 30%–
40% of the saturated depth interval are more conservative for
design purposes. As discussed in more detail in Chapter  8,
pilot testing can be completed to confirm the oxygen mass
transfer efficiency using an inert tracer gas or by monitor-
ing oxygen concentrations at monitoring wells within the
expected sparge radius.
Whether a focused or barrier-based well network, suffi-
cient oxygen must be delivered to groundwater to overcome
the reduced groundwater geochemistry and enable complete
transformation of the target compounds. A conceptual repre-
sentation of soil oxygen measurements as a function of oxy-
gen utilization within the saturated zone over the course of
a biosparge system operation is provided in Figure 6.38. In
this example, observed oxygen within the vadose zone is not
detectable until labile soil minerals and reduced inorganic
species have been converted to their oxidized form. Once
achieved, soil oxygen partial pressures increase over time
depending on both delivery and microbial utilization. As
shown in this example, several periods of sparge shutdown
are plotted to demonstrate the decline in oxygen attributed
to microbial consumption. While DO measurements can be
obtained within the saturated zone, vadose zone gas measure-
ments allow broad assessment of dynamics within the under-
lying treatment zone.
As part of the design process, the air delivery rate, oxy-
gen transfer efficiency, site-specific groundwater velocity, and
total oxygen demand are all used to determine the placement
of delivery wells required to achieve sufficient residence time
in order to achieve treatment objectives. This process is com-
pleted by balancing two primary variables: (1) the length of
time for oxygen supply to meet the demand and (2) the resi-
dence time of groundwater within the sparge area. The total
mass of oxygen required to achieve the treatment demand
(mO2) is determined based on the stoichiometric ratio of oxy-
gen to the estimated mass of the target contaminant (e.g., 3.1
pounds of oxygen per pound of benzene) within the sparge
area as shown in Equation 6.34:
moles of oxygen
mO2 = p ´ rsparge
2
´ h ´ C0 ´ (6.34)
moles of contaminant
where
rsparge represents the radial distribution of oxygen from a
sparge well
h represents the height of the water column above the
sparge depth
C0 represents the maximum contaminant concentrations to
be treated
Injected Reagent–Based Remedies
0.20
Soil oxygen partial pressure, pO2
0.15
0.10
0.05
0
1
Fe2+
Mn2+
NO2–
SO3
2–
H2S
Air inject
FIGURE 6.38  Observed soil oxygen partial pressures over various cycles of biosparge operation. (1) Biosparge initiation where oxidation
of reduced geochemical species occurs. (2) Observed oxygen consumption during periods of sparge shutdown. (3) Relative differences in
oxygen utilization as a result of microbial community growth.
If known, a measurement of the biological oxygen demand
can also be used in lieu of (or in conjunction with) the con-
taminant concentration.
The total duration of time necessary to achieve the above
oxygen demand is then obtained by solving for the following
where Qsparge is the sparge flow rate (in SCFM), COg 2 is the
oxygen concentration per unit volume of sparge gas (mg/ft3), η
is the overall oxygen mass transfer efficiency to groundwater,
and tcycle is the sparge operational time (in hours or days):
ttreatment =
( )
Qsparge ´ COg 2 ´ h ´ tcycle
In this equation, mass transfer efficiencies for sparge systems
range from a maximum of 1% to a more typical 0.1 to 0.01%.
Once the minimum duration required to achieve oxy-
gen delivery has been determined using Equation 6.35, this
value is used to determine the required sparge well network
to achieve the necessary residence time. The total residence
time within the sparge area is determined by dividing the total
travel length of groundwater migrating through the sparge
area (lsparge) by the groundwater velocity (vgw) as presented in
Equation 6.36:
tresidence =
Within the biosparge area, groundwater must have enough
residence time to receive the necessary mass of oxygen for
219
pO2 = 0.20 atm
3
2
pO2 = 0.00 atm
Fe3+
MnO2
NO3– Lag-time in free O2 due to oxidation of reactive, reduced ions
SO42–
S(s)
Air inject Air inject
Off Off Off
treatment, so values of tresidence must be equal to or greater than
that of ttreatment. Therefore, a review of the outputs of Equations
6.35 and 6.36 allows for an iterative design assessment, and
modifications can be made to the cycle times (more or less
oxygen delivered), the sparge point depth (affecting radial dis-
tribution), or the well network (by adding additional wells) to
accommodate the design needs.
6.2.2.3.2  Aqueous Oxygen Delivery
While successful oxygen delivery has been achieved using
mO2
(6.35) sparged air applications for several decades, changes in the
way we view hydrogeology, contaminant transport, and mass
flux have enabled innovation around this conventional treat-
ment remedy. As discussed in Chapter 5, the observed benefits
of recirculation techniques have allowed development of inte-
grated strategies that leverage enhanced aquifer pore volume
exchange with supplemental in situ treatment. Similar to bio-
sparge applications, aqueous oxygen delivery techniques rely
on delivering a sufficient amount of oxygen to promote con-
taminant degradation to the treatment objectives. Oxygenated
water injections, however, rely on achieving oxygen saturation
in water (up to 30–40 mg/L) above grade prior to injection.
When coupled as part of a continuous recirculation setup, the
combined treatment program includes groundwater extrac-
lsparge tion, ex situ treatment (preferably with an air stripper), water
(6.36)
vgw oxygenation, and directed reinjection into the subsurface.
Where aquifer permeability is sufficient, the combination of
these techniques can be an effective means of leveraging both
physical and biological treatment mechanisms.
220
The design of an oxygenated water recirculation system
is similar to that of a dynamic groundwater recirculation
(DGR) system, with design operational durations developed
based on the total aquifer pore volume and required number
of pore exchanges to physically sweep contaminants from
the treatment area. The addition of oxygen, however, pro-
vides an additional advantage by overcoming the geochemi-
cal demand and enhancing the overall rate of biodegradation.
In determining design time frames, a similar approach to
that detailed in Section 6.1.4.2 can be followed to account
for the necessary pore volume exchange, but these estimates
can be corrected for the equivalent contaminant mass that is
oxidized by the mass of oxygen delivered over the life-cycle
operation. Subsurface oxygen longevity is expected to change
over the course of operation, with more rapid oxygen utiliza-
tion observed at start-up as it is utilized to oxidize reduced
metals, but the overall longevity will increase as an aerobic
geochemical poise is reestablished. The system components
required to achieve oxygen delivery are usually staged in a
mobile trailer or within a small storage shed, with effluent
groundwater from the treatment vessel amended by an oxygen
generator in-line prior to recirculation.
A permanent recirculation setup is not a requirement for
aqueous oxygen delivery. In some instances, hydrogen perox-
ide (H2O2) is used as a dissolved source of oxygen. Peroxide
serves a dual purpose as both a short-term oxidant and a
means to achieve substantially greater dissolved oxygen con-
centrations than via air saturation. In most cases, dilute perox-
ide is injected according to pulse and drift strategies similar
to those described in Section 6.1.4.1.
The naturally reduced groundwater conditions at sites
with elevated contaminant concentrations (sites with residual
LNAPL or elevated sorbed concentrations) represent one of the
primary challenges for oxygenated water delivery programs.
The introduction of oxygen-enriched water directly into the
reduced groundwater system will result in rapid precipitation of
iron, manganese, and other labile metals, and the development
of aerobic biomass within the vicinity of the injection well can
also result in biofilm and biomass growth within the well annu-
lus, reducing performance. Upfront assessment of these param-
eters prior to implementation can help support troubleshooting
activities (well redevelopment) and can support extraction and
injection well designs to eliminate fouling. Nontoxic chelating
agents can also be amended to the injection stream during the
onset of treatment to also avoid these challenges.
Compared to biosparge applications, during which oxy-
gen migrates upward through the groundwater to the vadose
zone, oxygenated water recirculation strategies are viewed
primarily as a dissolved-phase treatment approach. Oxygen
concentrations are both injected and consumed in the aque-
ous phase, so injection and extraction well screens should be
placed to intersect the contaminant vertical distribution to
enable treatment. Where LNAPL exists or considerable smear
zone mass is present, which are not readily available in the
dissolved phase, alternative treatment options may be more
viable to address these impacts or in advance of implementing
a dissolved-phase program.
Remediation Engineering
6.2.2.3.3  Solid (Oxygen Release Compounds)
As a complement to either gaseous or aqueous-phase oxygen
delivery, solid-phase ORM represents an applicable means
to provide focused oxygen delivery and sustain dissolved
oxygen concentrations for an extended period of time (9 to
18  months). With a variety of formulations available, these
materials are generally composed of calcium and magnesium
oxides, peroxides, or hydroxides that are sparingly soluble in
water and provide an extended source of dissolved oxygen
when hydrated. Depending on the starting material, material
decomposition results in oxygen generation via a series of fol-
lowing mechanisms:
2CaO2 + 2H 2O ® 2Ca(OH)2 + O2 (g) (6.37)
2MgO2 + 2H 2O ® 2Mg(OH)2 + O2 (g) (6.38)
While these mechanisms represent the formulations that are
most wildly available, other materials containing calcium
oxyhydroxide (CaO(OH)2) and combinations of ORM and
persulfate are also available. Under mildly acidic to acidic
pH, the aforementioned decomposition reactions result in
increased ratios of peroxide to oxygen, which then serves as a
short-term oxidant and source of oxygen. The by-products of
the reaction (magnesium hydroxide, calcium hydroxide) also
provide moderation of pH within the treatment area but can
also result in significant pH excursions (above 11–12 S.U.) and
be detrimental to biodegradation when insufficient mixing is
achieved.
These materials have been regularly applied as polishing
techniques after open-hole excavations (e.g., underground
storage tank [UST] removal) and can be directly spread,
mixed, or evenly layered in soil backfill. Due to the solid
nature of the material, however, the primary design challenge
associated with in situ ORM use is selecting an appropriate
method for delivery. While the materials are produced as a
fine powder, the grain size is too large for injection via per-
manent wells and too large to migrate through the soil matrix.
Instead, these materials are delivered as a slurry via pressured
direct-push injection or hydraulic fracturing techniques to
establish enriched seams in which the ORM is emplaced and
can subsequently dissolve. As described in Section 6.1.2.2,
fracture intervals are selected across the vertical interval of
contaminant impact, and points are spaced in close proximity
to establish overlap and coverage between the delivery points.
While this is the preferred means to achieve delivery, the solid
nature of the ORM material, the rapid utilization of oxygen in
the subsurface, and the loosely or sparingly connected frac-
ture intervals can result in residual contaminant mass that is
left untreated between injection intervals. As a result, multiple
delivery events are typically required.
6.2.2.4  Nutrient Addition
Like any living organism, macronutrients serve as essential
building blocks of proteins, enzymes, and nucleic acids. While
the necessary organic and inorganic nutrients to sustain micro-
bial growth are generally present in groundwater systems, are
Injected Reagent–Based Remedies
recharged from the atmosphere, and are periodically recycled
via endogenous cellular decay processes, robust population
growth and development of cellular biomass in response to
oxygen delivery can lead to conditions in which nitrogen and
phosphorus macronutrients are limited. The conventional rule
of thumb for aerobic systems indicate that the ratio of C:N:P
should be approximately 100:5:1 for optimal aerobic cell
growth, and systems may require periodic dosing with select
macronutrients as part of the delivery schemes. Nutrient sup-
plements can come in a variety of different forms, but com-
monly used substrates include triethyl phosphate, which can be
delivered as a gas via biosparge wells, or diammonium phos-
phate, which can be dissolved and injected as an aqueous solu-
tion. Nutrient monitoring over the course of remedial operation
is often not a requirement, but upfront baseline sampling and
intermittent confirmation events can be useful in determining
whether concentrations are sufficient or warrant augmentation.
6.2.2.5 Monitoring
In addition to understanding contaminant distribution and
transport, biogeochemical characterization is a key element
in understanding site conditions prior to implementation of an
aerobic treatment program. There are numerous geochemi-
cal parameters to choose from, and each designer has their
own preferred analytes for use in evaluating conditions prior
to treatment and then tracking them once treatment is under-
way. Site characterization programs will provide information
pertaining to the vertical and spatial distribution of contami-
nant impacts and the specific soil stratigraphy in which mass
is retained. The utilization of high-resolution sampling tools
or LNAPL test kits also helps understand the overall distribu-
tion of mass and its relative accessibility to oxygen delivery
strategies. This information will also help bias monitoring
programs to focus on demonstrating remedial success within
areas requiring treatment. With this understanding, an appro-
priate suite of biogeochemical parameters can be incorporated
into the sampling program to assess the relative concentrations
of dissolved-phase electron acceptors (oxygen, nitrate, sulfate),
reduced metal species (iron, manganese), dissolved gases (car-
bon dioxide, methane), and other relevant geochemical species
(total organic carbon [TOC], Total Kjeldahl Nitrogen [TKN],
ORP, pH, etc.) to correlate the geochemical profiles with the
understanding of contaminant distribution. A summary of the
key baseline analytes and both primary and secondary perfor-
mance monitoring analytes is presented in Table 6.8.
As part of baseline sampling, selection of at least one or
two background monitoring locations for geochemical sam-
pling is recommended to allow comparison between the plume
source area, the plume fringes, and native groundwater con-
ditions. This information provides information regarding the
influence of contaminants on the developed redox conditions.
For PHC sites, it is very common to observe highly reduc-
ing conditions (sulfate reducing to methanogenic) within the
vicinity of the source coupled with gradational shifts toward
mildly anoxic or aerobic conditions along the length of the
plume (Figure 6.39). While these redox gradients are antici-
pated to vary based on the natural availability of electron
221
TABLE 6.8
Sample Monitoring Program for Oxygen-Based
Treatment Applications
Baseline Primary Secondary
Contaminant(s) Contaminant(s) CO2
BOD TKN
TOC TOC
Ferrous iron Sulfate
Manganese Ferrous iron
Sulfate Manganese
Methane Methane
Field parameters Field parameters Field parameters
Note: Field parameters include ORP, DO, pH, temperature, specific conduc-
tivity, and turbidity.
acceptors, understanding these shifts provides insight into the
rate of response to oxygen delivery and the potential duration
required to overcome the background geochemical demand.
While a full suite of geochemical parameters is useful and
often necessary to support design, it is expected that the pro-
cess and performance monitoring programs can be fine-tuned
as operation is initiated. Understanding that available oxygen
is going to serve as the primary electron acceptor and that
increased oxygen concentrations will be an indicator that the
background geochemical demand has been satisfied, opera-
tional programs can focus on tracking oxygen concentrations
as a benchmark indicator of overall progress—demonstrat-
ing both influence from delivery and serving as the primary
reactant for enhancing treatment. This is reflected in the ana-
lytes provided in Table 6.8, which reflects a highly focused
monitoring program on the key parameters that drive decision
making. The secondary analytes are all supporting param-
eters that can be woven into the performance monitoring
program as necessary for troubleshooting purposes or can be
sampled more sparingly over the course of the program as
secondary lines of evidence to document treatment.
6.2.3 Anaerobic Processes
The energy microbial species obtained from a given meta-
bolic process is directly tied to the difference in reduction
potential between the electron donor and electron acceptor
involved. As oxygen represents the strongest available oxi-
dant, its utilization in aerobic systems allows the release of
considerably more energy for utilization by the aerobic micro-
bial consortia. As described in the preceding sections, a wide
variety of organisms are adapted to utilize this robust energy
supply to spur rapid microbial growth rates and significant
generation of cellular biomass and to excrete extracellular
material. Comparatively, the reduction potential of alternative
electron acceptors in anaerobic systems yields less overall
energy to individual microbial species and has driven anaero-
bic and facultative organisms to become highly efficient in the
presence of reduced energetics. As discussed in the following
222
Aerobic
Nitrate reducing
Iron reducing (until Fe3+ depleted)
Sulfate reducing
Methanogenic
FIGURE 6.39  Anticipated geochemical signatures downgradient of a leaking fuel UST, assuming background conditions are aerobic.
sections, isolating individual species within anaerobic micro-
bial consortia is challenging due to their reliance on one
another and the necessity of syntrophic relationships to per-
form their primary metabolic functions. Many organisms are
facultative and will utilize the most energy-yielding electron
acceptors based on availability, while others are true anaer-
obes and are highly adapted to carry out day-to-day activities
in lean energy conditions.
6.2.3.1  Microbial Reduction
Microbial reduction takes place when the compound is used
as an electron acceptor (primary growth substrate) during
reductive reactions (Figure 6.23). Most interest in reductive
transformations of environmental contaminants involves
dechlorination of aliphatic and aromatic organic compounds
and the reduction of nitroaromatic compounds. Other exam-
ples of reductive transformations that may occur in the sub-
surface environment include the reduction of ethers, azo
compounds, disulfides, and sulfoxides.
Many of the metabolic steps in anaerobic respiration are
not the classic reduction–oxidation half-cell reactions in
which one compound (the electron donor) is oxidized and a
second compound (the electron acceptor) is reduced. In anaer-
obic systems, oxidation and reduction often occur simultane-
ously through the action of enzymes on a single compound, a
process known to chemists as disproportionation and to biolo-
gists as fermentation. The anaerobic metabolism that can be
sustained by fermentation and by oxidation–reduction reac-
tions that consume alternative electron acceptors yields much
less energy than oxidative metabolism. Under anaerobic con-
ditions, the oxidation of glucose yields only 2 moles of ATP
per mole of glucose, clearly not a competitive strategy when
oxygen is present (with a theoretical yield of 38 moles).
It is important to note that dissolved oxygen levels in the
aquifer decrease, and the concentration gradient through the
vadose zone increases in magnitude to support the additional
demand. Aerobic metabolism of simple sugars often used to
engineer reductive IRZs can be accomplished within a sin-
gle organism. The first metabolic phase is aerobic glycoly-
sis, producing pyruvate. The pyruvate then enters the citric
acid cycle, yielding carbon dioxide. The entire process yields
Remediation Engineering
Aerobic
Nitrate reducing
Iron reducing (until Fe3+ depleted)
Sulfate reducing
Solid Fe3+
precipitation
38  moles of ATP for every mole of glucose that enters the
aerobic glycolysis metabolic pathway.
Many phylogenetic classifications of bacteria participate
in the aerobic carbohydrate metabolism and the carbohydrate
fermentation that occurs in the upgradient portions of an
ERD zone. However, the portion of the reactive zone that car-
ries out reductive dechlorination is populated by only a few
metabolic classifications of bacteria. These groups behave
very differently from one another and include methanogens,
sulfate-reducing bacteria, and dehalorespiring bacteria.
6.2.3.1.1 Biogeochemistry
Aquifer microbial communities adapt quickly and predict-
ably to changes in the electron donor and acceptor loadings,
and this gives us an opportunity to engineer the continuum
to create an IRZ for the destruction of contaminants. When
highly degradable organic carbon is injected into the ground-
water flow, bacterial biomass increases and is sustained as
long as the loading continues. As presented in Figure 6.40, a
geochemical cascade is initiated and results in the preferen-
tial depletion of available electron acceptors in the order of
energetic benefit. When electron donor loadings are sufficient
to induce consumption of alternative electron acceptors, the
composition of the aquifer microbial community undergoes
a fundamental shift. Microbial consumption of dissolved
organic carbon (DOC) drives a succession of habitat changes
that lead to a continuum of decreasing redox potential and
the associated progressive shift of terminal electron accep-
tors. Reactions in the upper portion of the cascade consume
electron acceptors, leaving reactions in the lower parts of the
cascade to be supported by other, potentially less energy-
yielding, electron acceptors. The subsurface geochemical
transition shown in Figure 6.41 develops under high electron
donor loads, and the various anaerobic metabolic processes
are carried out by distinct groups of organisms (unlike aerobic
degradation, which can be completed with competitive energy
yields by a single organism).
These metabolic processes occur in several steps and, at
any point in the cascade, the most likely next reaction is deter-
mined by the concentration of donors and acceptors and the
energy that competing organisms can gain from the reaction.
Injected Reagent–Based Remedies
TOC
Concentration NO3– (when NH4+ was present)
NO3–
O2
O2 CO2 + H2O NO3–
Aerobic
oxidation
FIGURE 6.40  Sequential pathways of microbial oxidation reactions. (Schwarzenbach, R.P. et al.: Environmental Organic Chemistry,
2nd ed., Wiley Interscience, New York, 2003. Copyright Wiley-VCH Verlag GmbH & Co. KGaA. Reproduced with permission.)
Degradable carbon (electron donor) injection
0 100
Days travel in groundwater
FIGURE 6.41  Zonation of dominant metabolic processes in the
aquifer microbial continuum, when electron donor loading is sus-
tained at levels that exceed electron acceptor recharge.
The reaction that gains the most energy at any point in the
cascade is thought to be the most competitive, therefore most
likely to occur. For example, in Figure 6.42, hydrogenotro-
phic methanogens compete with lithotrophic sulfate reducers
for hydrogen as an electron donor (these organisms will also
require a source of carbon for growth). When hydrogen sup-
plies are limited, the sulfate reducers are expected to outcom-
pete the methanogens, because they gain more energy from
the oxidation of hydrogen (they use a more energetic electron
acceptor). It is important to note that when hydrogen is abun-
dant, sulfate reducers and methanogens can coexist—they
may compete for other resources, but the energy disadvantage
of CO2 as an electron acceptor is not a major factor.
6.2.3.1.2 Substrates
Numerous organic carbon substrates have been success-
fully applied to promote development of reductive IRZs.
223
S2–(Concentration pH
SO42– dependent)
CH4
N2 SO42 S2– CO2 CH4
Anaerobic oxidation
MnO2 Mn2+
Fe3+ Fe2+
These substrates include a variety of soluble (lactate, ethanol,
methanol, whey, molasses, corn syrup, glycerin), insoluble
(neat soybean oil, EVOs), and solid (chitin, mulch) carbon
sources. While each of these carbon compounds has unique
soluble carbon release profiles and is fermented through dif-
ferent intermediate carbon species, all are intended for the
same purpose: to provide a sustained source of dissolved
hydrogen. The following sections provide an overview of the
200 variety of fermentation pathways associated with the organic
electron donor utilization and the design nuances of how each
is generally applied.
Microbial ecology data from active reductive dechlorina-
tion communities indicate that dehalogenating bacteria make
up less than 1% of the total microbial biomass (Lee et  al.,
2004). If possible, engineered applications for chlorinated ali-
phatic treatment would allow focused electron donor delivery
to dehalogenators alone, but the complexity of the microbial
community that grows in response to carbon addition coupled
with the low percentage of dehalogenating bacteria makes the
wide-scale consumption of carbon substrate and associated
fermentation products by nontarget organisms unavoidable.
These other organisms mediate a variety of other oxidation–
reduction processes that are candidates for nondehalogenating
IRZs, several of which are discussed later in this chapter.
For injection programs reliant on the periodic or routine
delivery of organic carbon, microbial biomass will build up
over time and result in increased carbon consumption by the
aquifer microbial continuum. This consumption increase
is reflected in a decreasing overall half-life of DOC in the
aquifer, so theoretically the same dose of organic carbon
will be consumed faster (Figure 6.43). While this is some-
what intuitive from an empirical standpoint (more organisms
224 Remediation Engineering

Electron
donors

Mixed
complex
organic
materials
Hydrolysis
Organic
monomers

Fermentation
Alcohol
and
acids

Acetate and hydrogen

formation

Acetate H2
Oxidation

Sulfate Sulfide

Iron (III) Iron (II)

Electron
acceptors End
Carbon
dioxide Methane

PCE TCE CDCE VC Ethane

FIGURE 6.42  Steps in the process of biodegradation of chlorinated ethenes by reductive dechlorination. Biodegradable organic matter is
used to supply electron donor to initiate the process, with different microorganisms involved at each stage. As shown at the bottom, available
electron donor is used for a variety of metabolic functions, meaning that sufficient electron donor must be available to overcome background
electron acceptor demand for chlorinated ethenes to serve as electron acceptors. (Adapted from McCarty, P.E. and Semprini, L., Groundwater
treatment for chlorinated solvents, in Handbook of Bioremediation, R.D. Norris et al., Eds., Lewis Publishers, Boca Raton, FL, 1994.)

consume more electron donor), the graphic representation in

Pretreatment
Figure 6.43 fails to acknowledge one significant detail: that
Dissolved organic carbon half-life (days)

microbial biomass is recycled via endogenous decay to pro-

vide a sustained source of usable carbon material. So while
new carbon substrate injected into the subsurface will be
consumed faster over time, stockpiled biomass by the micro-
bial consortium—if injections are completed routinely—will
result in as-measured DOC half-lives that contradict Figure
6.43 and increase over the course of remedial operation. This
Microbial biomass is reflected conceptually in Figure 6.44 for a theoretical injec-
30 development Mature microbial
community tion program in which quarterly injections are completed over
20 a three-year period. Incremental carbon dosing (sucrose) over
this time period is correlated with the biomass derived from
sucrose addition, biomass loss due to decay, and the quan-
tity of recycled biomass based on an 80% degradable frac-
0 200 400 600
tion.48 The projected biomass buildup and its endogenous
Duration of increased loading (days)
recycling in this case may result in approximately four addi-
tional years of organic carbon availability following the last
FIGURE 6.43  Response of the microbial community to increased
dissolved organic carbon loading. In its pretreatment condition, dis- injection event. Thus, where multiyear injection programs are
solved organic carbon consumption is balanced by recharge and the completed, residual carbon concentrations may remain for an
apparent half-life is longer. When dissolved organic carbon loading extended time period to provide low levels of hydrogen and
is increased, microbial biomass increases and the half-life declines. support follow-on polishing to prevent rebound.49–52
Injected Reagent–Based Remedies
6000
5000
Estimated biomass (lb)
4000
3000
2000
1000
0 0
0 500 1000
Days
Projected biomas—injection phase
Injection events
FIGURE 6.44  Projected biomass growth and decay during theoretical injection and postinjection remediation phases. Injection mod-
eled with sucrose as electron donor and 3 years of quarterly injection. Biomass accumulation represents net difference between biomass
generated from sucrose and that generated from carbon liberated via endogenous cell decay minus inert carbon lost via microbial decay.
Assumed stoichiometric biomass production of 0.35 pounds per pound of sucrose using TCE as an electron acceptor, a first-order decay rate
of 0.015 day−1, and a biomass reducing potential of 20 mole reducing equivalent per mole of electron donor.
6.2.3.1.2.1  Fermentation Reactions  The production of
H2 by different microorganisms is intimately linked with their
respective energy metabolisms. The production of H2 is one of
the specific mechanisms to dispose excess electrons through
the activity of hydrogenase present in H2-producing microor-
ganisms.53,54 Production of H2 by obligate anaerobic micro-
organisms has optimum stoichiometry (1:4, with glucose as
substrate) compared with facultative anaerobes (1:2), although
the latter process is comparatively simpler than the former.53
Under natural conditions, fermentation is the process that
generates the hydrogen used in microbial reduction reactions.
In the absence of externally available electron acceptors, many
organisms perform internally balanced (different portions of
the same substrate are oxidized and reduced) oxidation–reduc-
tion reactions of organic compounds with the release of energy,
and this process is called fermentation. Since only partial oxi-
dation of the carbon atoms of the organic compound occurs,
fermentation yields substantially less energy per unit of sub-
strate compared to oxidation reactions. (Oxidation reactions
occur in those external electron acceptors that participate in
the reaction.) For instance, the fermentation of glucose to etha-
nol and CO2 has a theoretical energy yield of 257 kcal mol21,
enough to produce about 6 ATPs. However, only 2 ATPs are
produced, which implies that the organism operates at consid-
erably less than maximum efficiency.53
In any fermentation reaction, there must be a balance
between oxidation and reduction. In a number of fermenta-
tion reactions, electron balance is maintained by the produc-
tion of molecular hydrogen, H2. In H2 production, protons
(H+) of the medium, derived from water, serve as electron
acceptors. The energetics of hydrogen production are actually
somewhat unfavorable, so that most fermentative organisms
only produce a relatively small amount of hydrogen along
with other fermentation products. Fermentation reactions that
have pyruvate as an intermediate product have the potential of
225
35,000
3 years injection
3,0000
12 total injection events
Sucrose injected (lb)
32,000 lb sucrose 25,000
Biomass decay: 4.7 years
20,000
15,000
10,000
5,000
1500 2000 2500
Projected biomas—decay phase
Total sucrose injected
producing more H2. Conversion of pyruvate to acetyl-CoA is
an oxidation process, and the excess electrons generated must
either be used to make a more reduced end product or can be
used in the production of H2.
Fermentation by bacteria can also be important in control-
ling the biogeochemical environment of anaerobic aquifers.
Bacterial fermentation can be divided into two categories46,54:
Primary fermentation: The fermentation of primary
substrates such as sugars, amino acids, and lipids
proceeds through multiple intermediates en route
to generating acetate, formate, CO2, and H2. These
intermediates are frequently referred to broadly as
volatile fatty acids (VFAs) and include lactate, suc-
cinate, propionate, and butyrate. Depending on the
starting carbon molecule, this process can also yield
ethanol. While primary fermentation often yields H2
as part of these primary steps, the production of H2 is
not required for these reactions to occur.
Secondary fermentation or coupled fermentation: The
secondary fermentation of intermediates generated
during primary fermentation products yields acetate,
formate, H2, and CO2. Bacteria that carry out these
reactions are called obligate proton reducers because
the reactions must produce hydrogen in order to bal-
ance the oxidation of the carbon substrates. These
secondary fermentation reactions are energetically
favorable only if hydrogen concentrations are very
low (10 −2–10 −4 atm or 8000 to 80 nM dissolved hydro-
gen, depending on the fermentation substrate). Thus,
these fermentation reactions occur only when the pro-
duced hydrogen is utilized by other bacteria, such as
methanogens that convert H2 and CO2 into CH4 and
H2O. The process by which hydrogen is produced by
one strain of bacteria and utilized by another is called
226 Remediation Engineering

Monomers
(sugars, amino
acids)

Clostridium
species
Mixed acid Fermentative
Butanediol Fermentative
Organic acids Uptake fermentation species
fermentation species
Acetone– (see below)
butanol
fermentation

Oxidation H2 + CO2 Acetate Organic acids Acetate Organic acids

Butanol Acetone
H2- producing
Acetogens Acetogenesis Fermentative
Desulfobivrio fatty-acid oxidizing
Acetogens species
methylotrophs Fermentation bacteria (syntrophs)
Carboxylation
Methanogens
Butanediol
2-Butanone H2 + CO2 Acetate CO2 + H2 Ethanol H2 + CO2
+ CO2
Acetogens
Methanogenesis
Uptake (see left)
Methanogenesis
Uptake by: Methanogens Methanogenesis
Acetogens (shown) 2-Butanone
Dehalorespirers CH4
Lithotrophic bacteria
(reduction of e-acceptors)

FIGURE 6.45  Generalized subsurface primary and fermentation pathways for select microbial species following injection of an organic
carbon electron donor.

interspecies hydrogen transfer. It should be noted that

the terminal products of anaerobic decomposition, TABLE 6.9
CH4 and CO2, respectively, are the most reduced and Common Injectable Organic Electron Donors
the most oxidized carbon compounds.46,54 Moles of Reducing
Equivalents (e–) Average Cost
A generalized summary of the aforementioned fermenta- Chemical per Mole Electron per Pound of
tion processes is shown in Figure 6.45. This figure highlights Carbon Source Structure Donor Substrate ($)
the variety of mediating species and primary and secondary Dissolved hydrogen H2 2 —
pathways that are expected for a nondescript carbon substrate. Acetate CH3CO2− 8 0.75
The intermediate species will vary based on the molecular Corn syrup C6H12O6 24 0.35
structure of the starting monomer, and these will be reflected (glucose)
in the relative ratios of the individual VFAs observed. These Lactate C3H6O3− 12 1.20
pathways also provide an explanation for the periodic obser- Molasses (sucrose) C12H22O11 48 0.15
vation of several ketone compounds (acetone and 2-butanone) Ethanol C2H6O 12 0.15
in some active IRZs, which are generated as primary fermen- Soybean oil C18H32O2 313 1.50
tation byproducts and then subsequently consumed. (linoleic acid)
Biomass Variable 20 —

6.2.3.1.2.2  Substrate Selection Considerations  All com-

mercially available carbon substrates have some characteris-
tics that are similar, including some degree of degradability
and solubility. They differ in the speed with which the mate-
rial becomes bioavailable and is degraded, in the complexity of
their composition, and in their cost. A comparison of candidate
electron donor and carbon substrate products for field applica-
tion is provided in Table 6.9. The representative moles of reduc-
ing equivalents per donor is provided, which when divided by
half is equivalent to the moles of dissolved hydrogen generated
per mole of electron donor. These values can then be coupled
with available target electron acceptors to obtain the overall
energy released during metabolic reactions (see Figure 2.2055).
Table 6.9 also provides a cost comparison, which highlights the
relative price differences on a cost per pound of electron donor.
While cost is a factor for consideration as part of design, these
substrates can exhibit significantly different subsurface behav-
ior and injection design applications so cost per pound should
not be the sole criterion for substrate selection.
A substrate’s physical characteristics and molecular com-
position determine whether they serve to provide a slow, low
concentration release of soluble carbon or are immediately
available at higher concentrations. This carbon release profile
is critical from a design standpoint, as DOC must be sustained
at sufficient strength to support development of the necessary
reducing conditions and provide a surplus of dissolved hydro-
gen for the target microorganisms. While some carbon sub-
strates are similar, no two are the same and each will exhibit
a unique behavior based on site-specific conditions; therefore,
substrate selection should be given as much attention as other
Injected Reagent–Based Remedies 227

critical elements of site characterization and injection design injection infrastructure, increase operational efficiency, and
parameters. In most cases, a given substrate is identified as thereby limit life-cycle costs associated with system operation.
part of the design and then ongoing performance monitoring The application of IRZs for any plume treatment should be
is used as a feedback loop to modify carbon dosing and tim- considered from two different perspectives: (1) source zone
ing of injection events or to select alternative substrates that treatment and (2) treatment of the dissolved contaminant foot-
may be best suited for a given site. print. Mass reduction mechanisms differ in these treatment
The geochemical character of the matrix and groundwater areas based on the location of the IRZ (where the contaminant
and hydrologic conditions such as groundwater velocity influ- and electron donor are present) and the physical flushing zones
ence the efficacy and spatial extent of the created IRZ. In cases (where contaminant is present and electron donor is depleted). A
where extensive contaminant plumes are being treated, it is cost-effective approach involves placing injection barriers ori-
desirable that carbon supplements are consumed at a rate high ented perpendicular to groundwater flow along the length of the
enough to lower the redox conditions rapidly but low enough contaminant plume. The intent of this design is to achieve com-
to propagate the maximum area of desired treatment from a plete treatment of the target contaminant(s) in the groundwater
given injection point. Excessive application can result in the carrying substrate (IRZ) as it flows toward the next barrier. As
production of increased levels of unwanted by-products such substrate concentrations are depleted to background groundwa-
as methane or organic acids. Also, an excessive consumption ter concentrations (or below the minimum design threshold),
rate can result in inadequate temporal distribution of the car- the system shifts from biological degradation as the dominant
bon substrate, requiring more frequent injection events or an removal mechanism to physical attenuation (Figure 6.41).
increased delivery network. It has been argued at length in A comparison of observed field treatment half-lives
the literature that a slow and steady release of hydrogen from for PCE, TCE, cis-DCE, and VC obtained by evaluating85
degradation of the electron donor is desirable to optimize the reductive dechlorination sites with more than three years of
biological conditions—but while this provision may be easily operation is presented in Table 6.10. Well locations used to
achievable in the lab, it may not always be technically viable, determine these values were located within the IRZ (with
cost-effective, or beneficial in field settings. sustained TOC and methane), the downgradient flushing zone
The economic application of soluble carbon substrates thus (no TOC but elevated methane from upgradient activities),
requires the ability to match the biogeochemical and hydro- and areas outside of the plume (no treatment influence). As
dynamic character of the aquifer to the biogeochemical char- these rates were compiled from IRZ monitoring wells over
acter of one or more sources of soluble carbon. The selection the course of treatment operation, the half-lives shown reflect
of a carbon substrate(s) will be primarily driven by overall the overall contribution of bulk treatment processes to treat-
reaction rates and advective carbon washout from the injec- ment duration observed in the field. In all cases, these half-
tion area, which are, in turn, controlled by the site conditions. lives are higher than those commonly reported in bench-scale
The primary goal should be to minimize overall project cost studies, as the half-life in Table 6.10 represents the overall net
by minimizing the number of required injection points, the
number of injection events, and reagent cost.
Where groundwater velocities are relatively high, the effect TABLE 6.10
of the carbon injections may be reduced by dilution into a large Reductive Dechlorination Rates Determined for Select
volume of oxygenated groundwater, and thus a high consump- Contaminants at Field Sites with at Least 3 Years of
tion of substrate may be necessary to induce anaerobic conditions Active Operation; Rates Representative of Treatment
required for treatment. In systems that are naturally aerobic, it
Completed Using Biostimulation Only
is necessary to use a highly soluble, rapidly acting carbon sub-
strate to quickly drive the redox potential down. Additionally, a Contaminant Regression Fit n Mean Half-Life
highly degradable substrate may aid in overcoming the micro- Tetrachloroethene All data 42 164
bial lag phase attributed to the facultative, anaerobic microbial R2 > 0.5 P < 0.1 35 145
populations that are targeted as part of reductive dechlorination R2 > 0.75 P < 0.01 17 127
IRZs. Once the necessary reducing conditions are achieved, the Trichloroethene All data 64 196
substrate dosing and frequencies can then be reduced to mini- R2 > 0.5 P < 0.1 42 155
mize cost while maintaining the optimum conditions. R2 > 0.75 P < 0.01 20 152
cis-1,2-Dichloroethene All data 56 244
6.2.3.1.2.3  Design Considerations  Cost-effective treat- R2 > 0.5 P < 0.1 36 187
ment of small and even moderately sized plumes may be R2 > 0.75 P < 0.01 12 128
possible via full-scale biological enhancement across the Vinyl chloride All data 38 205
R2 > 0.5 P < 0.1 19 144
contaminant footprint. However, focusing on plume-wide
R2 > 0.75 P < 0.01 8 154
biological reduction as the primary removal process for
large contaminant footprints is often cost prohibitive. In these Source: Schnobrich, M. et al., Optimized Design of Large Plume Enhanced
situations, IRZ implementation is generally a hybrid design Reductive Dechlorination (ERD) Systems: An Analysis of 85 Sites.
approach that utilizes a combination of enhanced microbial Proceedings from the RemTEC Summit, March 2011.
treatment and physical attenuation processes to reduce the
228 Remediation Engineering

100 days Design 100 days Design

travel time time frame travel time time frame

Biological reactive zone

Biological reactive zone

flushing zone

flushing zone
reactive zone

reactive zone
Biological

Biological
Physical

Physical
First injection Second injection First injection Second injection
barrier barrier barrier barrier
(a) (b)

FIGURE 6.46  Conceptual remedial strategies associated with reactive and flushing zones in soluble carbon approaches or under faster
groundwater flow conditions (a) and in insoluble substrate approaches or under slower groundwater flow conditions (b).

contribution of both mass loss (due to biological degradation, 160

abiotic degradation, and dilution) and mass gain (desorption, 140 0.05 ft/day
0.1 ft/day
Flushing distance (ft)

NAPL dissolution) during treatment. Therefore, these values
are representative estimates for designers projecting the over-
all duration of a given IRZ treatment program.
Attenuation rates in the physical flushing zone are signifi-
cantly slower than those observed in the biological reactive
zone and include ambient physical attenuation mechanisms
such as sorption, advection, and diffusion. These mecha-
nisms will occur as the treated groundwater leaving the
biological reactive zone (and no longer containing substrate)
is mixed into the untreated groundwater present between
injection barriers along the plume flow path. The time frame
required for the physical attenuation of impacted ground-
water located between biological reactive zones can be
estimated using the batch flush model56–58 as discussed in
Section 6.1.4.2.
In this simple model, the total time required to achieve
treatment is dependent on the time it takes for the treated
water coming from an upgradient IRZ to flush through the
physical attenuation zone for the required number of pore
volumes in order to achieve the targeted treatment endpoints.
Because of this, the relationship between groundwater veloc-
ity and transect spacing must be carefully considered to mini-
mize life-cycle costs. The importance of this is highlighted in
Figures 6.46 and 6.47, where wide barrier spacing at sites with
slow groundwater velocities can result in significant extension
of remediation time.
Enhanced treatment rates are dependent on the sustained
presence of organic carbon above baseline conditions,59
and injection frequency and loading concentrations are two
mechanisms to control overall organic carbon longevity
and the transport distance over which the reactive zone is
observed.59 There is an upper limit to dosing strength, how-
ever, given the potential for decreases in pH resulting from
fermentation reactions. Injection frequency is influenced
120 0.2 ft/day
100 1.0 ft/day
80
60
40
20
0
0 2 4 6 8 10 12 14 16 18 20
Flushing time (years)
FIGURE 6.47  Depiction of required flushing time to achieve
remedial endpoint based on transect spacing and groundwater veloc-
ity. Estimates based on C0 (TCE) of 1000 µg/L, C (TCE) of 5 µg/L,
soil density of 2.65 kg/m3, Koc (TCE) of 94.94, foc of 0.001 kg/kg, and
a porosity of 35%.
by two conditions: (1) the rate of carbon washout attributed
to groundwater flux and (2) the rate of carbon utilization
due to fermentation and microbial consumption processes.
These conditions are governed by groundwater velocity, as
described below.
Faster groundwater velocity—Advective transport of
organic carbon will control the overall distance over which
the reactive zone can be established. In faster groundwater
flow systems, more frequent application events are required to
replenish carbon as it flushes away from the injection zone when
compared to slower-moving systems. Inject and drift substrate
application with soluble substrates allows for significant exten-
sion of the biological reactive zone (Figure  6.46). Therefore,
while faster groundwater velocity will result in more frequent
substrate application events, the cost associated with the overall
system operation can be balanced by reducing the number of
injection barriers (because organic carbon travels further) and
capitalizing on the shorter physical flushing durations.
Injected Reagent–Based Remedies
Slower groundwater velocity—Carbon washout from the
injection area is minimal and application frequency will be
governed by the intrinsic rate of carbon consumption. In these
systems, the resulting footprint over which carbon is observed
will be generally limited to the vicinity of the injection area,
leading to a relatively short biological reactive zone (Figure
6.46). To achieve similar remediation time frames to that of a
faster flowing system, injection barriers must be positioned in
closer proximity to minimize the overall distance over which
ambient flushing is required.
The differences represented in Figure 6.46 highlight the
importance of tailoring the carbon substrate to the site ground-
water velocity and the remediation design and infrastructure.
For soluble substrates, there is a distinct advantage of using
more complex sugar substrates (e.g., fructose, sucrose) that
undergo multiple fermentation steps and have longer in  situ
half-lives in comparison to shorter, small carbon compounds
(acetate, butyrate, propionate) at sites where groundwater flow
can support inject and drift strategies. Application of less
soluble or solid substrates, which are generally immobile, in
faster groundwater systems must consider the shortened reac-
tive zone (i.e., reduced groundwater residence time within
the area where TOC is elevated) to ensure that contaminant
breakthrough on the downgradient edge of the barrier does
not occur. This can be overcome by employing multiple
stacked barriers or grid-style application to ensure that suf-
ficient residence time is achieved.
Less soluble or solid carbon applications are ideal to
slower groundwater flow systems since DOC hydrolyzing
from these substrates facilitates treatment within the reac-
tive zones over longer residence times. In the case of EVO,
the recommended contaminant residence time within the
area of oil application is recommended to be approximately
2–4 months,60 which is consistent to the 100-day time frame
highlighted by others for soluble substrate applications.61
Outside of the injection area, smaller DOC compounds are
readily consumed and do not travel a significant distance
beyond the injection area. Therefore, while greater EVO car-
bon longevity requires less frequent reapplication events, the
number of injection barriers must be increased to offset the
longer treatment duration associated with the slower physical
flushing mechanisms between barriers.
As discussed in Section 6.2.3.1.2, the buildup of microbial
biomass over the course of an injection program will extend
the overall longevity of as-measured DOC concentrations
within the IRZ. Ongoing process monitoring over the course
of the remedial program is the most appropriate means by
which to quantify the initial reagent half-lives versus the per-
ceived half-life over the course of the program. This aware-
ness then informs decision making pertaining to the timing
of injection events once the IRZ is well established and may
allow the elimination of unnecessary late-stage injection
events to reduce operation and maintenance costs.
6.2.3.1.3  Enhanced Reductive Dechlorination
The terms reductive dechlorination, dehalorespiration, and
dehalogenation are all used interchangeably to refer to the
229
process by which microorganisms utilize chlorinated com-
pounds as electron acceptors. Reductive dechlorination is a
biologically mediated reaction that entails transferring elec-
trons to the chlorinated contaminant of interest from the elec-
tron donors. In this process, the chlorinated hydrocarbon is
used directly as an electron acceptor and dissolved hydrogen
is used directly as an electron donor. As described in Section
6.2.3.1.2, a variety of electron donor substrates are used to
stimulate this process and serve as indirect electron donors
that are fermented in situ to yield hydrogen.
This class of compounds targeted for reductive dechlori-
nation includes widely used solvents such as CT, MC, TCA,
trichloroethene (TCE), and tetrachloroethene (PCE). Other
industrial compounds include a wide variety of chlorinated
organics such as chlorofluorocarbons, chlorinated phenolics,
and chlorinated benzenes, representing products with diverse
end uses as solvents, degreasers, fumigants, biocides, dielec-
tric fluids, flame retardants, and chemical intermediates. The
more oxidized the chlorinated compound is, the more suscep-
tible it is to reduction. The reduction of chlorinated solvent
molecules entails the cleavage of individual chlorine atoms
which are then each replaced with a hydrogen atom. This pro-
cess results in the sequential dechlorination pattern observed
in many contaminated aquifers (Figure 6.48, shown for PCE
and TCE).
Microorganisms have evolved different strategies to
remove the chlorine substituent and utilize these chlorinated
compounds for their own benefit. Commonly observed met-
abolic mechanisms for dechlorination are (1) oxygenolytic
dechlorination, where under aerobic conditions the chlorine is
replaced by a hydroxyl group derived from oxygen; (2) hydro-
lytic dechlorination, where the chlorine is replaced by the
hydroxyl group derived from water; (3) reductive dechlorina-
tion, where mostly under anaerobic conditions the chlorine is
replaced by hydrogen (also referred to as hydrogenolysis); and
(4) elimination (Figure 6.49). Of these mechanisms, reductive
dechlorination is the most dominant and prevalent microbial
reaction responsible for the complete transformation of chlo-
rinated organics.62
The energy gained by bacteria in metabolic reactions is
determined by the nature of the electron acceptor and electron
donor compounds. Chlorinated solvent molecules yield very
little energy to the bacteria that utilize them as electron accep-
tors. As a result, the populations of bacteria that can utilize
chlorinated solvents as electron acceptors can be suppressed by
competing species that utilize more beneficial electron accep-
tors such as oxygen, nitrate, and oxidized forms of iron and
manganese (Figure 6.50). That is why reductive dechlorination
is only observed in aquifers where oxygen and nitrate replen-
ishment is minimal or cut off, or they have been consumed
in the degradation of available carbon supplies. Bacterial con-
sumption of the degradable carbon consumes matching quanti-
ties of electron acceptor compounds, according to constituent
stoichiometry. When the rate of carbon consumption exceeds
the rate of high-yield electron acceptor recharge, an anaero-
bic IRZ is created that provides full dechlorination of target
alkenes and other chlorinated compounds.
230 Remediation Engineering

Perchloroethene Electron
e– H2
Cl Cl flow
C C
Cl Cl

Trichloroethene
Cl Cl + Cl– H+ ion

C C
Cl H

(Predominant biological reaction)

cis-Dichloroethene
Cl Cl
C C
H H

Vinyl chloride
H Cl
C C
H H

Fermentation (Reductive dechlorination) Fermentation Direct oxidation

acetogenesis ethene
H h
C C Chlorethanol CO2, Cl–
Acetate
H H

Sulfate reducing CO2, (CH4)

CO2, CH4, Cl– methanogenic

O C O

(Methanogenic)
ethane
H H
H C C H
H H

FIGURE 6.48  Transformation of reactions of PCE during reductive dechlorination with H2 acting as the electron donor and the chlori-
nated compounds acting as electron acceptors.

In practice, ERD can be implemented in a variety of differ-
ent well-based configurations similar to those shown in Figure
6.13, can be performed via combination of extraction and injec-
tion wells to expedite carbon distribution, or can be achieved
via fractured delivery techniques. The objective of any of these
designs is to achieve uniform carbon delivery in order to foster
an in situ bioreactor downgradient of the injection points. The
system is initiated by delivering sufficient carbon substrate to
promote oxygen and nitrate metabolism near the injection line
and sulfate reduction, methanogenesis, and reductive dechlo-
rination further downgradient (Figure 6.41). The technology
operates most effectively when groundwater is passing through
the sulfate-reducing zone, still bearing a degradable carbon
load that will support methanogenesis and reductive dechlo-
rination. Under these circumstances, cis-DCE is degraded to
ethene or ethane without significant accumulation of VC.
A “high-performance” reductive dechlorination system can
only be achieved when the rate of electron donor consumption
Injected Reagent–Based Remedies 231

a. Oxygenolytic C C OH C O substantially exceeds the rate of electron acceptor recharge.

dechlorination The carbon source must be highly mobile and highly degrad-
1 O2 Cl
2 able and injected at rates commensurate with the overall flux
b. Hydrolytic
of groundwater, electron acceptors, and chlorinated aliphatic
dechlorination C OH hydrocarbons (CAHs) that move into the treatment zone. The
C Cl (H2O) organic acids that form must be buffered by aquifer carbonates
+ Cl–
or by the addition of carbonates and bicarbonates to the injec-
c. Reductive tion mix. Certain site hydrogeologic characteristics will neces-
dechlorination C H sitate modification of the high-performance approach, but
2e–, 2H+ most sites can still be treated by ERD systems that are more
cost-effective than many alternative approaches. Examples of
d. Elimination C
sites requiring modification are those with very low and very
high groundwater flow velocities and those with high electron
FIGURE 6.49  Four fundamental dechlorination mechanisms
acceptor recharge rates.
capable of cleaving the carbon–chlorine bond. (Adapted from
Logan, B.E., Bioremed. J., 69, 1998.)
6.2.3.1.3.1  Degradation Pathways  ERD technology
Electron donor (s) implemented within an IRZ is intended to facilitate and expe-
dite the biological reductive dechlorination of chlorinated
organics through the well-documented mechanisms shown in
Table 6.11 and Figures 6.51 and 6.52. Microbially catalyzed
Reducing processes that take place within an IRZ during ERD are a
power result of the interaction between the biochemical conditions
[H] pool engineered and the complex, dynamic, and unique bacte-
Acetogenesis rial community. Ecological selection pressures including the
Aerobic changing availability of electron acceptors, pH, and elec-
respiration Methanogenesis
tron donor availability will define the site-specific reductive
Denitrification Sulfidogenesis dechlorination bacterial community. While Dehalococcoides
Iron reduction Dehalorespiration species are the most well known as the only genus capable of
performing all chlorinated ethene dehalogenation steps, there
FIGURE 6.50  Variety of metabolic processes supported by elec- is no one biochemical mechanism or any one single bacte-
tron donor delivery, highlighting competition for available H2 elec- rium that is completely “responsible” for the complete trans-
tron donor within anaerobic systems. formation process. It is a consortium of microorganisms and

TABLE 6.11
Reductive Dechlorination Processes
Process PCE TCE cis-DCE VC TCA DCA CT CF DCM
Direct aerobic N N Y&N Y N N N N Y
Cometabolic (methanotrophic) N Y Y Y Y&N N* N Y NR
Cometabolic (organic substance) N Y Y Y N N* N Y&N NR
Cometabolic w/NH4 N Y Y Y Y N* N Y NR
Direct anaerobic N N N Y N N N N Y
Anaerobic/denitrification Y&N Y&N N* N* N* N* Y Y&N NR
Anaerobic/sulfate reduction Y Y Y Y Y Y Y Y NR
Anaerobic/methanogenic Y Y Y Y Y Y Y Y NR

Sources: ITRC Training Session. (2002). Technical protocol for using soluble carbohydrates to enhance reductive
dechlorination of chlorinated aliphatic hydrocarbons. Prepared for Air Force Center for Environmental
Excellence (AFCEE) and Environmental Security Technology Certification Program (ESTCP). December
19. Interstate Techology and Regulatory Cooperation (ITRC) Work Group. (1998). Technical and regula-
tory requirements for enhanced in situ bioremediation of chlorinated solvents in groundwater. December.
http://www.itrcweb.org.
Notes: N, not documented in the literature; Y, documented in the literature many times (consensus opinion); Y&N,
both occurrence and absence documented in the literature more than once; N*, not documented in the litera-
ture to date, but not investigated significantly; NR, process may occur but is not relevant because competing
process occurs more rapidly.
232 Remediation Engineering

PCE CT bacteria: (1) as carbon or energy source or both, (2) as sub-

strate of cometabolic activity, and (3) as terminal electron
acceptor in an anaerobic process (dehalorespiration). The
TCE 1,1,1-TCA CF utilization of chlorinated compounds as growth substrates is
restricted to very few compounds and organisms. In contrast,
the main metabolic processes observed in reductive dechlori-
cis-DCE* 1,1-DCE 1,1-DCA DCM nation are cometabolism and dehalorespiration.
Table 6.12 shows free energies of reaction for several
dechlorination reactions, as well as key metabolic reactions
VC CA CM of the aquifer microbial community. The standard free energy
of each reaction, ∆G 0′, was calculated using Equation 6.30,
using values for free energy of formation of reactants and
Ethene Acetic acid
products given in Table 6.3. Data for dechlorination reac-
tions under nonstandard conditions show that energy yields
exceed the ATP formation minimum of 20 kJ/mol under
Ethane CO2, H2O,
Cl– most temperature and pH conditions examined. The smallest
energy gains are associated with dechlorination of cis-DCE
and the largest with dechlorination of PCE, for any specified
Biotic reactions Abiotic reactions * Primary reactions physical–chemical conditions.
Thermodynamic analysis shows that each of the chlori-
FIGURE 6.51  Biological and abiotic degradation pathways of the nated alkenes in the PCE-to-ethene degradation sequence can
common chlorinated compounds encountered at contaminated sites. be used as alternative electron acceptors with energy yields
far above the ATP formation threshold. Under nonstandard
a variety of mechanisms that bring about the desired transfor- conditions, including low H2 levels, low temperatures, and
mation pathways of the target contaminant. low pH, the reactions remain strongly exergonic. This shows
A variety of metabolic processes have been identified in that the differences in utilization of these compounds as elec-
anaerobic dechlorinating bacteria. Chlorinated compounds tron acceptors are more likely related to enzyme kinetics than
can serve three different metabolic functions in anaerobic to chemical thermodynamics.

Carbon
Tetrachloroethene
tetrachloride
Reductive 1,1,1-Trichloroethane 1,1,2-Trichloroethane
dechlorination
Elimination Reductive
Chloroform Trichloroethene dechlorination

Reductive Reductive 1,1-Dichloroethane

dechlorination dechlorination
1,1-Dichloroethane 1,2-Dichloroethane
Anaerobic Dichloromethane 1,2-Dichloroethene
Reductive Reductive
oxidation
Reductive dechlorination dechlorination
Reductive dechlorination
dechlorination Chloroethane Di-halo
Hydrolysis
elimination
Chloromethane Vinyl chloride
Reductive
Reductive dechlorination Hydrolysis
Reductive
dechlorination
dechlorination

Acetic acid Methane Ethene Acetic acid Ethane Ethanol Ethene

CO2
Aerobic mineralization to CO2
Aerobic cometabolism to CO2
Aerobic cometabolism to CO2 in presence of methane
Biotic reactions (anaerobic conditions)
Abiotic reactions (anaerobic or aerobic conditions)

FIGURE 6.52  Common degradation pathways. (From Interstate Technology and Regulatory Council, Overview of In Situ Bioremediation
of Chlorinated Ethene DNAPL Source Zones. October 2005.)
Injected Reagent–Based Remedies 233

TABLE 6.12
Gibbs Free Energy Yield for Reactions in Standard Biochemical Conditions (298 K, 1 atm, pH 7)
and at Four Nonstandard Conditions (a through d) of Interest in Aquifer Formations
Reaction ΔG0 (kJ/mol) ΔGa (kJ/mol) ΔGb (kJ/mol) ΔGc (kJ/mol) ΔGd (kJ/mol)
Reductive dechlorination reactions
PCE to TCE
C2Cl4 + H2 → C2HCI3 + H + + Cl− −173 −162 −156 −171 −150
TCE to cis-DCE
C2HCl3 + H2 → C2H2Cl2 + H + + Cl− −169 −157 −152 −167 −145
cis-DCE to VC
C2H2Cl3 + H2 → C2H3Cl + H + + Cl− −139 −128 −122 −137 −115
VC to ethane
C2 H 3Cl + H 2 ® C2 H 4 + H + + Cl - −149 −138 −132 −148 −126

Native microbial metabolism

Hydrogenotrophic methanogenesis
CO2 + 4H2 → CH4 + 2H2O −130 −130 −62 −130 −130
Acetoclastic methanogenesis
CH3COO− + H2O → CH4 + HCO3− −1 −31 −31 −31 −31
Lithotrophic sulfate reduction
SO22− + 4H2 + H + → HS− + 4H2O −152 −163 −83 −154 −94
Acetate-oxidizing sulfate reduction
CH3COO− + SO42− → HS− + 2HCO3− −48 −48 −48 −48 −48
pH 7 5 7 7 6
H2 (atm) 1.0 1.0 0.001 1.0 0.001
Temperature (°C) 25 25 25 10 10
PCE (M) 1 1 1 1 1
TCE (M) 1 1 1 1 1
cis-DCE (M) 1 1 1 1 1
VC (M) 1 1 1 1 1

Considerable recent attention has been dedicated toward
identifying the primary reductase enzymes responsible for
the individual dechlorination steps. Much of this research
has centered on the Dehalococcoides genus, several strains
of which have fully sequenced genomes and at least six have
been described with dehalogenation capability.63 Among
known dehalogenating bacteria (next section), a variety of
different reductive dehalogenase (RDase) genes have been
identified that support CAH respiration. From these, sev-
eral specific genes have been identified that are now used
as biomarkers to support determinations as to whether
the necessary microbial community is present and active
in the subsurface. The tceA gene present in several strains
codes for an enzyme responsible for TCE transformation to
both cis-DCE and VC and then supports the cometabolic
generation of ethene from VC.63 The reductase coded for
by the vcrA gene reduces both cis-DCE and trans-DCE to
VC, and bvcA reductase metabolizes VC to ethene. While
these three serve as representative biomarkers for a deha-
logenating microbial consortia (and the Dehalococcoides
species present), they are not all synthesized by the same
Dehalococcoides strain. Further, anywhere from 11 to 32
other RDase genes are synthesized by Dehalococcoides
species of which the substrate specificity and function
remain unknown.63,64
As highlighted earlier for the tceA reductase enzyme,
reductive dechlorination can also be a cometabolic process
in which enzymes and cofactors produced for other pur-
poses perform dechlorination reactions. These cometabolic
reactions are linked to bacteria that are surviving by means
other than reductive dechlorination but that produce enzymes
and cofactors that reduce chlorinated solvents. Bacteria can-
not gain energy for growth by cometabolic reactions, so it is
necessary to provide electron donors, electron acceptors, and
a carbon source to support populations of a density that can
perform meaningful cometabolic dechlorination.
6.2.3.1.3.2  Dechlorinating Organisms  Even though  the
conventional assumption is that chlorinated alkenes and
alkanes were introduced into the environment only in the last
50–60 years, volcanic emissions have been shown to contain
significant amounts of chlorinated alkanes and alkenes and
chlorinated benzoates.65,66 Significant amounts of chloroor-
ganic compounds that are of biogenic and geogenic origin
have been identified in both marine and terrestrial habitats.
The fact that these chloroorganic compounds did not accumu-
late in the environment indicates that many microorganisms
have evolved strategies to benefit from the presence of these
compounds, possibly from the earliest stages of microbial
evolution. A number of bacteria that obtain energy for growth
234
TABLE 6.13
Identified Dehalogenating Microbial General
Microbial Genus Natural Metabolic Function
Dehalococcoides Dehalorespiring
Dehalobacter Dehalorespiring (obligate)
Desulfitobacterium Dehalorespiring
Sulfate reducing
Othera
Sulfurospirillum Dehalorespiring
Dehalospirillum Dehalorespiring
Clostridium Dehalorespiring
Desulfuromonas Dehalorespiring
Sulfate reducing
Iron reducing
Geobacter Iron reducing
Desulfomonile Dehalorespiring
Sulfate reducing
Enterobacter Facultative anaerobe
a Other electron acceptors include nitrate, metals, and humic acids.
by metabolizing chlorinated compounds have been recovered
over the last few decades from contaminated and uncontami-
nated sites. These findings suggest that nature has provided
appropriate mechanisms for long-term microbial adaptation
and for the evolution of enzyme systems specific for chloroor-
ganic compounds.62
One of the earliest observations of reductive dehalogena-
tion was reported by researchers at the University of California
in 1966. Their mixed culture soil enrichment dehalogenated
EDB, an exact analog of 1,2-DCA, to ethene by a dihaloe-
limination reaction.67 Increasing awareness of surface water
and sediment contamination by chlorinated compounds led
to an expanding interest in the fate of these compounds in
the environment, particularly their degradation mechanisms.
Early studies were based on cultures of well-known bacterial
species. For example, the biochemical feasibility for micro-
bial degradation of insecticide residues was demonstrated for
DDT using cell membranes isolated from Escherichia coli and
by cell-free extracts of Clostridium rectum for lindane.68–70
Dechlorination of hexachlorocyclohexanes (which include
lindane) in intact cultures of Clostridium sphenoides was also
demonstrated.69 Ongoing parallel research was conducted to
isolate bacteria from river sediments and wastewater sludges
in a search for dechlorinating species, which provided numer-
ous examples of dehalogenating species and consortia, even
in uncontaminated river sediment environments.46
As reported extensively in the literature, significant
progress has been achieved over the course of the past two
decades to shed insights on the transformation of chlo-
rinated compounds by anaerobic bacteria. As detailed
in the previous section, much of this has centered on the
Dehalococcoides genus. In addition to Dehalococcoides,
however, a range of microbial genera have been identi-
fied that perform at least one of the dehalogenation steps
Remediation Engineering
Transformation Step(s) Reference
PCE → TCE → cDCE → VC → Ethene [71]
PCE → TCE → cDCE/tDCE [71–73]
PCE → TCE [72–75]
PCE → TCE → cDCE/tDCE [72, 73]
PCE → TCE → cDCE/tDCE [71–73]
PCE → TCE → cDCE/tDCE [72]
PCE → TCE → cDCE/tDCE [71–73]
PCE → TCE → cDCE/tDCE [72,73,76]
PCE → TCE → cDCE/tDCE [72]
PCE → TCE → cDCE/tDCE [71,72]
(Table 6.13). Many of these contain species that participate
in the anaerobic processes previously highlighted in Table
6.11. Considering that many of these genera contain multiple
organisms capable of reductive dechlorination and the fact
that the dechlorinating abilities of available cultures have
not been comprehensively explored, it is very likely and
almost certain that a large number of new dechlorinating
species await discovery. What has been clearly demonstrated
is that reductive dechlorination can be a growth-supporting
process, in which chlorinated alkenes are used as terminal
electron acceptors in the oxidative metabolism of electron
donors that include molecular hydrogen, C1 compounds
(CO2, CH3OH, CH2OO −, and CH2O), acetate (CH3COO −),
and other low-molecular-weight organic compounds, all of
which can be formed in the anaerobic metabolism of higher-
molecular-weight carbohydrates.
On a global scale, the distribution of well-understood bac-
teria such as methanogens and SRBs is assumed to be uni-
versal by microbiologists.77,78 Since both of these bacteria
are obligately anaerobic, larger concentrations are expected
in  anaerobic environments. Even in aerobic soil environ-
ments, anaerobic “microsites” provide for the survival of obli-
gately anaerobic bacteria. Additionally, some types of SRBs
can form spores under adverse conditions, which germinate
upon the reestablishment of suitable growth conditions.
Methanogens are obligate anaerobic bacteria that are
capable of reducing carbon dioxide to methane. Many metha-
nogens use hydrogen as their electron donor while reducing
carbon dioxide. These bacteria are autotrophic, since they use
both an inorganic electron donor and acceptor for metabo-
lism. Some species of methanogens can also reduce formate,
carbon monoxide, methanol, various amines, and acetate
to methane. Many of these methanogenic electron accep-
tors are produced within an ERD system via fermentation.
Injected Reagent–Based Remedies 235

Methanogens are also capable of degrading CAH compounds,

although this process occurs cometabolically. Methanogens TABLE 6.14
reductively dechlorinate compounds such as tetrachlorometh- Sample Monitoring Program for Reductive
ane and trichloromethane, 1,2-DCA, and tetrachloroethene. Dechlorination Programs
The purified corrinoid containing carbon monoxide dehy-
Baseline Primary Secondary
drogenase of Methanosarcina thermophila, an acetoclastic
Contaminant(s) Contaminant(s) TDS
methanogen, has been reported to dechlorinate TCE, mainly
End products (ethene/ethane) End products Alkalinity
to cis-DCE and to traces of VC and ethane.79 TOC (ethene/ethane) Nitrate
While Table 6.13 represents a summary of microbial spe- Alkalinity TOC Nitrite
cies that directly or indirectly dehalogenate, abiotic trans- Nitrate Methane Ferrous iron
formation pathways have garnered attention over the past Ferrous iron (field filtered) Manganese
10 years as direct interaction between chlorinated ethene spe- Manganese Arsenic
cies and reduced iron minerals can exhibit expedited rates of Sulfate Sulfate
decay. While multiple sulfate-reducing bacteria also perform Methane Sulfide
metabolic dehalogenation steps, sulfide produced during sul- Dissolved hydrogen
fate reduction reacts readily with dissolved Fe(II) present in Volatile fatty acids
Microbial analyses
groundwater under reducing conditions. For chlorinated eth-
Reductase enzymes
enes, these transformation steps proceed via dichloroacety-
Field parameters Field parameters Field parameters
lene, chloroacetylene, or acetylene intermediates depending
on the starting compound (PCE, TCE, and cis-DCE, respec- Note: Field parameters include ORP, DO, pH, temperature, specific con-
tively) opposed to the traditional microbially mediated path- ductivity, and turbidity.
ways through cis-DCE and VC.80 These species also play a
significant role in reducing carbon tetrachloride to chloro-
form, which occurs slowly via biological processes. Iron sul- operational sampling. This reflects the upfront characteriza-
fide minerals (specifically mackinawite and pyrite) formed tion activities required to understand the background geo-
in anaerobic IRZs therefore provide a secondary means of chemical conditions (i.e., pH, redox poise, competing electron
degrading CAH compounds through end products. While acceptors) and the degree of ongoing reductive dechlorination
these reduced metal species can be widely distributed within processes (parent species, dehalogenation daughter products,
an IRZ, they often form embedded within microbial biofilms and end products). As the suite of available sampling param-
and may not be readily accessible to contaminants passing in eters can be extensive and the operational period for reductive
groundwater.81 dechlorination programs spans multiple years, it is imperative
to select a refined set of parameters that are directly tied to
6.2.3.1.3.3  Monitoring  There are a wide array of sam- key remedial decision making for a given site. In general, the
pling tools and analytical parameters that can be potentially primary decision-making steps revolve around the following
employed during reductive dechlorination treatment pro- key questions:
grams. These include the contaminants and associated ter-
minal end products; geochemical parameters used to assess 1. Is sufficient organic carbon donor available to
the consumption of background electron acceptors and devel- enhance treatment?
opment of the appropriate reducing conditions; and micro- 2. Have the necessary geochemical conditions been
bial sampling techniques to quantify the presence of select established?
microbial communities (e.g., Dehalococcoides), their change 3. Is complete dechlorination being achieved through
over the course of treatment operation, and target reductase daughter and end products?
enzymes excreted for dehalogenation purposes. There are a
variety of sampling parameters that can also be used to assess As discussed in Section 6.1.3.2, injection program monitoring
reagent availability and fermentation, including TOC, DOC, networks utilize well locations positioned at variable spacing
and VFA analyses. Other monitoring parameters are specifi- from the injection points and along the longitudinal flow path
cally related to managing secondary by-products formed dur- of the IRZ and dissolved-phase plume. These wells will there-
ing IRZ operation such as regulated labile metals (ferrous fore have different operational monitoring functions depend-
iron, manganese, arsenic), methane that can represent a poten- ing on their proximity to the known source area, injection
tial vapor intrusion concern, or the development of conditions wells or injection barrier transects, or compliance points. As
adverse to the target microbial consortia (pH). an example, monitoring wells positioned in close proximity
A typical sampling program for reductive dechlorination to the injection wells are likely to be used to assess substrate
treatment programs is provided in Table 6.14, which reflects distribution and longevity in support of reinjection frequency
not an exhaustive list of available parameters but those that decisions, while others more distant will be used to confirm
are integral to guiding treatment operations. As reflected in declines in the target contaminants, which may occur in the
Table 6.14, it is expected that there will be considerable dif- absence of substrate arrival. Accordingly, each of these loca-
ferences between baseline sampling activities and remedial tions should have its own unique set of analytes and sampling
236
frequency that is tailored to treatment rate expectations and
operational considerations.
The following discussion is organized with a focus on the
Point degradation half-life
aforementioned questions and the related sampling param-
eters applicable to support operational decisions and perfor-
mance assessment.
6.2.3.1.3.3.1  Is Sufficient Organic Carbon Donor
Available to Enhance Treatment?  Organic carbon is
required to provide a source of dissolved hydrogen electron
donor that fosters and sustains a highly reduced biogeo-
chemical environment. While dissolved hydrogen represents
the primary electron donor and can be monitored directly,
dissolved hydrogen analysis is expensive relative to standard
TOC and DOC analyses, is susceptible to greater error or
loss during sample handling, and does not provide a com-
prehensive summary of the pool of electron donor available
within the IRZ. As detailed in Section 6.2.3.1.2.1, the avail-
able pool of organic carbon substrate is gradually fermented
to generate dissolved hydrogen—with hydrogen being the
primary end product of interest. Dissolved hydrogen con-
centrations therefore represent the instantaneous hydrogen
electron donor at the time of sampling and do not quantify
the potential for future dissolved hydrogen concentrations
that will be generated from available carbon substrates as
part of ongoing fermentation processes. For these reasons,
sampling programs are best focused to capture the bulk res-
ervoir of residual substrate concentrations over the course
of operation.
The longevity of a given carbon substrate will be variable
based on the complexity of the primary carbon molecule and
the associated fermentation mechanisms. Simple, soluble
carbon substrates such as acetate and ethanol (both C2 com-
pounds) are readily fermented and exhibit rapid half-lives
that can be less than 15 days. Lactate (C3) exhibits a longer
relative half-life (15–30  days), reflecting both primary and
secondary fermentation processes used to generate dissolved
hydrogen. Other more complex soluble substrates like corn
syrup (glucose and fructose—both C6), molasses (sucrose
[C12]), or whey (lactose [C12]) contain larger primary car-
bon molecules, which proceed through multiple fermentation
stages, generate more dissolved hydrogen per unit weight,
and exhibit longer half-lives (30–60 days). Compared to the
soluble substrates, vegetable oils (either emulsified or neat)
contain a variety of different long-chain fatty acids that are
slowly hydrolyzed to release smaller chained soluble carbon
compounds (generally acetate and glycerol) that migrate with
groundwater flow. While the soluble species released from
vegetable oils are readily consumed, the fatty acid hydro-
lysis mechanisms occur far more gradually and provide an
extended source of dissolved carbon species. Understanding
the relative differences in fermentation mechanisms is there-
fore important in selecting a carbon substrate for use and then
monitoring its consumption.
Multiple sampling techniques can be used to assess
residual carbon availability. TOC and DOC analyses are
the most straightforward, are inexpensive, and can be easily
Remediation Engineering
1100
1000 PCE
900 TCE
800
700
600
500
400
300
200
100
0
1 10 100 1,000 10,000
Mean TOC concentration (mg/L)
FIGURE 6.53  Observed relationship between total organic carbon
concentrations and PCE and TCE dechlorination half-lives in moni-
toring wells at active treatment sites (biostimulation alone). TOC
concentrations represent mean concentration observed at the moni-
toring well over the course of an injection program at least 3 years
in length.
collected via grab sampling, low-flow, or equivalent sam-
pling procedures. Conventional rules of thumb are a­ vailable
whether TOC concentrations are sufficient, with target con-
centrations being at least 10–20 mg/L above the baseline
sampling analysis. As long as TOC concentrations are sus-
tained above this threshold and an appropriate microbial
community is established, dechlorination rates are generally
constant (Figure 6.53) as the rates of fermentation and dis-
solved hydrogen production are controlled by the mediating
microbial species. Other sampling parameters that can be
used to assess fermentation activity are VFA analyses. While
considerably more expensive than standard TOC and DOC
analyses, VFA sampling provides definitive proof that fer-
mentation processes are underway and can provide insights
into the discrete fermentation steps for a given substrate—as
shown in the comparison between lactate and molasses fer-
mentation in Figure 6.54a and b. VFA sampling for soluble
substrate applications is generally unnecessary, as a general
awareness that each substrate will have a unique fermentation
signature (which can be site dependent) is likely sufficient
and TOC or DOC analyses will capture the VFA contribu-
tions as part of the bulk parameter response. VFA analyses
can be valuable as a secondary monitoring parameter during
vegetable oil applications, as the observed dissolved carbon
concentrations released from residual vegetable oil sorbed to
the soil matrix can be very close to the minimum threshold
requirements for enhanced treatment (i.e., 10 to 20 mg/L). In
these cases, VFA analyses can be used to supplement TOC/
DOC analyses to document the existence of soluble vegeta-
ble oil derivatives and demonstrate that sufficient substrate
remains in the subsurface.
6.2.3.1.3.3.2  Have the Necessary Geochemical
Conditions Been Established?  Most of the sampling and
analyses required for biogeochemical characterization are
routine analyses for evaluating soil and groundwater systems.
Injected Reagent–Based Remedies 237

7000 7000
Acetic acid Acetic acid
6000 Propionic acid 6000 Propionic acid
Butyric acid Butyric acid
5000 TOC 5000 TOC
Concentration (mg/L)

Concentration (mg/L)
4000 4000

3000 3000

2000 2000

1000 1000

0 0
(a) Baseline Q1 Q2 Q3 Q4 (b) Baseline Q1 Q2 Q3 Q4

FIGURE 6.54  Relationship between observed TOC concentrations and individual VFA intermediate fermentation species following
­side-by-side injection of molasses (a) and lactate (b). Data collected by authors as part of field pilot testing.

Geochemical sampling is an important part of predesign and
baseline sampling activities as it is used to assess the rela-
tive redox poise within the contaminant plume and provide
multiple lines of evidence to demonstrate that reductive
dechlorination can be achieved within the IRZ. Most of the
parameters listed in Table 6.14 are typically analyzed off-site,
but the various field parameters (DO, pH, ORP, conductivity,
temperature, turbidity), sulfide, and dissolved metal filtration
steps should be done in the field.
As part of baseline sampling activities, an expanded geo-
chemistry screen is advantageous as a relative comparison
of DO, nitrate, ferrous iron, manganese, sulfate, and meth-
ane concentrations is useful in assessing redox conditions
within the plume compared to background groundwater.
These analytes provide an understanding of the background
electron acceptor demand that must be overcome by carbon
substrate delivery, support assessment of observed dechlori-
nation trends that may be naturally occurring, and provide
insights into the anticipated durations for IRZ development
and dechlorination lag time. Sampling of the anion couples
for several of these inorganics (nitrite from nitrate, sulfide
monitoring program should be used, however, which can
integrate additional secondary analytes into the plan for
troubleshooting purposes or to answer specific remedial
decisions, as applicable.
The collection of field parameters is often a requirement at
sites where low-flow sampling techniques are being deployed.
As a result, many sites with extended historical monitoring
durations likely have a deep repository of pH, ORP, DO, tem-
perature, conductivity, and turbidity data that can be used to
support both baseline review and for comparison to observa-
tions over the period of operation. Of these parameters, pH
represents the most critical parameter for IRZ performance,
as Dehalococcoides, sulfate-reducing bacteria, and methano-
gens are all adversely affected at low pH. The overall rate of
dechlorination is strongly dependent on pH (Figure 6.55), and
complete dechlorination is not achievable at values outside
of a target range. The ideal pH range at which chlorinated
aliphatic degradation is fastest falls between 6.2 and 8,84 but
100
Extent of PCE dechlorination (%)

from sulfate) can also be helpful in understanding whether 80

ongoing reduction of background electron acceptors is under-
way. Guidance pertaining to typical geochemical parameters
60
and the ranges necessary for dechlorination are available.46,83
As geochemistry is always site specific and will be unique to
the interval in which a monitoring well is screened (which 40
may straddle multiple groundwater horizons where variable
redox conditions exist), it is good practice to assess the rela- 20
tive difference in these parameters opposed to specific thresh-
old values. 0
As routine delivery of organic carbon promotes redox 3 4 5 6 7 8 9 10
transition from the baseline conditions (e.g., aerobic, iron pH
reducing) to methanogenic, much of the geochemical FIGURE 6.55  Relationship between pH and observed PCE dechlo-
sampling suite can be reduced and methane can be used rination extent. (Chappelle, F.H.: Groundwater Microbiology and
as the stand-alone primary indicator that highly reduced Geochemistry, John Wiley & Sons, New York, 2001. Copyright Wiley-
groundwater conditions have been achieved. An adaptive VCH Verlag GmbH & Co. KGaA. Reproduced with permission.)
238
complete dechlorination can still be achieved at pH values out-
side of this range (generally between pH 5 and 9) depending
on the extent and distribution of subsurface biomass, which
can shield dehalogenating organisms from potentially adverse
groundwater conditions. In addition to evaluating whether
natural groundwater conditions are conducive to treatment,
pH monitoring is also important to confirm the delivered
carbon substrates are not adversely impacting overall treat-
ment. VFA production during organic carbon fermentation
will generate acidity that can reduce pH in poorly buffered
groundwater systems or following excessive carbon substrate
delivery (Figure 6.56). pH monitoring can therefore be used
to reduce carbon dosing to avoid transient pH depression or
used to identify an appropriate means to modify the injection
solution with base (to achieve a more alkaline titration) or a
buffering agent (e.g., bicarbonate).
DO and ORP measurements collected as part of monitor-
ing programs are useful qualitative indicators of both back-
ground electron acceptor availability and general redox poise.
Many guidance documents highlight these as key sampling
parameters for performance assessment, but both should be
viewed qualitatively compared to laboratory analytical tech-
niques. DO measurements collected with a field sampling
probe can be subject to individual operator calibration and
temperature, salinity, and dissolved gas interferences. For
these reasons, it is not uncommon to encounter DO concen-
trations between 1 and 2 mg/L in wells that also contain dis-
solved iron, sulfide, or elevated methane concentrations that
are representative of anaerobic groundwater conditions. As an
alternative, downhole optical sensing probes can offer more
reliable DO measurements, specifically at low concentra-
tions. The ORP value for groundwater is a measurement of
electron activity and an indicator of the relative tendency of
a biogeochemical system to accept or transfer electrons. In
very oxidizing environments, the activity of electrons is low
(positive ORP values), and in very reducing environments, the
activity of electrons is high (negative ORP values). In reduc-
ing IRZs, increased electron transfer results in increasingly
Electron donor injection zone
High
pH
neutral
Near
Low
pH
Fermentation
reactions depress pH
Distance
Upgradient
FIGURE 6.56  Potential pH changes in groundwater as a result of organic carbon injection and primary and secondary fermentation pro-
cesses. Above line demonstrates natural acidity neutralization by the soil matrix and groundwater buffering capacity; lower line reflects
sustained pH depression following carbon delivery in the absence of sufficient matrix neutralization and buffering capacity.
Remediation Engineering
negative ORP values, and this methodology has been used
historically to assess the relative redox conditions. Similar
to DO measurements, however, ORP measurements are also
only qualitative as they are affected by all reactions occurring
on the probe electrode and can drift based on ionic strength
or impurities on the electrode surface. Further, ORP measure-
ment (and related EH) assumes that the system being moni-
tored is in thermodynamic equilibrium—which is inherently
flawed due to the dynamic biological system being monitored.
In addition to the geochemical assessment parameters dis-
cussed earlier, a number of other parameters may be useful or
necessary depending on regulatory concerns or the nature of
the aquifer being treated. These potentially include total dis-
solved solid (TDS) (used to qualify the usability of some aqui-
fers), alkalinity, or reduced metal species. The fermentation
and utilization of organic carbon will generate alkalinity over
the course of an injection program. As shown in Figure 6.56,
transient pH depression occurring immediately following car-
bon injection is related to primary fermentation processes that
produce VFAs. This acidity is then neutralized by the native
aquifer matrix mineralogy, and additional alkalinity also sup-
ports a restoration in groundwater pH.
The mobilization of labile iron, manganese, and arse-
nic metal species is an expected secondary effect of IRZ
applications. Fe(III) reduction releases Fe(II) that can react
with sulfide to form iron sulfide precipitates (and contrib-
ute abiotic treatment as detailed in 6.2.3.1.3.2) or can inter-
act with oxygen to form iron hydroxide, oxyhydroxides, or
other precipitates—which can contribute to well fouling. As
detailed in Section 6.3 and Chapter 7, iron dissolution and
precipitation mechanisms play a role in a number of other
metal interactions. Notable in organic carbon IRZs is the for-
mation of dissolved arsenic (As[III]), which either exists as
arsenate (As[V]) within the soil mineralogy or as a copre-
cipitate with Fe(III). While secondary water quality standards
exist for iron and manganese minerals and can drive sampling
requirement, dissolved arsenic can be of increased concern
due to its relative toxicity. While arsenic mobilization may
Aquifer matrix buffers pH back
to normal range
Excessive carbon loading
overcomes aquifer buffering
capacity
Downgradient
Injected Reagent–Based Remedies
100000
10000
Cation concentration (µg/L)
1000
100
10
1
Reactive zone
0.1
0 200
Downgradient travel time (days)
FIGURE 6.57  Reduced metal species in groundwater downgradient of an active reductive dechlorination IRZ. Iron and arsenic mobiliza-
tion observed where reduced groundwater conditions persist; both species coprecipitate from groundwater as reduced groundwater mixes
with downgradient ambient aerobic groundwater conditions.
be expected to occur in an IRZ, arsenic solubility is closely
linked to that of iron and they form complexes that reprecipi-
tate from groundwater within the redox recovery zone. An
example of this is highlighted in Figure 6.57, where both dis-
solved iron and arsenic behavior are closely correlated within
and downgradient of the IRZ location. Dissolved metal sam-
ples should be field filtered prior to transmittal to a laboratory,
as oxygen entrained in solution as part of sampling or trans-
mittal to the lab can generate similar precipitates and prevent
accurate measurement.
6.2.3.1.3.3.3   Is Complete Dechlorination Being
Achieved through Daughter and End Products?  While
this represents the ultimate objectives of IRZ treatment appli-
cations, the answers to this question are more straightforward
than the nuanced geochemical assessment highlighted ear-
lier. One of the primary advantages of reductive dechlorina-
tion monitoring programs is the definitive demonstration that
treatment is ongoing. Regardless of the chlorinated aliphatic
parent compound (PCE, TCE, 1,1,1-TCA, CT, 1,1,2,2-TeCA),
each species is transformed to equivalent molar concentra-
tions of their respective daughter products, which are then
converted to the molar equivalent end product. While a com-
plete mass balance for this process is often obtainable in a
laboratory microcosm, field-scale IRZs are open systems and
contain residual DNAPL or sorbed-phase mass that generally
impede completion of a perfect stoichiometric balance. As
shown in Figure 6.58, these transformation steps provide com-
pelling lines of evidence to document that the target treatment
objectives have been achieved. To demonstrate these changes,
standard VOC analyses and dissolved gas sampling are neces-
sary as part of baseline and ongoing performance monitoring
activities. While dissolved gas analyses are focused primarily
on ethene and ethane, acetylene could also be added to these
parameters to assess potential abiotic treatment contributions
to the overall change in contaminant concentrations.
239
Arsenic
Ferrous iron
Manganese
400 600 800 1000
The observation of incomplete dechlorination may be attrib-
uted to several primary factors, many of which are related to
the first two performance questions. The inability to distribute
and sustain sufficient organic carbon concentrations translates
to inadequate dissolved hydrogen for use in reducing compet-
ing electron acceptors and providing sufficient electron donor
for treatment. Low pH conditions affect Dehalococcoides
and their reductase enzyme synthesis, which represents the
primary microbial genera and enzymes responsible for com-
plete PCE and TCE transformation through ethene. Sulfate-
reducing bacteria, which can also perform PCE dechlorination
through cis-DCE, are less affected under these conditions, and
therefore observations of accumulating cis-DCE (with no VC
or ethene) can be encountered. In other instances, while lim-
ited, Dehalococcoides species may not be present and bioaug-
mentation may be a requirement. In these instances, adding
in supplemental microbial analyses similar to those discussed
in Section 6.2.1.3 can provide value in determining whether
the target microbial species are present (via direct microbial
community quantification) or whether they are actively exud-
ing reductase enzymes (via focused mRNA qPCR analyses).
Collectively, all of these lines of evidence can be integrated to
perform potential remedial troubleshooting.
6.2.3.1.4  Explosives Degradation
Explosives are materials that, when suitably initiated, result
in the rapid release of energy. Detonation of a solid explosive
generates expanding hot gases, and this expansion creates a
shock wave that exerts high pressures on the surroundings,
causing an explosion. Explosives generally have high nitrogen
and oxygen contents, which aid the formation of the gaseous
products, typically including carbon dioxide, carbon mon-
oxide, nitrogen, and water vapor. The history of explosives
can be defined from the first mixture of gunpowder to the
industrialization of explosives manufacturing to provide both
greater power and control.
240 Remediation Engineering

2500 20,000

TOC and sulfate (mg/L)

2000 16,000

Methane (µg/L)
1500 12,000
1000 8,000
TOC
500 4,000 Sulfate
Methane
0 0
0 500 1000 1500 2000 2500 3000
pH
9
8
7
pH

6
5
4
0 500 1000 1500 2000 2500 3000
Chlroinated ethenes (µmol/L)

Ethene and ethane (µmol/L)

60 25
50 20
40
15
30 Trichloroethene
10 cis-1,2-Dichloroethene
20
Vinyl chloride
10 5
Ethene
0 0 Ethane
0 500 1000 1500 2000 2500 3000
Days elapsed

FIGURE 6.58  Visual data assessment of primary decision-making analytes over the course of reductive dechlorination IRZ application.
Increased TOC concentrations correlate with the onset of methanogenesis, which is followed by sequential chlorinated ethene transforma-
tion in the presence of sustained organic carbon availability. Data reflect biostimulation response alone.

The manufacture, use, and disposal of explosives from NO2 NO2 CH3
military operations have resulted in extensive contamina- N N O2N NO2
tion of soils and groundwater.86,87 Of the nearly 20 differ- O2N N
ent energetic compounds used in conventional munitions by N N N NO2
O2N NO2 N
the military today, hexahydro-1,3,5-trinitro-1,3,5-triazine
NO2 NO2
(RDX) and octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine
(HMX) are the most powerful and the most commonly used. (a) (b) (c)
RDX and HMX are acronyms that stand for royal demolition
explosive and high melting explosive, respectively. Another FIGURE 6.59  Molecular structure of three explosives: (a) RDX,
commonly used military explosive is 2,4,6-trinitrotoluene (b) HMX, and (c) TNT.
(TNT). Figure 6.59 illustrates the molecular structure of
these three compounds. toxicological exposure limits have not been determined for
The release of these contaminants, resulting in significant explosive compounds. In addition, explosive compounds are
soil and groundwater contamination, has been associated with also considered to be highly recalcitrant.
various commercial and military activities including manu- A characteristic of explosives is the presence of multiple
facturing, waste discharge, testing and training, open burn- nitro (–NO2) groups on the molecule (Figure 6.59). Although
ing, and open detonation. It has been estimated that during TNT reductive transformation has been known for some time,
RDX manufacturing up to 12 mg/L can be discharged into the only recently have TNT reductive transformation products
environment in process wastewaters. Major factors affecting been routinely measured in laboratory and field studies.79
the fate and transport of TNT in the subsurface are transfor- Possible TNT transformations include reduction of one, two,
mation, sorption, and irreversible soil binding. In addition to or all three of the nitro-moieties to amines and coupling of
dilution and dispersion, processes important to groundwater amino transformation products to form dimers. Formation
transport of explosives include biotic and abiotic transforma- of the two monoamino transformation products, 2-amino-
tions, covalent bonding to soil organic matter, and adsorption 4,6-dinitrotoluene (2ADNT) and 4-amino-2,6-dinitrotoluene
by soils. (4ADNT), is favored, and they are typically observed in
In addition to their destructive capacity, explosives com- TNT-contaminated soils and groundwater. Since the diamino
monly have toxic effects on ecological systems. All explo- products are energetically more difficult to form, they are
sives exhibit harmful effects to varying degrees; however, observed less frequently and typically at lower concentration
Injected Reagent–Based Remedies 241

than the monoamino products. The triamino product is rarely
observed not only because it is more energetically difficult to
form but also because once formed, it does not persist, but is
likely to be immobilized by chemical reactions with soil com-
ponents or by microbial degradation. The reductions can be
enzymatically catalyzed or, under proper reducing conditions,
occur via abiotic transformation.
The amino transformation products are amenable to sev-
eral attenuation mechanisms in soils. These include covalent
bonding to functional groups on soil organic matter such as
described for similar amines, reactions at mineral surfaces,
sequestration, and reversible adsorption. Although these
mechanisms for attenuation of TNT have received attention
in laboratory and field studies in the last several years, lit-
tle data have been reported on their occurrence in the field
beyond detection of the amino transformation products in
soil and groundwater and decline in TNT concentrations over
time.88,89 Hence, there is a school of thought that TNT tends to
undergo only transformation reactions rather than mineraliza-
tion. The transformation products bind to the soil and become
unextractable.
While TNT biodegradation is problematic, toluene, ben-
zene, and phenols with one or two nitro groups on the mol-
ecule are more subject to biodegradation and mineralization.
Initial monooxygenation or dioxygenation reactions can lead
to the release of –NO2 groups and substitution of –OH. This
can lead to mineralization. In some cases, the nitro group is
reduced to an amino group, and the resulting amino aromatics
accumulate as dead-end products.89
In principle, TNT should be biodegradable by a two-stage
reductive/oxidative process (Figure 6.60). Due to the stability
of the aromatic ring and the electron-withdrawing properties
of the nitro group, microbial action on compounds such as
TNT generally proceeds via reduction of the nitro groups,
reducing them successively to nitroso, hydroxylamino, and
amino groups. Candidates for key metabolites in such a
pathway are the products of reduction of the nitro groups or
the aromatic ring system. For example, the hydroxylamino
toluenes could be substrates for mutases or hydroxyaminoly-
ases, which generate aminophenols or catechols. The amino
derivatives, in particular, are also very stable and adsorb very
strongly to soil, factors that strongly hinder further break-
down in the subsurface environment. In addition, the hydrox-
ylamino and amino derivatives can dimerize to form azo and
azoxy dimers, which are resistant to further metabolism.90
Such compounds and the triaminotoluene (TAT) from
complete reduction of TNT or its hydride complexes harbor
structural features and sufficient chemical reactivities to be
potential parent compounds of complete, mainly oxidation
pathways. The potential function of TAT as a key metabolite

CH3
O2N NO2

NO2 Path b

Path a

O2N CH3 CH3

O2N NO O2N NO2
H2C NO2
H
H
N NO2 NO2

H2C NO2 CH3 CH3

O2N NHCH O2N NO2
O2N H
H
H H
NO2 NO2

CH3
O2N NH2 NO2– + ?

NO2

FIGURE 6.60  Microbial transformation of TNT. Path a. TNT can undergo reduction of the nitro groups through nitroso, hydroxylamino,
and amino derivatives. Each of the nitro groups may undergo reduction, although triaminotoluene only forms under anaerobic conditions.
Azo and azoxy dimers can form from nitroso and hydroxylamino dimerization. Path b. TNT can also undergo hydride addition to form
hydride- and dihydride-Meisenheimer complexes.
242
in a two-stage reductive/oxidative process is limited, how-
ever, by its high reactivity toward oxygen, which gives rise to
extensive misrouting and finally the generation of dark high-
molecular-weight products.89,91,92,94
The research conducted thus far shows tentatively that bio-
degradation of RDX and HMX under both aerobic and anaer-
obic conditions is feasible. Unlike TNT, which is subject to
biotransformation rather than mineralization, the two cyclic
nitramines RDX and HMX undergo ring cleavage following
initial transformation of the molecules by anaerobic sludge.
Under reducing conditions, small organic molecules (HCHO,
HCOOH, CO, CO2) and small nitrogen-containing products
(NO2−, NO3−, CN−, and NH3) are produced. Mineralization of
either RDX or HMX under anaerobic conditions is extensive
(60% with anaerobic sludge). Under aerobic conditions, the
biodegradation of the two explosives is clearly far from being
understood and certainly further research is needed. In gen-
eral, the current understanding of the biodegradation of cyclic
nitramines, particularly with respect to the microbial popula-
tions and enzymes involved, is incomplete.88,89,93 It should be
noted that RDX can also be broken down by alkaline hydroly-
sis under the right conditions. The mechanism by which this
reaction is proposed to occur involves the abstraction of a pro-
ton by the alkali, with the simultaneous loss of nitrite (NO2−),
to form an unstable intermediate that further degrades.95
RDX contains chemical groups, such as the nitramine
group, which were not previously found in nature. It could be
proposed that the novelty of these compounds would mean
that the environmental microflora would not possess enzymes
that could degrade or transform them. However, laboratory,
field, and composting studies indicate microorganisms are
able to remove the nitramine explosives.
RDX is much more amenable to biodegradation than TNT.
With no aromaticity, it appears to be able to undergo several
types of reaction (Figure 6.61). Under anaerobic conditions,
reduction of the nitro groups forms nitroso intermediates that
subsequently break down further.96 Under aerobic conditions,
nitrite has been seen to accumulate. Unlike the nitrate ester
and nitroaromatic explosives, there has been no identifica-
tion of enzymes responsible for any of the reactions that RDX
undergoes. This interesting and fundamental area remains to
be investigated.97
There are only a few reports of microbial activity on
HMX. Products of the anaerobic degradation of HMX include
nitroso derivatives, indicating a mechanism similar to the
anaerobic degradation of RDX, and also at a slower rate than
RDX. Aerobic removal of HMX has also been reported.97 The
reduced microbial activities against these compounds may
be due to the lower solubility than RDX, the greater steric
effects within transition states, and the higher bond dissocia-
tion energy of the N–NO2 bond.
One clear conclusion that can be reached from the litera-
ture reports is that once the ring in cyclic nitramine cleaves,
the resulting degradation products are expected to be ther-
mally unstable and to hydrolyze readily in water. Such abiotic
reactions would compete with other biological reactions dur-
ing attempted biodegradation. If the biodegradation reactions
Remediation Engineering
are considerably slower, it would be impossible to evaluate the
degradation process at the microbial level unless some inno-
vative research is undertaken to either slow down the abiotic
processes or enhance the enzymatic ones.93
Recent studies indicate that hydrogen is a key factor in
stimulating the anaerobic biotransformation of TNT, RDX,
and HMX. It was shown that electron donors that produce
H2 support the biodegradation of these compounds.98 The
authors’ experience in field tests indicates that TNT, RDX,
and HMX degradation can be achieved within anaerobic
reducing IRZs created with organic carbon electron donor.
The capacity constant for sorption of RDX onto soil is
relatively low, indicating that RDX is not extensively sorbed
by soil, but once it occurs, sorption is reported to be nearly
irreversible.99 Because the desorption isotherm lies above the
sorption isotherm and the capacity constants for desorption
are significantly higher than that for sorption, there is consid-
erable sorption–desorption hysteresis. Therefore, it appears
that a proportion of the RDX may be irreversibly bound to the
soil and desorption should not be significant in the presence of
organic carbon electron donors—as occurs in other microbial
IRZs due to microbial surfactant and cosolvent effects.
Similar to RDX, TNT can be irreversibly sorbed by soils.
However, reactions that remove TNT from solution and bind
its transformation products to soil in an unextractable man-
ner can be mistaken for adsorption. The reaction products
of TNT, particularly hydroxylaminodinitrotoluene and TAT,
have been demonstrated to bind irreversibly to soil compo-
nents. Substantially fewer data are available on the sorption of
HMX; however, it is apparently sorbed less than TNT by soils.
In summary, soil–water partitioning coefficients for RDX and
HMX (Kd, 1) are less than those reported for TNT (Kd. 4),
indicating that the nitramines are more mobile than TNT and
capable of migration through subsurface soil to groundwater
supplies. TNT transformation products bind irreversibly to
soil and are immobilized.
The threshold concentrations at which these compounds
become toxic in aqueous solution cannot be achieved as they
are relatively insoluble in water and cannot reach toxic lev-
els. At 20°C to 25°C, the reported solubilities for TNT, RDX,
and HMX are 140 mg/L, 42 mg/L, and 5 mg/L, respectively.
However, the toxicity of these explosives when adsorbed by
soil is another matter. In general, TNT is the most toxic of
these explosives to soil microorganisms, while RDX and
HMX are also toxic at certain concentrations.
Under anaerobic conditions, at redox potentials below
−200 mV, the transformation of TNT to triaminotoluene
(TAT) has been reported. However, further degradation of
this compound has not been conclusively proven. There are
some reports that hydroxylated toluene derivatives form but
these reports have not yet been substantiated. In general, the
anaerobic mode of attack on TNT looks more promising as a
process leading to mineralization because aerobic attack ends
up forming dead-end products.
Neither RDX nor HMX contains any carbon-to-carbon
bonds and is metabolized by methylotrophic bacteria that
have the capacity to degrade and assimilate these compounds.
Injected Reagent–Based Remedies 243

NO2
N

N N
O2N NO2

Anaerobic sludge

NO2

O2N NO2 N
N N HOH2C CH2OH
H H RDX
Methylenedinitramine Bis(hydroxylmethyl)nitramine
O2N NO2 O2N O2N
N N N N N N

N N N
HOH2C N NO2 H2N NO2 N2O
H NO2 NO2– NO2 NO2–
+ HOHO
H2O 2H2O
Acetogens NO2 NO2
OH
HCOOH + MeOH
O 2N
C2H5N3O3 + N H NH
Methanogens CO2 HCHO [NH2CHO] H
N NH OH
CO2 + CH4 NH3 H
(a) (b)

RDX MNX DNX TNX

O2N NO2 O2N NO2 O2N NO ON NO
N N N N N N N N

N N N N
NO2 NO NO NO

O2N NO2 O2N NHOH ON NHOH

N N N N N N

N N N
NHOH NO NO

[Ring cleavage products]

CH3OH (methanol) HCHO (formaldehyde) +

H2N-NH (hydrazine) +
1,1-dimethylhydrazine +
(c) 1,2-dimethylhydrazine

FIGURE 6.61  (a) Second putative pathway for RDX degradation by anaerobic sludge. Compounds identified include methylenedinit-
ramine, bis(hydroxymethyl)nitramine, formaldehyde, formate, methanol, nitrous oxide, methane, and carbon dioxide. Two hypothetical
intermediates are also shown in brackets. Traces of nitrogen gas and nitrite were also detected, along with some soluble, nonextractable
degradation products. (Adapted from Zhuang, P. and Pavlostathis, S.G., Chemosphere, 31(6), 3537, 1995.) (b) Proposed mechanism of RDX
biodegradation by Rhodococcus sp. strain DN22. Denitration as an enzymatic first step creates unstable intermediates that undergo ring
cleavage. NO2−, N2O, NH3, HCHHO, and CO2 were identified as products of RDX degradation, as well as the dead-end product C2H3N3O3.
Hypothetical components of the pathway are shown in brackets. (c) Putative pathway for the anaerobic biodegradation of RDX via nitroso
intermediates. Compounds identified include the three nitroso derivatives, formaldehyde, methanol, and hydrazine, and the two dimethyl-
hydrazines. The hydroxylamino derivatives and ring cleavage products are hypothetical intermediates and are shown in brackets. (Adapted
from Spain, J.C., Biodegradation of Nitroaromatic Compounds, Plenum Press, New York, 1995.)
244
This may account for the suggestions that RDX degradation
is primarily a cometabolic process as only certain members
of any soilborne microbial population will be able to uti-
lize RDX and HMX as a source of carbon and an electron
donor for respiration. These explosives may be more readily
biodegraded as a nitrogen source in the presence of a read-
ily degradable carbon source. Hence, it may be important to
choose an organic substrate with the lowest C:N ratio to create
the reducing IRZ for explosives degradation while maintain-
ing sulfate-reducing or methanogenic conditions.
6.2.3.1.5  Perchlorate Degradation
Perchloric acid and its salts have been used extensively in a num-
ber of commercial applications such as wet digestions, organic
syntheses, electropolishing of metals, animal feed additives,
explosives, pyrotechnics, missile propellants, and herbicides.
Perchlorate (ClO4−) is the soluble anion associated with the
solid salts of ammonium, potassium, and sodium perchlorate.
Ammonium perchlorate is used as an energetics booster or
oxidant in solid propellant for rockets and missiles. Ammonium
perchlorate is also used in certain fireworks, the manufacture
of matches, as a component of airbag inflators, and in analyti-
cal chemistry to preserve ionic strength. Large-scale produc-
tion of ammonium perchlorate began in the United States in
the mid-1940s. Ammonium perchlorate has a limited shelf life
and must be periodically replaced in munitions and rockets.
This had led to the disposal of large volumes of this compound
since the 1940s in Nevada, California, Utah, and other states.
The anion perchlorate poses potential environmental con-
cerns because its ionic radius and charge are similar to that of
iodine, which allows perchlorate to competitively block thy-
roid iodine uptake.100,101 The first concerns about perchlorate
in the environment surfaced in 1896 when sodium and potas-
sium salts of perchlorate found in Chilean potassium nitrate
deposits were noted to be harmful to certain agricultural
crops.101 These deposits (Chilean saltpeter) have been used in
the manufacture of some chemical fertilizers.
Since the discovery of the naturally occurring perchlo-
rate in Chilean saltpeter, additional natural occurrences of
perchlorate have been identified in natural potash-bearing
evaporite, hanksite, and playa crust samples.102 All of these
perchlorate sources are in arid climates and associated with
evaporite deposits. Since naturally occurring concentrations
of perchlorate are too low to be of any economic benefit, it
is not surprising that until the recent emergence of concern
about perchlorate as a contaminant, few efforts have been
made to map its distribution in geologic materials.
While the mechanism for the natural formation of perchlo-
rate is not well understood, it has been hypothesized that per-
chlorate can be formed in the atmosphere by the reaction of
tropospheric ozone with chlorine.103,104 It is unlikely that this
mechanism would produce substantial quantities of perchlo-
rate that would reach the surface via precipitation, as the con-
centration of reactive chlorine existing in the troposphere is
low. However, it has been postulated that the reaction between
the ozone and halogenated acid gases and chlorinated vola-
tile organics produced in the combustion zone of forest fires
Remediation Engineering
(favored by the high heat of the fire near ground surface) could
lead to perchlorate formation at the soil particle surfaces or on
the surfaces of atmospheric particulates created by the for-
est fire itself. Perchlorate produced by this mechanism could
reach the ground surface through wet deposition and could be
transported by the oxic rainwater.
The postulated chemical mechanisms that would produce
perchlorate are oxidative in nature: reaction of ozone with chlo-
rine is an example of an oxidation reaction. However, oxidized
materials that are subsequently buried become isolated from
the oxygen in the atmosphere, and they may become anaerobic
where reduced minerals or organic carbon is available. As an
example, a natural process could be envisioned where perchlo-
rate was naturally produced during forest fires and then subse-
quently buried by rapid sedimentation where it was precipitated
and concentrated as a salt under evaporative conditions. In the
presence of naturally occurring organic carbon (e.g., impartial
combustion products), perchlorate would then be subject to
biological reduction and dechlorination by bacteria utilizing
the organic carbon and perchlorate as reductant and oxidants,
respectively. In this example, naturally formed perchlorate
would be short-lived due to a natural biogeochemical process.
Natural geologic settings that would preserve or have
preserved perchlorate over long time frames can be called
“permissive geological units.” Two examples of such settings
include the following:
Oxidation poise setting.  This would involve deposition
of perchlorate within oxidized materials with other
natural materials that contribute oxidation equiva-
lents over a long time frame (nitrate deposits are
examples of this, where nitrate would tend to oxidize
any reductants within the system, including reduced
sulfide, iron, manganese, and organic carbon). In
such systems, it is not required that the naturally
occurring oxidant be at a higher formal oxidation
potential than perchlorate but rather that the oxidant
be either in great molar excess (percentage-level
nitrate vs. ppm-level perchlorate) or that it be physi-
cally or geochemically in a more reactive position
(such as layered around the perchlorate) within the
formation. Geologic units in contact with the atmo-
sphere where rainfall is also limited could also com-
prise an oxidation poise setting, where oxygen from
the atmosphere supplies the oxidation equivalents.
Biogeochemical inhibitor setting.  This would involve
deposition of perchlorate within a geologic formation
that contains other materials that generally prevent
biological oxidation–reduction reactions from occur-
ring. Examples of this mechanism could include
direct inhibition mechanisms, such as the presence
of specific compounds in the formation that would
act as poisons for biological electron transport, pre-
venting perchlorate reduction by biochemical inhibi-
tion, or indirect inhibition mechanisms, such as low
water availability in a brine or evaporite materials,
which generally inhibit all biological processes.
Injected Reagent–Based Remedies
These two speculative mechanisms may explain the distribu-
tion of naturally occurring perchlorate in some regions of the
United States.
Most of the anthropogenic perchlorate contamination in
the groundwater originates from the historical legal discharge
of then unregulated waste effluents containing high levels of
ammonium perchlorate. Although ammonium perchlorate
was released initially, the salt is highly soluble and dissociates
completely to ammonium and perchlorate ions upon dissolv-
ing in water:
NH 4ClO 4 ® NH 4 + + ClO 4 - (6.39)
It is likely that most of the ammonium has been biodegraded
and the cation is now best viewed as mostly Na+ or possibly
H+, especially where perchlorate (ClO4−) levels are below
100  ppb. At those sites where contamination dates back
decades, very little (if any) ammonium has been found.105
The persistence of perchlorate in aquifers results primar-
ily from a combination of aerobic conditions and lack of an
electron donor. A number of bacteria that synthesize nitrate
reductases are capable of dissimilatory reduction of perchlo-
rate.105,106 Many mixed cultures have reduced perchlorate,
chlorate, chlorite, nitrate, nitrite, and sulfate under the right
conditions. Inhibition of perchlorate reduction also has been
observed in the presence of other substrates, particularly
chlorate, chlorite, and sulfate.105 Chlorate reductase has been
isolated from microorganisms that also possess nitrate reduc-
tase. Although most perchlorate strains may be denitrifying
facultative anaerobes, not all denitrifiers are (per)chlorate
reducers. Simultaneous reduction of NO3− and ClO4− has been
demonstrated in many laboratory and field studies.105,106
Microbially catalyzed perchlorate reduction is metaboli-
cally promising because the chlorine atom within the per-
chlorate molecule is in its highest oxidation state (17). Hence,
the reduction of perchlorate is highly thermodynamically
favorable. Thermodynamic data indicate that perchlorate is
a strong oxidant and could provide a large amount of energy
to microorganisms as an electron acceptor. Some research-
ers have claimed that chlorite (ClO2−) is the microbial per-
chlorate (ClO4−) reduction end product because it has been
demonstrated that the microbially mediated transformation of
ClO2− to Cl− is a dismutation reaction that yields no energy for
perchlorate-reducing microorganisms.107,108
Denitrifying microorganisms that have the enzyme chlo-
rate dismutase can use the denitrification pathway to reduce
(per)chlorate, and there is evidence in some microorgan-
isms that an enzyme system may exist that is not involved
in NO3− reduction and is also able to reduce ClO3− and
ClO4 −.109,110 So far, perchlorate-degrading isolates reported
have been mostly heterotrophic and require organic sub-
strates for synthesizing cellular materials. However, the
isolation of a novel chemolithoautotrophic, perchlorate-
reducing, hydrogen-oxidizing bacterium (Dechloromonas
sp. strain HZ) has been reported,111 which was grown using
acetate as the electron donor with chlorate, nitrate, or oxy-
gen as electron acceptors.
245
The conversion of chlorine in perchlorate to chloride requires
the overall transfer of eight electrons. The sequence of inter-
mediates involved in perchlorate reduction is as follows:
ClO 4 - ® ClO3- ® ClO2 - ® O2 + + Cl -
(perchlorate) (chlorate) (chlorite) (chloride) (6.40)
Although oxygen is produced, it is used by the perchlorate-
respiring bacteria and does not accumulate in solution.109 The
breakdown intermediates ClO3− and ClO2− do not accumulate
to measurable levels (Figure 6.62b).112
In  situ bioremediation via IRZ deployment is the most
economically feasible, fastest, and easiest means of dealing
with perchlorate-laden groundwater at all concentrations.
Microbial transformation of perchlorate to chlorite occurs
in the absence of oxygen as a result of anaerobic respiration.
Implementation of an IRZ with the introduction of easily bio-
degradable electron donors (e.g., acetate, lactate) is highly
effective in reducing dissolved ClO4−. Laboratory column
experiments have demonstrated that perchlorate degradation
can be rapidly achieved at influent levels ranging from 0.1 to
1000 mg/L.109 The effluent levels achieved were in the range
of 0.005 mg/L, which is lower than the state of California
drinking water action level of 0.018 mg/L.
The elevated perchlorate solubility and decades-old age
of many perchlorate plumes can result significant groundwa-
ter plume evolution, specifically within aerobic groundwater
systems where the oxidative poise contributes to ongoing
persistence. Matching an appropriate electron donor that
minimizes overall treatment cost while overcoming naturally
aerobic groundwater conditions is therefore important. There
are many reports in the literature where ethanol, methanol,
acetate, acetic acid, whey, corn syrup, lactate, lactate polymer,
and vegetable oil have all been applied as the source of the
degradable organic carbon to create the mildly reducing IRZs
for perchlorate degradation. As only iron-reducing conditions
are required to achieve complete perchlorate treatment, dos-
ing considerations are often less than what would be other-
wise applied for chlorinated aliphatic dehalogenation.
Two example data sets are provided in Figure 6.62b and c
to reflect the overall magnitude of achievable perchlorate treat-
ment in situ. Both examples demonstrate that complete biodeg-
radation of perchlorate within anaerobic IRZs can be achieved
to cleanup goals within a reasonably short time frame. A com-
parison of TOC concentrations and associated ORP response
for TCE and ClO4− is presented in Figure 6.63. As shown, the
operational basis for implementing perchlorate IRZ applica-
tions is to maintain the redox conditions within the denitrify-
ing to iron-reducing range. Injection frequency, electron donor
selection, and carbon dosing considerations should therefore
be balanced to achieve the required mildly reducing conditions
to achieve ClO4− degradation while avoiding the development
of highly reducing (e.g., sulfate-reducing to methanogenic)
conditions—where treatment can stall. This is reflected in
Figure 6.63, where organic carbon concentrations are signifi-
cantly lower compared to other microbially reducing IRZs.
246 Remediation Engineering

(a)

300,000 35,000 36

30,000
ClO4– concentration (µg L–1)

250,000 Nitrate 30
TOC

Nitrate concentration (mg/L)

TOC concentration (mg/L)
ClO4– 25,000
200,000 Injection event 24
20,000
150,000 18
15,000
100,000 12
10,000

50,000 5,000 6

0 0 0
May-02

May-03
Jun-01
Jul-01
Aug-01
Sep-01
Oct-01
Nov-01
Dec-01
Jan-02
Feb-02
Mar-02
Apr-02

Jun-02
Jul-02
Aug-02
Sep-02
Oct-02
Nov-02
Dec-02
Jan-03
Feb-03
Mar-03
Apr-03

Jun-03
Jul-03
(b) Date

180,000 6000 30

160,000
5000 25
140,000 Nitrate
Nitrate concentration (mg/L)
ClO4– concentration (µg L–1)

TOC concentration (mg/L)

TOC
120,000 ClO4– 4000 20
Injection event
100,000
3000 15
80,000

60,000 2000 10

40,000
1000 5
20,000

0 0 0
May-02

May-03
Sep-01
Oct-01

Dec-01
Jan-02
Feb-02
Mar-02
Apr-02

Jun-02
Jul-02
Aug-02
Sep-02
Oct-02

Dec-02
Jan-03
Feb-03
Mar-03
Apr-03

Jun-03
Jul-03
Nov-01

Nov-02

(c) Date

FIGURE 6.62  (a) Perchlorate. (b) Performance data from an IRZ system for perchlorate degradation. (c) Performance data from an IRZ
system for perchlorate degradation.

Anaerobic reduction can also represent a viable remedial
strategy for perchlorate in soils. While exhibiting a high solu-
bility, perchlorate will adsorb slightly to variable-charge soils
or soils with high anion exchange capacity in low pH envi-
ronments.113 As a result, sites with decades-old perchlorate
impacts may also contain elevated soil impacts in the area
of release. As described further earlier, perchlorate will be
naturally reduced in the presence of natural soil organic
matter, so perchlorate longevity is inversely correlated with
the quantity of native soil organics. Conditions  needed for
Injected Reagent–Based Remedies
TOC (mg/L)
300 TOC (TCE)
200
100
0 0
2 4 6 8
(weeks)
ORP (TCE)
For reductive dechlorination
FIGURE 6.63  Biogeochemical operating principles of an IRZ system for perchlorate degradation.
biodegradation in soils include anaerobic conditions and the
presence of sufficient carbon. The presence of perchlorate-
degrading bacteria is an important factor, as indigenous
perchlorate-degrading microbes take a long time to develop
a population large enough to reduce perchlorate, even when
a carbon source is available.114 Due to the limited natural
occurrence of perchlorate in the environment, the lag time
for microbial species that facilitate perchlorate reduction can
be much longer than the lag time for NO32 reduction in soils
not previously exposed to perchlorate. Growth of microbial
populations able to degrade perchlorate and/or the induction
of enzymes able to degrade perchlorate may strongly affect
whether perchlorate or NO3− is used first as a terminal elec-
tron acceptor.
Engineering perchlorate reduction in vadose zone soils
requires sufficient delivery and infiltration of an organic
carbon source through the area of impact. These applica-
tions can be achieved via delivery points within the vadose
zone or via direct surficial application of carbon substrate.
Above  the saturated zone, it should be expected that grav-
ity infiltration will facilitate downward carbon delivery, and
horizontal transport will be controlled primarily by the soil
strata and degree of lower permeability bedding planes. As
shown in Table  6.15, however, where carbon delivery can
be achieved, treatment extent is similar to that observed in
the dissolved phase. In this example, corn syrup was uti-
lized as the primary carbon substrate and was delivered into
the vadose zone in two different areas to achieve treatment.
Significant to complete degradation was achieved within
these pilot plots within a period of 6 weeks, with extended
treatment benefit ongoing until 19 weeks postapplication.
This pilot study demonstrated that perchlorate contamina-
tion present in soil can be biodegraded in situ by injecting
an appropriate organic carbon and maintaining optimum
biogeochemical conditions.
247
REDOX (mV)
250 mV
200
150
TOC (ClO4–)
100
50
For perchlorate
10 12 14
reduction –50
–100
–)
ORP (ClO4 –150
–200
–250
–300
–350
–400 mV
6.2.3.1.6 Denitrification
Nitrogen can form a variety of compounds due to its differ-
ent oxidation states. In the natural ecosystem, most changes
from one oxidation state to another are biologically induced.
Nitrogen species of primary interest in relation to the subsur-
face environment are provided in Table 6.16.
As detailed in Chapter 2, nitrogen in the environment can
be introduced by many anthropogenic activities in addition to
the natural nitrogen cycling through the environment. Waste
produced by humans and animals are important sources of
nitrogen in any area characterized by significant human or
animal populations. Nitrates from such waste can exhibit the
characteristics of either point or nonpoint source pollution.
Nitrogen is the most common element used as a fertilizer
supplement and other anthropogenic nitrogen sources can be
associated with the testing and usage of explosives and indus-
trial activities and waste discharge. Nitrate’s high solubility
and low sorptivity make it an excellent fertilizer component.
Nitrate is a major element in the manufacture of explosives,
which primarily uses ammonium nitrate as a raw material.
Nitrogen compounds are also used extensively in industrial
settings in the form of anhydrous ammonia, aqua ammonia,
nitric acid, ammonium nitrate, and urea. Plastic manufactur-
ing, metal processing, textile industry, acid production, refrig-
eration, pulp, and paper are some of the industries that use
significant amounts of nitrogen compounds.
The neutral, molecular ammonia exists in equilibrium with
the ammonium ion, the distribution of which depends upon
the pH and temperature of the biogeochemical system; in
fact, very little ammonia exists at pH levels less than neutral.
Transformation of nitrogen compounds can occur through
several mechanisms, including fixation, ammonification, syn-
thesis, nitrification, and denitrification. Ammonification refers
to the change from organic nitrogen to the ammonium form.
In general, ammonification occurs during decomposition of
248 Remediation Engineering

TABLE 6.15
Field Demonstration of Biological Remediation of Perchlorate Present in Soil
Perchlorate Concentrations in Soil (µg kg−1)
Historic Baseline 1 Week 6 Weeks 19 Weeks
Depth (ft bgs) 9/12/2003 12/3/2003 1/7/2004 2/10/2004 5/10/2004
Area 1
5 510 1,800 4,900 2,200 770
10 1,700 250 3,600 3,400 <10
20 310 4,600 4,300 21 <10
30 13,000 170 290 3,700 920
40 100 39 <10 <10 <10
50 — — 10 <10 —
60 — — 11 <10 —
70 — — 16 — —
Totals: 15,620 6,859 13,090 9,321 1,690 89%
Remaining TOC in pore water (mg/L) 2,100 reduction
Perchlorate Concentrations in Soil (µg kg−1)
Baseline 1 Week 6 Weeks 19 Weeks
Depth (ft bgs) 12/3/2003 1/7/2004 2/10/2004 5/10/2004
Area 2
5 85 54 170 <10
10 440 66 23 <10
20 3,200 3,300 <10 <10
30 9,700 330 990 <10
40 <10 <10 <10 <10
50 — <10 <10 —
60 — <10 <10 —
Totals: 13,425 3,750 1,183 0 100%
Remaining TOC in pore water (mg/L) 110 reduction

The transformation reactions are generally coupled and pro-

TABLE 6.16 ceed rapidly to the nitrate form.
Nitrogen Forms Present in the Subsurface Environment In  situ denitrification can be accomplished by organ-
Nitrogen Compound Formula Oxidation State
isms belonging to the genera Micrococcus, Pseudomonas,
Denitrobacillus, Spirillum, Bacillus, Achromobacter,
Ammonia NH3 −3 Acinetobacter, Gluconobacter, Alcaligenes, and Thiobacillus,
Ammonium ion NH4+ −3
which are present in the groundwater environment.
Nitrogen gas N2 0
Denitrifying organisms will utilize nitrate or nitrite in the
Nitrite ion NO2− +3
absence of oxygen as the terminal electron acceptor for their
Nitrate ion NO3− +5
metabolic activity. If any oxygen is present in the environ-
ment, it will probably be used preferentially. The energy
animal and plant tissue and animal fecal matter and can be for the denitrifying reactions is released by organic carbon
expressed as follows: sources that act as electron donors. The microbial pathways
of denitrification include the reduction of nitrate to nitrite and
Organic nitrogen + Ammonifying microorganisms
the subsequent reduction of nitrite to nitrogen gas:
® NH 3 /NH 4 + (6.41) NO3- ® NO2 - ® N 2( g ) (6.43)

Nitrification refers to the biological oxidation of ammonium In biological wastewater treatment processes employing deni-
ions under aerobic conditions by chemoautotrophic nitrifiers. trification, a cheap, external carbon source such as methanol
Two specific chemoautotrophic bacterial genera are involved, (where necessary) is added as the electron donor. It has long
using inorganic carbon as their source of cellular carbon: been known that NO3− can be converted to N2 gas in anaerobic
NH 4 + + O2 (Nitrosomonas) groundwater zones in the presence of a labile carbon source.
In situ microbial denitrification is based on the same prin-
® NO2 - + O2 (Nitrobacter ) ® NO3- (6.42) ciple as conventional biological wastewater treatment systems,
Injected Reagent–Based Remedies
except that it is carried out in the subsurface by injecting the
appropriate organic carbon source. Since methanol could be an
objectionable substrate from a regulatory point of view, any of
the soluble or semisoluble carbon substrates shown in Table 6.9
could be injected to accelerate the rate of denitrification and con-
vert nitrate to nitrogen gas within the reactive zone. Within the
hierarchy of redox reactions, NO3− is the most favored electron
acceptor after dissolved oxygen. Similar to perchlorate reduc-
tion discussed earlier, nitrate reduction only requires mildly
reducing conditions and the degree of carbon loading and sub-
strate selection are expected to be considerably lower than that
required for chlorinated aliphatic reduction. Hence, considerable
attention should be focused in maintaining the redox potential in
the optimum range in order to eliminate electron donor scaveng-
ing for use in supporting Mn(IV), Fe(III), or sulfate reduction.
6.2.3.2  Anaerobic Oxidation
Source zones associated with organic contaminants such as
petroleum, ketones, or other nonchlorinated aromatics serve
as large reservoirs of electron donor that are utilized by indig-
enous microorganisms in the presence of naturally available
electron acceptors. The rapid depletion of available dissolved
oxygen drives the microbial community to utilize substitute
electron acceptors including nitrate, Mn(VI), Fe(III), and
sulfate, which result in highly anaerobic and methanogenic
conditions. This redox sequence for biological oxidation is
sometimes referred to as oxic (aerobic), suboxic (denitrifi-
cation, manganese reduction), and anoxic (iron reduction,
sulfate reduction, and methanogenesis) conditions.115 Of the
nonoxygen electron acceptors, sulfate represents the domi-
nant terminal electron acceptor process, is often the natural
electron acceptor in largest supply, and accounts for approxi-
mately 70% of the natural biodegradation capacity.46
TABLE 6.17
Comparison of Various Electron Acceptors and Their Potential to Degrade Benzene
Reaction Yield:
Effective Maximum Benzene Degraded
Concentration in per Unit Mass
Electron Acceptor Water (mg/L) Electron Acceptor
Oxygen (ambient air) 9–10 0.33
Oxygen (pure) 60–70 0.33
Nitrate 670,000 (NaNO3) 0.21
1.1 × 105 (Mg(NO3)2)
Iron (III) 0–1 0.024
Sulfate 48,000 (Na2SO4) 0.22
140,000 (MgSO4)
Source: Leahy, J.G. and Colwell, R.R., Microbiol. Rev., 52(3), 305, 1990.
249
There are a number of advantages to applying anaerobic
biological oxidation (ABOx) systems as part of an IRZ rem-
edy. Electron acceptor reagents such as nitrate and sulfate have
high aqueous solubilities and are therefore considerably easier
to deliver at elevated doses into the reactive zone. As shown in
Table 6.17, the comparative solubility between these reagents
and oxygen is significant, which can eliminate the need for a
sustained delivery methodology as described previously for aer-
obic treatment applications. Table 6.17 also provides a summary
of the stoichiometric relationship of benzene mass mineralized
per unit mass of each electron acceptor and the corresponding
biodegradation yield that could theoretically be realized based
on the achievable dissolved electron acceptor concentrations.
The elevated feasible concentrations that can be achieved with
sulfate result in an oxidizing payload that is orders of magnitude
larger than oxygen-based systems, with only a secondary maxi-
mum contaminant level (MCL) to be aware of in terms of resid-
ual sulfate concentrations. While the solubility limits reflected
in Table 6.17 are intended to provide a relative comparison
between feasible electron acceptor dosing, this magnitude is not
always applied in field-scale engineered systems. Instead, dos-
ing strategies seek to generally maintain concentrations within a
target range to achieve enhanced treatment rates.
The relationship between rate-limiting substrate concen-
trations (S) and the overall reaction rate (v) is provided for
sulfate-based oxidation reactions in Figure 6.64. Classical
microbial kinetic analyses show that at lower concentrations
of a rate-limiting substrate, the microbial-mediated rate of
reaction proceeds as first order.21 As the concentration of the
rate-limiting substrate is increased, v will approach zero order
where the rate of reaction is no longer dependent on substrate
concentration. Engineered systems that increase sulfate avail-
ability can enhance the rate of PHC oxidation by more than
Potential
Maximum
Benzene
Degraded (mg/L) Potential Complications
3.0–3.3 • Limited solubility
19.8–23.1 • Numerous nontarget scavengers
• Potential aquifer clogging through
biofouling and precipitation of iron
140,000 • Primary MCL of 10 mg/L NO3-N
220,000 (45 mg/L NO3)
0–0.024 • Not practical to inject—very low
solubility at neutral aquifer pH
9,000 • Secondary MCL for sulfate—250 mg/L
25,000 • Hydrogen sulfide produced as a
by-product; rarely documented as an
issue in the field
250
vmax
v (mg/L/day)
No longer
Sulfate limited sulfate limited
~2000 mg/LSO42–
[S] (mg/L)
FIGURE 6.64  The relationship between rate-limiting substrate
concentration (S) and overall reaction rate (v) in microbially medi-
ated reactions. Rate-limiting sulfate concentrations based on kinetic
data presented in Reference 108.
one order of magnitude above intrinsic or nonengineered
conditions. Generally, the recommended minimum threshold
sulfate concentration to sustain treatment is approximately
100 mg/L, equivalent to the concentration at which microor-
ganisms conduct intercellular sulfate storage and operate most
efficiently (Habicht et al., 2005). As indicated in Figure 6.64,
increased reaction rates are observed up to a maximum sul-
fate concentration of approximately 2000 mg/L, above which
excess sulfate concentrations do not result in an overall change
in oxidation rate.
Other advantages of sulfate or nitrate addition to ground-
water systems include the lack of scavenging reactions that
play a significant role in aerobic treatment applications.116
These reagents are resistant to abiotic reactions and are uti-
lized by a variety of nitrate- or sulfate-reducing bacteria that
are generally ubiquitous and able to metabolize the organic
contaminants. Further, sulfate-reducing bacteria are prolific
and capable of metabolizing broad classes of PHCs.21 As a
remediation reagent, low-cost sulfate or nitrate salts are com-
mercially available at the industrial scale.
6.2.3.2.1 Biogeochemistry
While nitrate, Mn(VI), Fe(III), and sulfate can all be used as
electron acceptors to support anaerobic oxidation processes,
nitrate and sulfate represent the most applicable reagents for
engineered injection application due to their high solubility
and low relative cost (Figure 6.65). More importantly, neither
of these species adds to the pool of reduced metals that can
precipitate within the IRZ and limit overall injectability. Both
Mn(VI) and Fe(III) represent electron acceptors that will
contribute to the collective anaerobic oxidation processes, but
these are generally avoided during injection applications due
to precipitate formation. With both nitrate and sulfate serv-
ing as the electron acceptors, the mineralization of benzene is
given by Equations 6.44 and 6.45 at neutral pH:
- +
C6H 6 + 6NO + 6H ® 6CO2 + 3N 2 + 6H 2O (6.44)
3 (6.47)
Remediation Engineering
Injection of NO3–, SO42–, and (O2 if necessary)
NO3– NO3– SO42–
SO42– SO 2–
4
(O2)
BTEX contamination
FIGURE 6.65  Expected biogeochemical zones during the injec-
tion of NO3−, SO42−, and O2 for microbial oxidation of BTEX
compounds.
C6H 6 + 3.75SO24 - + H 2O
® 1.875H 2S + 1.875HS- + 6HCO3- + 0.375H + (6.45)
Sulfate reduction produces reactive sulfide (i.e., H2S and HS−
from Equation 6.45). If not controlled, the accumulation of
reactive sulfide can eventually become inhibitory to sulfate-
reducing bacteria. In situ, sulfide inhibition has been reported
to reduce the rate of sulfate reduction by approximately one-
third at concentrations between 8.5 and 320 milligrams per
liter (mg/L).117 This chemistry reflects the fact that the utiliza-
tion of sulfate to support the ABOx process can have a variety
of geochemical secondary effects that must be understood to
best implement the technology. If not adequately understood
and accounted for, these geochemical factors can limit the
effectiveness of the technology.
In general, the specific concentration range at which hydro-
gen sulfide will be inhibitory is likely tied to the site-specific
microbial community and site-specific geochemistry. There
are a number of natural mechanisms that help suppress sul-
fide accumulation, the most predominant of which involves
direct reaction with naturally occurring iron from the soil
matrix. Naturally occurring iron will help support sulfide
control in two ways: (1) through direct oxidation–reduction
reactions between iron in the aquifer soils and the sulfide,
where sulfide is oxidized (primarily to elemental sulfur) and
the iron is reduced to ferrous form (Fe2+), and (2) through
the formation and precipitation of iron sulfide precipitates
by the reaction of sulfide with available ferrous iron. Several
of the mechanisms serving as sulfide sinks are shown in the
following equations:
- -
4Fe(OH)3 (s) + 3H 2S + 3HS ® 2S + 4FeS(s) + 9H 2O + 3OH
0
 (6.46)
- 2+ -
4Fe(OH)3 (s) + 3H 2S + 3HS ® 2S + 4Fe + 3H 2O + 9OH
0
Injected Reagent–Based Remedies
4Fe(OH)3 (s) + 1.28H 2S + 1.28HS- + 3.48HCO3-
® 2S0 + 0.52FeS(s) + 3.43FeCO3 + 7H 2O + 4.72OH - (6.48)
Ultimately, the ability to suppress sulfide accumulation will
be a balance between the rate of its production and the rate
of its reactions. Based on the natural abundance of iron in
the subsurface, and assuming a reasonable level of control on
sulfate dosing, the accumulation of sulfide will be limited at
most sites; observed sulfide concentrations within the reac-
tive zone have been generally less than 1–10 mg/L, with some
sites maintaining nondetected sulfide concentrations through
intrinsic control (i.e., Equations 6.46 through 6.48) following
repeat sulfate applications.
In addition, sulfide oxidation in the presence of oxygen
can be very rapid, with half-lives in the order of minutes to
a few hours.116 So, while iron-related reactions generally rep-
resent the dominant mechanism for sulfide control within the
biologically active zone, outside of that zone, the presence of
oxygen (or nitrate) adds another mechanism that will limit its
persistence.118
As indicated in Equation 6.45 describing the anaero-
bic oxidation of benzene, the anaerobic metabolism of PHC
yields alkalinity in the form of bicarbonate. This bicarbon-
ate will neutralize acidity in the aquifer, building up alkalin-
ity and likely raising the pH of the groundwater system over
time. These effects can support the precipitation of calcite
(calcium carbonate), which if not managed can lead to perma-
nent reductions in aquifer permeability. An uncontrolled rise
in alkalinity and aquifer pH can also inhibit the activity of
sulfate-reducing bacteria. The optimal pH range for sulfate-
reducing bacteria is generally between 7.5 and 8, with inhibi-
tion effects observed at values outside of the 5.5–9 range.119
Potential pH excursions (i.e., greater than 9) have been
observed at ABOx sites with limited ambient buffering capac-
ity. As with sulfide accumulation, short-term pH excursions
will be a balance between the rate of alkalinity production
and the rate of its neutralization.
The introduction of soluble sulfate salts will result in a
buildup of TDS and increased ionic strength within the reac-
tive zone. The increase in TDS can cause density-driven
migration of injection solutions downward, which should
be considered in the delivery design, and can also act as a
stressor to the microbial community, reducing overall treat-
ment efficiency. TDS is also used as a qualifying parameter
to designate drinking water supply aquifers. While the rela-
tive loading of TDS from injection locations will be diluted
with bulk groundwater within the aquifer and will decline
with distance away from the injection points, changes in TDS
concentration as a result of electron acceptor loading should
still be considered when the aquifer being treated is intended
for beneficial reuse.
In addition to the iron sulfate relationships, calcium-rich
aquifer systems can contribute to near instantaneous pre-
cipitation of gypsum solids following injection, where the
sulfate concentrations being applied lead to an exceedance
of the saturation index for that mineral. While gypsum is
251
highly soluble and will still be a viable source of sulfate
to sulfate-reducing bacteria, the precipitation of significant
amounts of gypsum can result in temporary reductions in
aquifer permeability that limit the ability to conduct effec-
tive repeat injections. Calcium ion relationships can also
represent a potential issue when excess sulfate loads are
being applied in contact with subgrade concrete structures
(building footers, subway infrastructure, sewer systems).
The sulfate concentrations expected during ABOx imple-
mentation typically lie in the moderate (150–1,500 ppm) to
severe (1,500–10,000 ppm) corrosion environment based
on ACI 201.2R-92 classification.120 The sulfate anion reacts
with hydration products present in hardened cement (e.g.,
tricalcium aluminate (3CaO · Al2O3), calcium hydroxide
(Ca(OH)2), and silicate hydrate) to form two reaction prod-
ucts: ettringite and gypsum (CaSO 4 · 2H 2O). The formation
of ettringite causes an approximate twofold increase in con-
crete matrix volume and leads to the physical expansion and
cracking of the hardened concrete. The process can result
in a reduction of the concrete’s mechanical properties (load
carrying capacity)121 and can lead to failure and collapse
of the concrete structure. While these deleterious reactions
can be cause for concern (or consideration of alternative
remedies) when subgrade concrete materials are present,
sulfate-resistant concretes are used in many coastal envi-
ronments and these concerns are generally more significant
when the concrete in place is considerably aged. Further,
these reactions occur on the concrete surface, so the degree
of concrete permeability is generally more important than
weathering reactions.
6.2.3.2.2  Petroleum Hydrocarbons
Traditional methods of remediating PHCs and other biologi-
cally oxidizable contaminants have historically focused on
strategies employing volatilization (i.e., in  situ air sparging
and soil vapor extraction) and/or aerobic biodegradation of the
water-soluble fraction of residual mass. As discussed earlier,
many PHC-impacted sites are associated with former leaking
USTs or bulk fuel terminals, from which considerably PHC
mass and LNAPL were released. The anaerobic conditions—
frequently methanogenic within the source area—developed
over time results in an established microbial community and
geochemical environment that is already conducive to ABOx
treatment. PHC degradation via ABOx pathways has been
reported in the literature for well over 30 years with the initial
focus on PHC releases in marine environments122 and more
recently in soil systems.123,124
Most PHC plumes that persist following source removal
are usually the result of residual mass present within a “smear
zone” located at or near the water table. Therefore, a viable
remedial strategy must be capable of addressing both the dis-
solved-phase PHCs and residual source mass. Through effec-
tive bio-oxidation of the water-soluble fraction and through
expedited “weathering” of residual source mass, ABOx has
been found to be effective as a polishing remedial approach
in achieving groundwater compliance concentrations. While
it can be effective in the dissolved phase, ABOx remedies
252
are generally not applicable for LNAPL or residual LNAPL.
While IRZ remedies can be effective for chlorinated aliphatic
DNAPLs (which are submerged beneath the water table),
LNAPL materials are by definition lighter than water and
large fractions of this source mass typically reside at or above
the groundwater interface. As a result, injection-based reme-
dies deployed for PHC source treatment fail to achieve contact
with the bulk source mass and require extended operation to
account for the slow rate of dissolution between the LNAPL
and dissolved phase. Even sites with elevated dissolved-phase
concentrations should be evaluated carefully as elevated aque-
ous concentrations are definitive indication of unidentified (or
identified) LNAPL presence. Based on experience deploying
ABOx remedies, threshold aqueous concentrations for typical
PHC indicator compounds that should be cause for careful
consideration include benzene (>3 mg/L), toluene (25 mg/L),
and xylene (>15 mg/L).
As in all biologically mediated treatment approaches, select-
ing the most cost-effective means by which to provide a steady,
sustained source of reagent within the target treatment area
is critical to success. Delivery strategies must account for the
site-specific rate of depletion to sustain sulfate concentrations
within a targeted range, in the targeted area of PHC impacts.
Dissolved-phase delivery mechanisms via batch injections into
permanent wells, groundwater recirculation via injection and
extraction wells, direct-push injection via temporary points,
and solid-phase application via placement in open excavations
or direct application of sulfate to the ground surface are all
potentially viable sulfate delivery strategies.
Achieving sustained electron acceptor availability is
an essential part of promoting ABOx treatment processes.
Typical half-lives for sulfate generally fall between 20 and
40 days at the onset of treatment application but will decrease
over time (10–20 days) as sulfate-reducing bacteria respond to
ongoing delivery. For nitrate, these half-lives are often shorter
and similar to other injection designs discussed in Section
6.1.4, the delivery program must balance the rate of electron
acceptor consumption, the rate of groundwater transport and
washout from the injection area, and the required minimum
concentration necessary to sustain treatment. There are some
nuances to ABOx injection program designs that are different
from those associated with chlorinated aliphatics. Due to the
relative difference in Koc values between PHC compounds
and TCE, for example, the degree of sorbed PHC mass within
a groundwater plume will be significantly greater than that
for TCE. The reduced half-life of sulfate and presence of sig-
nificantly higher sorbed mass diminishes the applicability of
pulse-and-drift or barrier-based injection strategies. Instead,
most sulfate delivery applications require wells on much
closer spacing that are more aligned with the example pro-
vided in Figure 6.13d.
Several nitrate-based products have been used to sup-
port ABOx treatment applications. These include calcium
nitrate, sodium nitrate, and ammonium nitrate, which are
often delivered at dissolved NO3− concentrations between
1000 and 3000 mg/L. For sulfate-based treatment applica-
tions, the most commonly applied substrates are magnesium
Remediation Engineering
sulfate heptahydrate (Epsom salt) or calcium sulfate dihydrate
(gypsum). While both serve as a source of dissolved sulfate,
there are considerable differences in their relative solubilities.
Epsom salt is readily dissolved and exhibits a solubility of
approximately 140 g/L at 20°C, where gypsum solubility is
approximately 2.5 g/L at 20°C. This significant contrast in
solubility affects considerations of how these materials are
best applied. Epsom salt is the preferred sulfate source for
well-based injection applications and must be periodically
reinjected over time to sustain concentrations in the IRZ.
Comparatively, gypsum is more applicable for slurried type
application (direct-push injection) or open-hole mixing where
its low solubility supports an extended sulfate supply as the
solid materials dissolve.
6.2.3.2.2.1  Degradation Pathways  At fuel release
sites, aromatic hydrocarbons (i.e., BTEX) and higher-
molecular-weight dissolved hydrocarbons (e.g., total petro-
leum hydrocarbon (TPH)-gasoline range organics [GRO],
TPH-diesel range organics [DRO]) serve as the collective
target compounds for bio-oxidation processes. In unweath-
ered gasoline, the total concentration of BTEX constituents
represents approximately 10 to 15% of the overall volume,
so the broad range of dissolved hydrocarbons present will be
significantly higher than that of BTEX. While many of these
broad-range PHCs are unregulated (outside of TPH analy-
ses, where required), they do serve as an electron donor
and a significant sink for applied electron acceptors—thus
reducing the sulfate available for BTEX transformation.
When present, sulfate utilized to deplete higher-weight con-
stituents will generate increasing quantities of lower-weight
molecules. In the application of ABOx for the treatment of
TPH-DRO, a review of TPH chromatograms of samples influ-
enced by ABOx processes shows a compositional shift of the
TPH-DRO constituents towards lighter partially oxidized
molecules.125 TPH-DRO composition is initially observed as
being dominated by compounds with longer gas chromato-
graph (GC) retention times and higher molecular weight.
Over time with exposure to ABOx processes, the TPH-DRO
composition comprises compounds with shorter GC retention
times and lower molecular weights. Many of these nondiffer-
entiated dissolved hydrocarbon compounds are not quantified
individually in standard compound-specific analyses but may
be captured in bulk compound analyses (e.g., TPH-GRO and
TPH-DRO). While the bulk concentration results may indi-
cate that hydrocarbon concentrations are relatively unchanged
(or slowly declining) in an engineered ABOx system, analysis
of the GCs can be used as qualitative indicators that degra-
dation and transformation of these compounds are ongoing.
There are also several degradation intermediates that might
offer direct evidence of biological transformations (i.e., phe-
nol for benzene, cresol for toluene).
Where aerobic degradation pathways include an initial
dioxygenase step, anaerobic microorganisms generally per-
form one of four general enzymatic activation steps: (1) the
addition of fumarate to form aromatic-substituted succinates,
(2) methylation, (3) hydroxylation via a dehydrogenase, or
Injected Reagent–Based Remedies
OH OH COO
2HO• –COO–
CO2
H2O OH–
COO–
FIGURE 6.66  Benzene transformation via anaerobic oxidation
mechanisms.
(4) carboxylation. Each of these steps transforms the primary
aromatic molecule into different metabolic intermediates,
which can include phenol, benzoate, or the corresponding
coenzyme A form, following which enzymatic ring cleav-
age produces 3-acetyl CoA and CO2.126 The starting step and
transformation intermediates will vary based on the aromatic
compound, the microbial species mediating the transforma-
tion, and the specific electron acceptor(s) used.
Based on its structure and the significant activation energy
required to remove hydrogen from the aromatic ring, benzene
is the most thermodynamically stable of the BTEX compounds
under anaerobic conditions. Benzene transformation has been
documented through hydroxylation, methylation, and car-
boxylation activation steps, following which transformation
occurs via benzoyl-CoA (Figure 6.66). While all three have
been documented, determination of the exact transformation
steps has been hampered by the inability to isolate individual
hydrocarbon degraders that rely on the broader anaerobic
consortia for syntrophic interaction.127 While several strains
have been identified that mediate complete mineralization,
these organisms represent a glimpse into one degradation
pathway—knowing that broader consortia cooperation facili-
tates other combinations of oxidation mechanisms.
Even for toluene, which represents the most readily degrad-
able and most widely studied BTEX compound under aerobic
and anaerobic conditions, our understanding of the specific
degradation pathways is complicated by the participation
of the microbial consortium in the various metabolic steps.
One model presented includes a combination of a syntroph, a
homoacetogen, an acetoclastic methanogen, and a hydrogeno-
trophic methanogen; but select single species have been iden-
tified that perform mineralization through CO2. The toluene
degradation pathway is initiated by the addition of fumarate
to the methyl group to yield benzyl-succinate, following which
the benzyl-succinate intermediate is oxidized to eventually
form benzoyl-CoA. This same fumarate activation pathway
is typically observed for both xylenes and ethylbenzene, with
hydroxylation also reported for ethylbenzene.127 Of the xylene
isomers (ortho-, meta-, and para-), both p-xylene and m-xylene
are more susceptible to degradation and will exhibit faster loss
from hydrocarbon source zones and dissolved-phase plumes.
Comparison of the relative shift in concentration ratios
between these three isomers can therefore be an assessment
technique in confirming that biodegradation is ongoing.
6.2.3.2.2.2  Microorganisms  Widespread research con-
ducted over the past four decades has been effective in iden-
tifying the variety of microorganisms responsible for aerobic
253
PHC degradation and the various mechanisms that they per-
form. While the majority of research has historically focused
on aerobic pathways, focus during the past two decades has
turned toward the microorganisms that facilitate anaerobic
PHC metabolism. This research is of great interest, in that
the majority of PHC-contaminated sites are naturally highly
anaerobic and these organisms perform the bulk of the heavy
lifting responsible for natural source zone depletion and atten-
uation processes. As highlighted in the preceding section, the
phylogenetic and physiological diversity of these communities
is broad, and these species are active in the presence of a wide
range of potential electron donors (advantageous considering
the variability of PHC compounds), pH conditions, salinity,
and temperature.128 Extensive reviews of PHC metabolism and
the microbial communities responsible have been conducted,
and readers are urged to consult these resources for a fully
informed perspective on the microbial diversity and primary
transformation pathways that have been identified.127–131 As
new microbial strains continue to be identified, this resource
will not do justice to the volumes of research developed to
date and that which continues to emerge.
The wide array of PHC molecules present in a given petro-
leum source material is matched and far exceeded by the
array of microorganisms that can degrade them. The impor-
tant awareness that any reader should have is that while bac-
terial genera that perform nitrate, iron, and sulfate reduction
and methanogens are generally ubiquitous, the microbial
community performing PHC metabolism will be site spe-
cific. Therefore, while it has been a challenge to glean the
specific transformation pathways and grow these organisms
in enriched culture lab experiments, we should be aware that
each given site will have a somewhat individualized and com-
plicated fingerprint of PHC species and transformation mech-
anisms. As an example, any given site could include Azoarcus
or Dechloromonas strains that can completely mineralize the
benzene ring; Geobacteraceae species that perform similar
or cooperative mechanisms under iron-reducing conditions;
Desulfovibrio, Desulfotomaculum, and Desulfobacteraceae
species that utilize sulfate as the ultimate electron accep-
tor of energy metabolism126,127; or Methanosaeta and
Methanospirillum methanogens.127 As a result, understand-
ing the individual species becomes less important com-
pared to contaminants like chlorinated aliphatics—where
one organism (Dehalococcoides) is responsible for complete
transformation.
From an engineering design standpoint, we therefore focus
on which electron acceptors will provide the broadest over-
all benefit to stimulate the native microbial consortium into
achieving treatment objectives. The naturally present anaer-
obic conditions are beneficial from an ABOx remediation
standpoint, as the nitrate-, iron-, or sulfate-reducing bacte-
ria and methanogenic communities can readily utilize these
electron acceptors in an IRZ application. These communities
are preprimed to respond to electron acceptor influx, which
limits the overall lag time associated with microbial stimu-
lation and acclimation and can expedite treatment success.
Even where baseline site biogeochemical characterization
254
data suggest little to no sulfate reduction activity occurring,
field results show successful microbial community stimula-
tion within 45  days of electron acceptor addition, which is
consistent with sulfate-reducing microbial lag times reported
in the literature.117,132–134
6.2.3.2.2.3  Monitoring  The objectives of individual ABOx
performance monitoring programs will differ based on the pri-
mary objectives and sampling needs to assess treatment and
optimize future applications (e.g., reagent dosing, injection fre-
quency). All are generally consistent in that they require assess-
ment of contaminant concentrations to document changes over
time and supporting biogeochemical lines of evidence that sup-
port assessment of electron acceptor distribution, longevity, and
utilization in mediating ABOx treatment mechanisms.
In general for all data sets, a baseline sampling event (prior
to and within approximately one month of an injection) is
important. This sampling event (or multiple events) is used
to assess the geochemical conditions and identify nuances in
reduced groundwater poise within the source areas and down-
gradient plume footprint. These programs often include at least
three to five wells (based on site specifics) that are strategi-
cally positioned upgradient, within, and downgradient of the
source such that a geochemical conceptual model can be identi-
fied to understand the relative abundance of terminal electron
acceptors in native groundwater and within the area of impact.
Ideally, monitoring wells with elongated data sets are prefer-
able as they provide relative insights into the degree of naturally
occurring degradation processes over  time—which the geo-
chemical CSM then builds upon. A summary of the key ana-
lytical and field sampling parameters is provided in Table 6.18.
TABLE 6.18
Sample Monitoring Program for ABOx Treatment
Applications
Baseline Primary Secondary
Contaminants (BTEX, TPH,a Contaminants Carbon dioxide
MTBE, TBA) Nitratec TKN
Nitrate Sulfatec TOC
Ferrous iron (field filtered) Sulfide Manganese
Manganese (field filtered) Ferrous iron (field (field filtered)
Sulfate filtered) Methane
Sulfide Unique reagent- Alkalinity
Methane related tracersb
Alkalinity
Unique reagent-related tracersb
Field parameters Field parameters Field parameters
Note: Field parameters include ORP, DO, pH, temperature, specific con-
ductivity, and turbidity.
a Performing TPH-G and TPH-D analyses with and without use of a silica
gel cleanup column can be highly advantageous in assessing the relative
contribution of partially degraded polar TPH constituents and unweath-
ered nonpolar (or native) TPH materials.
b Generally the complementary cation for electron acceptor material.
c Depending on use as the primary treatment electron acceptor.
Remediation Engineering
Assessing the relative changes in contaminant concentra-
tions (BTEX, TPH species) can be done with an eye on the
expected order of overall biodegradability. Historical research
indicates that BTEX constituents generally degrade in the fol-
lowing order: toluene and o-xylene; p-xylene and m-xylene;
ethylbenzene; and benzene (from most to least susceptible).
While the relative abundance of these materials will be unique
to different gasoline formulations, these constituents degrade
at different rates and will exhibit relative shifts as part of
naturally occurring biodegradation or once IRZ treatment is
underway. It is therefore important to evaluate each constitu-
ent separately rather than looking at trends in “total BTEX” or
“total unleaded gasoline (ULG)” constituents, for example. As
described earlier, even if declines in TPH-GRO and TPH-DRO
bulk parameter concentrations are not observed during active
treatment, shifts in the composition of the TPH-DRO signature
is expected which may be masked by the variety of molecules
quantified with this sampling method. Partial and incomplete
oxidation of TPH molecules will result in the enrichment of
smaller compounds with shorter GC elution times. As identi-
fied in Table 6.18, for sites requiring TPH-G and TPH-D analy-
ses, running samples with and without a silica gel cleanup step
at the analytical laboratory can be a highly effective means
to assess the relative contributions of polar PHC compounds
that are partially degraded (containing hydroxyl, carboxyl, or
other polar ligands) and contribute to the overall TPH bulk
parameter measurement. Native, unweathered PHC materials
are exhibited to contain no polar subgroups and would still be
captured as part of the sampling response. So while the bulk
TPH parameter measurements may not change significantly at
the onset of treatment, the silica gel cleanup method can quan-
tify the fraction of hydrocarbon mass that has been subjected
to at least partial degradation. A comparison of these data over
time can then be used to assess the relative extent of unweath-
ered LNAPL source material.
Following initiation of injection activities, data should be
collected at least quarterly to support performance assessment
and treatment response. More frequent sampling can also be
used at the outset of treatment to confirm electron acceptor
longevity, distribution, and transport away from the injec-
tion wells. In general, the operational monitoring analytes
are typically fewer than those sampled as part of the baseline
activities and should be focused on the key decision-making
parameters (i.e., contaminant concentrations, selected elec-
tron acceptor cation and anions) to guide future operations
(Table 6.18).
A typical injection frequency for PHC-impacted sites is
one injection every two months. Site-specific injection fre-
quencies should be based on the electron acceptor utilization
half-life, which can be calculated after the first injection has
been completed using the in situ starting concentration (C0)
and at least one postinjection data point (C at a given postin-
jection time t). As the rate of electron acceptor utilization can
change over time, performing this evaluation using each indi-
vidual sampling event can be advantageous to adapt the injec-
tion program accordingly. Similar to this assessment, relative
comparisons between the electron acceptor anion (nitrate or
Injected Reagent–Based Remedies
sulfate) and their associated cation (sodium, calcium, mag-
nesium) can also be a valuable method to evaluate the rate of
utilization versus dilution in the subsurface. While both will
be diluted over time with advective groundwater flow, prefer-
ential depletion of the electron acceptor compared to its cation
provides further utilization information and supports distri-
bution assessment in the subsurface. It should be noted that
this assessment is somewhat qualitative, given that dissolved
metal species are not inert tracers and would be expected to
react with the subsurface soil geochemistry and precipitate.
Other supporting parameters that are beneficial to include
are sulfide (for sulfate-based delivery strategies) to confirm
that sustained accumulation is not occurring, which could
otherwise reduce microbial performance. As sulfide will pre-
cipitate in the presence of ferrous iron, both of these ions are
valuable to assess overall geochemical change—or to iden-
tify mitigation steps, if warranted. Nutrient analysis for TKN
and TOC can be valuable as secondary assessment criteria to
ensure that nutrients and carbon sources are within accept-
able ranges to support biostimulation. Generally, if TKN is
less than 5 mg/L, a nitrogen amendment may be considered
so that nitrogen is not a potential limiting nutrient. Analytical
results of TOC that are less than approximately 10 mg/L may
imply carbon substrate limitation to biological growth, poten-
tially limiting the extent or efficiency of ABOx treatment.
6.2.3.2.3  Fuel Oxygenates
Like many contaminants discussed in this section, MTBE
was originally thought to be completely resistant to biodegra-
dation due to the tertiary carbon structure and ether linkage.
As research paid closer attention, however, MTBE biological
oxidation was observed under both aerobic and anaerobic con-
ditions. Like other oxygen-based treatment strategies, MTBE
degradation occurs faster than anaerobic biodegradation.
Early studies that focused on anaerobic biodegradation of
MTBE were somewhat inconclusive but led to a general specu-
lation that MTBE will not biodegrade in the absence of oxy-
gen. While additional work has been conducted to demonstrate
that MTBE can biodegrade under nitrate-reducing, Mn(VI)-
reducing, Fe(III)-reducing, sulfate-reducing, and methano-
genic conditions, the pile of research is still significantly
smaller than that available for aerobic MTBE degradation
(Haggblom reports 12 studies conducted between 1993 and
2007135). While MTBE degradation has been reported under
these various conditions, there is considerable inconsistency in
the research conducted, which demonstrates that degradation
pathways are highly site specific. Some studies have shown
MTBE mineralization concurrent with nitrate reduction, but
not under sulfate-reducing or methanogenic conditions.136
Others have shown MTBE degradation concurrent with sulfate
reduction, but not under methanogenic, nitrate-reducing, or
Fe(III)-reducing conditions.137 The body of the science there-
fore points to site-specific consortia that are uniquely adapted
to MTBE utilization, and we still have limited information
pertaining to the specific microorganisms responsible.43,135
Under anaerobic conditions, MTBE loss is coupled with
stoichiometric increases in TBA, suggesting that initial
255
transformation is similar for aerobic and anaerobic pathways.
Transformation of MTBE to TBA occurs via demethylation,
removing the terminal methyl group to produce an alcohol.
TBA is subsequently converted to 2-hydroxy-isobutyric acid
(HIBA), which is then converted via several alternative inter-
mediate pathways leading to either acetyl-CoA or pyruvate,
which are funneled into the microbial Krebs cycle. TBA
degradation has been reported across different reducing con-
ditions, but this degradation step is not known to be energy
yielding, occurs cometabolically, and therefore requires a
supplemental growth substrate. This is not likely to be an
issue in gasoline site source areas, where residual PHC mate-
rials can fulfill this need, but portions of dissolved plumes
that are depleted of hydrocarbon contaminants or at sites
containing only MTBE and TBA, extensive lag times may
be observed for TBA degradation. The fermentation of TBA
is feasible based on the relative energetics, with free energy
yield (∆rG°(w)) values determined to be relatively similar
between oxygen (−2659 kJ) and nitrate (−2360 kJ) compared
to ferric iron (−814 kJ), sulfate (−171 kJ), or methanogenesis
(−72.06)138; but 14C isotopic studies have documented that the
methane generated from TBA fermentation under sulfate-
reducing to methanogenic conditions was considerably lower
than that anticipated based on the TBA loss observed.139
The natural conversion of MTBE to TBA under anaero-
bic conditions in many PHC-contaminated sites demon-
strates that ABOx applications are appropriate where MTBE
is a primary regulatory driver. As TBA degradation can be
highly site specific and dependent on the presence of an
alternative carbon source for microbial growth, stand-alone
ABOx treatment should be considered carefully and weighed
against alternative TBA treatment remedies (e.g., aerobic
biodegradation)—particularly in cases where the TBA plume
is detached from the source area and organic carbon con-
centrations in groundwater are limited. TBA does not have
a federal MCL within the United States and has an identi-
fied cleanup standard in only a minority of U.S. states. As
aerobic degradation mechanisms occur far more readily than
anaerobic steps (and are in some cases energy yielding), the
background dissolved oxygen concentration along the distal
toe of the PHC plume can be sufficient to control the plume
and limit overall transport.140
As MTBE and TBA are most frequently encountered in
PHC sites, the sample monitoring program proposed within
Table 6.18 is generally appropriate for anaerobic applications.
For aerobic applications, Table 6.18 is also appropriate.
6.2.4 Cometabolic Degradation
As detailed in the preceding sections, cometabolic degrada-
tion processes can play a significant role in contaminant trans-
formation. Cometabolic processes involve the degradation of
the contaminant by an enzyme produced by the microorgan-
ism for another reason, resulting in fortuitous degradation
of the contaminant with no direct benefit for the responsible
organism. These processes are related to the broad spectrum
of metabolic reactions carried out by microbial consortia and
256
the limited specificity of some primary enzymes produced
during these processes. This section captures some notable
cometabolic interactions, the contaminants affected, and their
relative contributions to aerobic or anaerobic IRZ treatment
applications.
As discussed earlier, organisms capable of aerobically
degrading contaminants such as PHCs do so through the pro-
duction of dioxygenase or monooxygenase enzymes. These
enzymes can support the transformation of MTBE to TBA
and subsequent TBA mineralization, and these are the pri-
mary mediating species for 1,4-dioxane treatment (discussed
further in the following). These can also fortuitously oxidize
a variety of different chlorinated contaminants by producing
unstable chlorinated epoxides that will quickly break down
via abiotic processes. Aerobic organisms that utilize phenol,
toluene, methane, ethane/ethene, propane/propene, butane,
isoprene, isopropylbenzene, and ammonia as primary growth
substrates produce the mono- and dioxygenase enzymes,
which result in cometabolic degradation of chlorinated eth-
enes.141,142 As many of these are encountered in PHC sites, it is
not uncommon for aerobic IRZ application for petroleum con-
tamination to also provide some chlorinated aliphatic treat-
ment in mixed contaminant plumes or source areas. Several
chlorinated hydrocarbons can also be utilized as growth sub-
strates for these processes including VC and chlorobenzene.142
Toluene, phenol, and cresol oxidizers, such as Pseudomonas
putida or P. cepacia, express the TCE transformation activity
upon induction by their aromatic substrates. These bacteria
have a great potential for remediation of groundwater aquifers
that are contaminated by mixtures of gasoline or jet fuel (or
other petroleum derivatives) and chlorinated solvents, such as
TCE, DCE, or VC. If the aromatic contaminants are not pres-
ent, however, bacterial growth substrates need to be injected
into the site in order to stimulate the transformation of chlori-
nated solvents. In this situation, methanotrophs become more
attractive agents of bioremediation: methane, their preferred
substrate, is a nontoxic and inexpensive chemical and is often
present naturally in petroleum-impacted sites. Once methane
(if not already present) and oxygen are injected into the sub-
surface, methanotrophs (if present) will start cometaboliz-
ing chlorinated solvents, as well as a great number of other
contaminants (see Table 6.11), and the accompanying hetero-
trophs will mineralize their transformation products.
Aerobic cometabolism of chlorinated compounds at low
concentrations by methane- and propane-utilizing bacteria
is well documented. In comparison, butane-utilizing bacte-
ria are less susceptible to the toxic effects of elevated chlo-
rinated compound concentrations. Butane is approximately
four times more soluble in groundwater than methane. Butane
injection results in large radii of influence at injection well-
heads, but the primary difficulty of utilizing alkanotrophic
bacteria stems from the low solubility of alkanes and the dif-
ficulty of maintaining homogeneous concentration of the dis-
solved alkane within the reactive zone.
Methanotrophic communities that initiate the oxidative
transformation and heterotrophs that subsequently utilize
the products of oxidation and hydrolysis are very active and
Remediation Engineering
can achieve complete degradation of chlorinated alkenes.
The same communities fail to transform PCE, however,
because this compound is too oxidized. Pure cultures of
methanotrophs such as Methylosinus trichosporium OB3b or
Methylomonas sp. MM2 have been shown to partially trans-
form TCE, trans-DCE, and cis-DCE.46,143 Other microor-
ganisms capable of transforming chlorinated alkenes belong
to the genera Pseudomonas, Alcaligenes, Mycobacterium,
and Nitrosomonas. All of these microorganisms, except the
genus Nitrosomonas, are heterotrophs that grow on various
organic substrates (e.g., toluene, cresol, phenols, propane);
Nitrosomonas is a chemolithotroph that derives energy from
oxidation of ammonia. All of them cometabolize chlorinated
compounds such as TCE or cis-1,2-DCE while growing on
their respective growth substrates; the chloroalkenes are only
fortuitously transformed, not utilized for growth. However, it
has been demonstrated that a Mycobacterium strain isolated
from soil contaminated by VC could grow on VC as sole car-
bon and energy source.144
Methanotrophs produce catabolic methane monooxygen-
ases (MMOs) that incorporate one atom of oxygen from the
oxygen molecule into methane to yield methanol.46,143–145 This
alcohol is further oxidized via a series of dehydrogenation
steps through formaldehyde and formic acid to CO2, which
is the final product of catabolism. MMO enzymes utilize
molecular oxygen as a reactant and require a reduced elec-
tron carrier to reduce the remaining oxygen atom to water.
Similar to mono- and dioxygenase enzymes, MMO enzymes
have relaxed substrate specificity and will oxygenate many
compounds that are not growth substrates for methanotrophs.
Such compounds include various alkanes, alkenes, ethers,
alicycles, aromatics, nitrogen heterocycles, and chlorinated
alkanes, alkenes, and aromatics.46,146,147 Based on the findings
with methanotrophs, it can be concluded that TCE is most
likely oxygenated to TCE-epoxide (Figure 6.49). The epox-
ide is unstable and is quickly nonenzymatically rearranged
in aqueous solution to yield various products including car-
bon monoxide, formic acid, glyoxylic acid, and a range of
chlorinated acids. Recent findings with purified MMO from
M. trichosporium OB3b indicate that TCE-epoxide is indeed
a product of TCE oxygenation. In nature, where cooperation
between the TCE oxidizers and other bacteria (most promi-
nently heterotrophs) occurs, TCE can be completely mineral-
ized to carbon dioxide, water, and chloride.
Two types of MMOs have been suggested: a particulate
(membrane bound) and a soluble enzyme.46 The soluble MMO
(purified from M. trichosporium OB3b and Methylococcus
capsulatus), which is produced under the conditions of copper
limitation and increased oxygen tension, has been considered
to have broader substrate specificity. It has been stated that
only the soluble MMO can transform TCE. However, recent
findings indicate that the particulate MMO in some metha-
notrophs may be as effective in the transformation of chlori-
nated solvents as the soluble MMO. Since the soluble MMO
is not constitutively expressed whereas the particulate MMO
is, the latter methanotrophs (Methylomonas sp.) have a signifi-
cant potential for in situ bioremediation.
Injected Reagent–Based Remedies
Mono- or dioxygenase enzyme formation requires both
the growth substrate and oxygen. This can complicate design
for chlorinated ethene cometabolic degradation as the pri-
mary growth substrate will compete for the mono- or dioxy-
genase enzymes and decrease the reaction efficiency with
chlorinated ethenes. There has been a significant amount
of research toward evaluating what specific mono- and
dioxygenase enzymes have greater specificity toward some
chlorinated compounds and also in engineering microbial
strains to express these oxygenases to improve degradation
efficiency.148
Mechanisms have been attempted to increase the over-
all efficiency of cometabolic degradation by selecting for
specific groups of microorganisms responsible for mono- or
dioxygenase synthesis. Substrates such as toluene, phenol,
methane, propane, ethene (for VC only), ethane (for VC only),
and butane (for CT) with the potential to stimulate microbial
production of oxygenase enzymes have been applied in con-
junction with nutrient amendment in an attempt to increase
chlorinated ethene degradation efficiency. While some posi-
tive evidence has been developed demonstrating that these
processes can be enhanced,142 other data are inconclusive.
Nutrient addition (both nitrogen and phosphorus) has been
observed to increase the number of methanotrophs (soluble
MMO expression) and TCE transformation potential com-
pared to systems without nutrient addition; but others have
exhibited very limited change in cultures when comparing
nitrogen-limited and nitrogen-fed systems.149
Regardless of nutrient addition, chlorinated ethene deg-
radation will not take place unless sufficient carbon growth
substrate and oxygen are present to stimulate the targeted
organisms into expressing the desired oxygenase enzymes.
Field application of substrate has ranged from use of liquid
injection or recirculation systems (injection of substrate/
extraction of groundwater) to create reactive zones with sub-
strates such as propane, phenol, and toluene.150,151 Gaseous
carbon substrates such as propane and methane can also be
applied via sparge techniques.152 The addition carbon sub-
strate is coupled with oxygen delivery (usually via air sparge
applications) to ensure that both electron donor and electron
acceptor are present concurrently. As mentioned earlier, it is
important to maintain a reasonable high and uniform O2 and
CH4 concentrations to achieve significant methanotrophic
degradation. Cometabolic oxidation often is not considered
a significant, long-term mechanism for nonengineered biore-
mediation of chloroethenes in groundwater but has been suc-
cessfully exploited within engineered IRZ systems.
A considerable body of more recent research has been
developed to detail the biodegradation of 1,4-dioxane under
aerobic conditions. Only a limited number of microorganisms
with the capacity to directly metabolize 1,4-dioxane as the
primary growth substrate have been identified,153–156 includ-
ing Amycolata sp. strain CB1190, Mycobacterium vaccae,
and two strains of Rhodococcus sp. As these species are not
ubiquitous to most groundwater systems and genetic surveys
to characterize the activity and abundance of these organisms
are not yet commercially available, cometabolic degradation
257
is currently viewed as the most widely applicable mechanism
by which 1,4-dioxane degrades in situ.
Soluble MMO produced by methanotrophic and propane
monooxygenase (PPO) produced by propanotrophic bacte-
ria both have the capacity to catalyze the cometabolism of
1,4-dioxane.154 Genetic surveys to quantify the genes that
encode these enzymes and their expression are available,
providing a potential line of evidence for the mechanism of
natural attenuation of 1,4-dioxane in groundwater. In addition
to 1,4-dioxane, soluble MMO can also catalyze cometabolic
degradation of chlorinated ethenes,157 as discussed earlier.
Demonstration that cometabolic degradation is ongoing
can be challenging using standard sampling techniques.
Relative comparisons of trend analyses and the disap-
pearance of the contaminants of interest can suggest that
cometabolic degradation is occurring, but it can be hard to
provide definitive proof in the absence of EMD and MBT
analyses. A sample data set using these tools is provided in
Figure 6.67, which integrates concentrations of the metha-
notrophic growth substrate (methane), dissolved oxygen
concentrations, and microbial DNA and RNA molecular
analyses used to assess both the presence and enzymatic
activity of methanotrophs in a groundwater system contain-
ing 1,4-dioxane. The results indicate that elevated methane
concentrations are present (>1000 µg/L) in conjunction
with low-level DO concentrations. The DNA-based analy-
ses indicate the potential for MMO production based on
the presence of methanotrophic DNA, and the RNA-based
analyses identified SMMO activity at the majority of sam-
pling locations. In conjunction with observed declines in
1,4-dioxane within plume monitoring wells, this sampling
technique can provide a significant line of evidence docu-
menting 1,4-dioxane transformation—opposed to via phys-
ical processes alone.
6.3  IN SITU CHEMICAL REMEDIATION
Groundwater containment (e.g., groundwater extraction and
treatment systems [GETS]) and physically enhanced removal
strategies (e.g., aquifer sparging) are fundamentally limited
by the dual-domain nature of porous media (Chapter 4). As
highlighted earlier in the chapter, the limitations of these
remedial strategies inspired a transition in the remediation
industry from containment and removal to in situ treatment
strategies. Rather than struggling to remove contaminant
mass from a heterogeneous and complex pore structure,
in  situ treatment facilitates proven destruction and immobi-
lization mechanisms within the contaminated aquifer. The
stakeholder preference for contaminant destruction naturally
kindled an interest in chemical reaction mechanisms. There is
a wide-ranging repertoire of reaction mechanisms that were
developed for ex situ water supply and wastewater treatment
systems, several of which were subsequently adopted for
in situ chemical remediation. Compared to above-grade treat-
ment processes, the major differences of applying chemical
reaction mechanisms in aquifers are the large volumes that
are engaged in reactions and the loss of reaction control.
258 Remediation Engineering

1,000,000 2000

1800
100,000
1600

Methane and dissolved oxygen (µg/L)

mRNA: transcript copies/bead 1400
10,000
DNA: cells/bead

1200

1,000 1000

800
100
600

400
10 SMMO DNA
SMMO mRNA
200
Methane
DO
1 0
MW-12-09 MW-14-62 MW-14-60 MW-03-07

FIGURE 6.67  Multiple lines of evidence used to assess potential for 1,4-dioxane cometabolic degradation. Data show correlation between
methane, DO, DNA from organisms known to excrete soluble methane monooxygenase (SMMO), and mRNA demonstrating that SMMO is
being actively transcribed. mRNA data from eubacteria (EBAC) shown as validation of SMMO mRNA quantification accuracy.

Nothing about in  situ chemical remediation is subtle. The
most reliable reaction mechanisms are simple and, generally,
energetic. The reactions engage many nontarget compounds,
and nontarget reaction losses typically dominate the reagent
budget. The fluid volume that must be injected to achieve com-
plete contact between reagents and contaminants is often quite
large, and the injection points must be spaced at appropriate
distances to achieve uniform distribution in order to overcome
physical limitations on the injected reagent. Despite these chal-
lenging attributes, in situ chemical remediation can be success-
ful and plays an important role in soil and groundwater cleanup.
Based on publication of field applications from academic
institutions and conference proceedings158–162 (and references
therein), it is clear that chemical oxidation historically has
been the dominant in  situ chemical remediation strategy,
with recurring demonstrations of permanganate (MnO4−) and
catalyzed hydrogen peroxide (CHP). In the past ten years,
chemical reduction has gained popularity, due in large part
to the effectiveness of ZVI ([Fe0]) and curious observations in
reductive dechlorination pathways.
In  situ chemical remediation has been deployed in source
zone treatments, reactive barriers, and comprehensive site
treatments for metals and organics. Success and failure of
in situ chemical remediation rely heavily upon a comprehen-
sive understanding of the CSM, most importantly the degree
of residual NAPL or adsorbed contamination. Chemical reme-
diation kinetics are comparatively faster than biological reme-
diation kinetics or MNA. An appropriately applied in  situ
chemical reactive zone may demonstrate dramatic concentra-
tion reduction on an abbreviated timeline. Chemical reactive
zones may cautiously be used for rapid source zone mass reduc-
tion, which would require other remediation technologies to
provide a holistic treatment program for a large-scale contami-
nant plume. Typical chemical reactive zone treatment mecha-
nisms and deployment methods are summarized in Table 6.19.
This section describes the chemistry that is associated with
in situ chemical remediation. Key concepts that are discussed
include chemical thermodynamics, which is used to deter-
mine whether a reaction is energetically feasible, and chemi-
cal kinetics, the study of reaction rates and the variables that

TABLE 6.19
Table of Commonly Deployed Processes in Chemical Reactive Zone Treatments
Applications Reactive Zone Treatment Mode
Chemical Treatment Mechanism Metals Organics Source Zone Reactive Barrier Comprehensive Treatment
Precipitation ✓ ✓ ✓ ✓
Chemical oxidation ✓ ✓ ✓ ✓
Chemical reduction ✓ ✓ ✓ ✓
Nucleophilic substitution ✓ ✓

Note: Chemical oxidation for metals is primarily during novel applications, mostly associated with arsenic pretreatment.
Injected Reagent–Based Remedies
affect them (e.g., temperature and concentration of reactants).
Thermodynamic feasibility has been determined for most
reactions of interest,163 so a greater emphasis is placed on
chemical kinetics and their influence on in situ chemical reac-
tive zone designs. Detailed descriptions of the major chemical
reactive zone technologies, including ISCO and in situ chemi-
cal reduction (ISCR) methods, are discussed conceptually
and illustrated through select case study examples. A com-
mentary on the limitations of in situ chemical remediation is
woven throughout the section.
6.3.1 Chemical Reactivity
The biologically mediated reactions examined in Chapter 2
and in Sections 6.1 and 6.2 are fundamentally similar to the
mechanisms associated with in  situ chemical remediation
(i.e., reductions and oxidations). The important difference is
that microbial reactions are catalyzed by enzymes that sig-
nificantly decrease the activation energy, increasing the rate
at which many reactions occur, especially at low reactant
concentrations (Figure  6.68). The catalytic systems built by
microbial communities are more persistent than the chemi-
cal reagents used for in situ chemical remediation. Chemical
remediation, lacking the catalytic capacities of biological
remediation, must operate at higher energy levels to achieve
the same level of treatment. This is accomplished through
the use of more energetic reagents (e.g., the hydroxyl radical
[OH•]), along with the use of high reagent concentrations.
This section provides a brief review of chemical reactiv-
ity, including chemical thermodynamics and reaction kinet-
ics. The objective is to describe some of the key variables that
control chemical reactivity in aquifers, allowing the reader to
critically examine reaction systems that might be considered
for deployment and to troubleshoot systems that have not met
remedial objectives. The greatest emphasis is placed on reac-
tion kinetics, because the performance of in  situ chemical
Gibbs free energy (kJ/mol)
∆G‡
∆G‡cat
∆Grxn
Reactants Activated Products
complex
FIGURE 6.68  Effect of enzyme participation on the activation
energy of an exergonic reaction. The activation energy reaction,
ΔG ‡, is dramatically reduced by the intervention of an enzyme in
the reaction, as depicted by the lower activation energy, DGcat
‡
. The
overall reaction energy yield, ΔGrxn, is unaffected by the presence
of a catalyst.
259
remediation is most often controlled by the concentrations of
target compounds and treatment reagents that can be estab-
lished in field applications. Finally, the treatment of chem-
istry fundamentals is not intended to be exhaustive, and
advanced readers are directed to Stumm and Morgan164 and
Schwarzenbach et al.165 as additional reading.
6.3.1.1  Oxidation States
The most common in situ chemical remediation involves oxi-
dation or reduction of target compounds. It is useful to rec-
ognize the oxidation states of molecules involved in these
reactions, particularly among the organic molecules that
might be targets of either chemical reduction or chemical oxi-
dation. The oxidation state of a molecule is calculated from
the oxidation numbers of its component atoms, according to
the following guidelines (after Kotz and Treichel)166:
1. Atoms of elements in their pure states (e.g., H2 and
O2) are assigned the oxidation state of 0.
2. Single-element ions (e.g., Fe2+ and Cl−) are assigned
an oxidation number equal to the charge on the ion.
3. The oxidation number for fluorine (F) is always 1 in
compounds with other elements.
4. Hydrogen (H+) is assigned +1 and oxygen is assigned
−2 with the following exceptions:
a. Metal hydrides: hydrogen in metal hydrides is
assigned −1 (e.g., calcium hydride [CaH2]).
b. Peroxides: oxygen in peroxides is assigned +1
(e.g., hydrogen peroxide [H2O2]).
5. Chlorine, bromine, and iodine are assigned −1,
except when they are compounded with oxygen or
fluorine (e.g., perchlorate [ClO4−] where the chlorine
carries the oxidation number +7).
6. The sum of oxidation numbers for atoms in a com-
pound equals the net charge on the compound. This
guideline, combined with those mentioned earlier, is
used to determine oxidation numbers for atoms that
have not been specified. For example, in the perman-
ganate ion (MnO4−), the oxygens total −8 (i.e., −2 ×
4), so the manganese is +7 (calculated as −1 = x +
4(−2)), which is represented as Mn+7.
The oxidation state of each carbon on an organic
molecule can be calculated by these guidelines, and
the overall oxidation state for an organic molecule
can be characterized by a mean oxidation number for
the carbons.167 The value of this analysis for organic
molecules is in the initial screening of potential
chemical mechanisms for treatment.
Calculation of the mean oxidation number for car-
bon compounds follows the aforementioned rules,
with one addition:
7. Carbon atoms are neutral with respect to oxida-
tion number in carbon–carbon bonds, regardless of
the number of bonds (single, double, or triple). For
example, each carbon atom in acetylene (HC≡CH)
has the oxidation state (−1), balancing the hydrogens
(+1) that each carries.
260
Carbon can assume oxidation numbers ranging from −4 to
+4. To calculate the mean oxidation number for a molecule,
the oxidation number is calculated for each carbon atom, and
then the oxidation numbers are averaged for all carbon atoms
in the molecule. Here are some examples:
• Carbon tetrachloride (CCl4). Four chlorines at −1
each indicate that the carbon in this molecule has
an oxidation state of +4. That is the maximum for
carbon, so additional oxidation is not likely to be
productive (it is possible to oxidize carbon tetrachlo-
ride to carbon dioxide, but the energy input would
be quite large, and by-product production would be
significant).
• Methane (CH4). Four hydrogens at +1 each indicate
that the carbon in this molecule has an oxidation state
of −4. That is the minimum for carbon, so additional
reduction is not possible. This explains why meth-
ane persists in reactive zone applications that rely on
chemical or biological reduction mechanisms.
• Tetrachloroethene (PCE; C2Cl4). Each carbon has
two chlorines at −2, so each carbon is assigned the
oxidation state +2, and the mean oxidation number
for the molecule is +2. Tetrachloroethene is the most
oxidized of the chlorinated ethenes, is more suscep-
tible to reduction and less susceptible to oxidation
than the other chlorinated ethenes.
• 1,1,1-Trichloroethane (1,1,1-TCA; C2H3Cl3). The
chlorine-bearing carbon has a +3 oxidation state,
balancing the three chlorines at −1 each, and the sat-
urated (–CH3) carbon has a −3 oxidation state, bal-
ancing the three hydrogens at +1 each. This gives the
molecule a mean oxidation number of 0. 1,1,1-TCA is
susceptible to either reduction or oxidation.
For organic molecules, the addition of hydrogen (H+) or the
loss of oxygen (O2) or halogen atoms yields a reduction in the
mean oxidation number and would be indicative of chemical
or biological reduction mechanisms at work. The addition of
oxygen (O2) or halogen molecules or the loss of hydrogen (H+)
yields an increase in the mean oxidation number, indicating
that a chemical or biological oxidation mechanism is at work.
6.3.1.2  Thermodynamics versus Kinetics
The thermodynamic properties of reactions can be used
as a screening tool to identify reactions that are energeti-
cally feasible. Thermodynamics does not, however, deter-
mine whether a reaction can be deployed effectively in situ.
Thermodynamics is part of the analysis of reactions, and
it quantifies the energy that can be gained from a reaction.
Thermodynamics does not reflect the rate at which a reac-
tion will occur, and a large thermodynamic energy yield does
not always lead to high reaction rates. In many cases, less
energy-yielding reactions occur more quickly, so the most
stable product is not always the first to form. Rate predictions
are the domain of chemical kinetics.
Remediation Engineering
In this section, specific discussion is provided on thermo-
dynamic and kinetic fundamentals, such as bond energies,
Gibbs free energy, the Nernst equation, and a detailed dis-
cussion on the different reaction orders and rate equations.
The most important distinction between thermodynamics
and kinetics is that thermodynamics informs whether or not a
reaction is energetically feasible, while reaction kinetics dic-
tate whether or not a reaction will occur within a meaningful
time frame in situ.
6.3.1.2.1  Bond Energies
Chemical reactions entail the breaking and making of bonds
between atoms. The strength of these bonds determines the
energy input required to initiate bond breakage and the energy
that will be gained when new bonds are formed at reaction
completion. Chemical reaction strategies for the destruction
of soil and groundwater contaminants are most often directed
at breaking bonds between carbon atoms and heteroatoms,
that is, atoms of elements other than carbon in organic mol-
ecules. Removal of heteroatoms from toxic organic compounds
normally reduces or eliminates their toxicity and typically
increases their mobility and susceptibility to natural attenua-
tion mechanisms such as biodegradation.
Dissociation energies for chemical bonds between atoms
in organic carbon molecules are summarized in Table 6.20.
From these data, the heteroatoms chlorine and bromine have
relatively lower dissociation energies than the bonds between
carbon atoms and oxygen or hydrogen. Bond energies between
carbon and halogens decrease with increasing halogen atomic
mass: F > Cl > Br > I. The decrease in bond strength is linked
to the increase in atomic radius, which leads to greater bond
lengths for the larger halogens.
6.3.1.2.2  Gibbs Free Energy
Gibbs free energy incorporates changes in enthalpy (ΔH) and
entropy (ΔS) to reflect the total energy change of any reac-
tion. When the Gibbs free energy associated with a reaction is
positive, the reaction requires energy input to occur, and the
reaction cannot occur spontaneously. When the Gibbs free
energy associated with a reaction is negative, the reaction
releases energy and can occur spontaneously. Spontaneous
reactions are those that can occur without the input of energy
into the system. Spontaneity does not imply speed.
Gibbs free energy is defined by the change in enthalpy (H)
and entropy (S) in a reaction and can be calculated by the
van’t Hoff equation (Equation 6.49):
DG = DH - TDS (6.49)
The change in Gibbs energy for a reaction (ΔGrxn) is calcu-
lated by the difference between the Gibbs energy of products
0 0
(G products ) and reactants (Greactants ), as shown in Equation 6.50:
DGrxn = åG 0
products - åG
0
reactants (6.50)
Injected Reagent–Based Remedies 261

6.3.1.2.2.1  Enthalpy Consideration  The first law of

TABLE 6.20 thermodynamics states that energy cannot be created nor
Selected Bond Dissociation Energies destroyed, but it can be transformed from one form to another.
Bond Bond Dissociation Energy (kJ/mol) In chemical reactions, this energy accounting is measured in
the form of heat flow, and enthalpy (H) is the key parameter to
Methyl bonds
describe this process thermodynamically. The definition of a
CH3–H 435
change in enthalpy (ΔH) is the quantity of heat absorbed by a
CH3–Cl 351
CH3–Br 293
system at constant temperature and pressure.170 Enthalpy (H)
CH3–OH 381
is defined by Equation 6.51 as
Primary carbon bonds
CH3CH2–H 410 H = E + PV (6.51)
CH3CH2–Cl 339
CH3CH2–Br 285
CH3CH2–OH 381
where
Secondary carbon bonds E is the internal energy
(CH3)2CH–H 397 P is the pressure
(CH3)2CH–Cl 335 V is the volume
(CH3)2CH–Br 285
(CH3)2CH–OH 381 Calculating the total enthalpy (H) of an aquifer would be
Tertiary carbon bonds extremely difficult and highly inaccurate, and therefore the
(CH3)3C–H 381 change in enthalpy (ΔH) is targeted for calculation. In reac-
(CH3)3C–Cl 331 tive zones that are relevant to in situ chemical remediation, the
(CH3)3C–Br 272 pressure and temperature are relatively constant (an assump-
(CH3)3C–OH 381 tion that should be challenged if temperature manipulation is
Carbon–carbon bonds
part of the treatment process). Through algebraic manipula-
CH3–CH3 368
tion of Equation 6.51 and the first law of thermodynamics,
CH3CH2–CH3 356
the expression for the change in enthalpy (ΔH) at constant
C=C (second bond) 264a
pressure is expressed as Equation 6.52:
Other bonds
Ph–Cl 402a

Source: Wade, L.G., Jr., Organic Chemistry, 4th ed., Prentice Hall, Upper
Saddle River, NJ, 1999, unless otherwise noted.
a Data from [168].
where G 0 are values for the standard free energy of formation
for individual compounds, referenced to a standard physical–
chemical state (viz., 1 atm pressure and 25°C [298.15 K]).
Values of G 0 for most compounds are typically tabulated in
standard data compendiums and available in Internet data-
bases such as the Handbook of Chemistry and Physics.163 The
change in Gibbs energy (ΔGrxn) for a reaction can be classified
according to the following:
1.
Endergonic reactions. Reactions that are energy
consuming as measured by an increase in Gibbs
free energy are termed endergonic. Endergonic
reactions cannot occur spontaneously. Metabolic
reaction sequences may include endergonic steps,
but the overall reaction must be exergonic to
proceed.
2.
Exergonic reactions. Reactions that are energy
releasing, as measured by a decrease in Gibbs free
energy, are termed exergonic. Exergonic reactions
may occur spontaneously.
DH = q p (6.52)
where qp is the heat absorbed at constant pressure.
Because the change in enthalpy (ΔH) is the main con-
tributor to the free energy calculation in Equation 6.49, a
similar concept is used to calculate the change in enthalpy
(ΔH). That is, based on a balanced equation for a chemical
reaction, the heat of the reaction is equal to the sum of the
standard enthalpies of the products minus the sum of
the  standard enthalpies of the reactants. A summary of
standard Gibbs free energies and enthalpies is tabulated
in Table 6.21 to facilitate the following example. Here, the
change in enthalpy (ΔH) of the complete mineralization of
benzene (C6H6) to carbon dioxide (CO2) by oxygen (O2) is
determined. The balanced chemical reaction is as follows
(Equation 6.53):
C6H 6(aq) + 7.5O2(aq) ® 6CO2(aq) + 3H 2O(l) (6.53)
Note the phase subscripts in Equation 6.53. Unique standard
enthalpies exist for different phases, and, in some instances,
the change in enthalpy (ΔH) can be appreciably different
based on the phase of the compound. When calculating the
change in enthalpy (ΔH), it is important to know the phase
262 Remediation Engineering

TABLE 6.21
Standard Gibbs Free Energy and Enthalpy Values for Selected Compounds
in Specified Phases at 25°C (298.15 K) and 1 atm
Compound Name Chemical Formula DGf0 (kJ/mol) Reference DHf0 (kJ/mol) Reference
Hydrogen ion H (aq)
+ 0 [171] 0 [171]
Neutral-pH hydrogen ion H+(10−7)(aq) −39.87 [172]
Hydrogen H2(aq) 17.57 [173] −4.18 [173]
Water H2O(l) −237.18 [174] −285.80 [174]
Hydrogen peroxide H2O2(aq) −134.097 [172] −191.13 [175]
Hydroxide ion OH− (aq) −157.2 [174] −230.0 [174]
Oxygen O2(aq) 16.32 [173] −11.71 [173]
Ozone O3(g) 165.7 [174] 142 [174]
Carbon dioxide CO2(aq) −386.23 [174] −412.92 [174]
Carbonic acid H2CO3(aq) −623 [174 −699 [174]
Bicarbonate HCO3− (aq) −586.85 [171] −692.00 [171]
Carbonate CO32− (aq) −527.80 [171] −677.10 [171]
Chloride ion Cl− (aq) −131.30 [174] −167.20 [174]
Ferrous iron Fe2+(aq) −78.87 [173] −89 [171]
Ferric iron Fe3+(aq) −4.60 [172] −48.5 [171]
Manganous manganese Mn2+(aq) −228.0 [173] −220.7 [173]
Ammonia NH3(aq) −26.65 [174] −80.83 [174]
Ammonium NH4+(aq) −79.37 [174] −132.50 [174]
Nitrate NO3− (aq) −111.34 [172] −207.4 [171]
Hydrogen sulfide H2S(aq) −27.87 [172] −39.3 [174]
Bisulfide HS− (aq) 12.05 [172] −17.6 [174]
Sulfide S2− (aq) 79.5 [171] 30.1 [171]
Sulfate SO42− (aq) −744.63 [172] −909.3 [171]
Benzene C6H6(aq) 133.9 [176]
Ethylbenzene C8H10(aq) 136 [176]
Toluene C7H8(aq) 127 [176]
m-Xylenes C8H10(aq) 122.9 [176]
o-Xylenes C8H10(aq) 124.6 [176]
p-Xylenes C8H10(aq) 125.2 [176]
Chloroethane C2H5Cl(aq) −36.83 [177]
Chloroethene C2H3Cl(aq) 59.65 [177]
1,1-Dichloroethane C2H4Cl2(aq) −68.69 [177]
1,2-Dichloroethane C2H4Cl2(aq) −72.93 [177]
1,1-Dichloroethene C2H2Cl2(aq) 32.23 [177]
cis-1,2-Dichloroethene C2H2Cl2(aq) 27.8 [177]
trans-1,2-Dichloroethene C2H2Cl2(aq) 32.06 [177]
1,1,1,2-Tetrachloroethane C2H2Cl4(aq) −77.75 [177]
1,1,2,2-Tetrachloroethane C2H2Cl4(aq) −88.92 [177]
Tetrachloroethene C2Cl4(aq) 27.59 [177]
1,1,1-Trichloroethane C2H3Cl3(aq) −69.04 [177]
1,1,2-Trichloroethane C2H3Cl3(aq) −77.64 [177]
Trichloroethene C2HCl3(aq) 25.41 [177]
Ethane C2H6(aq) −17.43 [177]
Ethene C2H4(aq) 81.43 [177]
Methane CH4(aq) −34.74 [177]

of each compound in the chemical reaction. The change in The superscript 0 indicates the standard heat of formation
enthalpy (ΔH) of Equation 6.53 is defined by Equation 6.54: with reactants and products at 1 atm and 25°C (298.15 K).
The standard enthalpies from Table 6.21 for the com-

åDH åDH
pounds in this example are as follows: benzene (C6H6) =
DH 0f = 0
products - 0
reactants (6.54)
48.95 kJ/mol, oxygen (O2) = −11.71 kJ/mol, carbon dioxide
Injected Reagent–Based Remedies
(CO2) = −412.92 kJ/mol, and water (H2O) = −285.80 kJ/mol.
Therefore,
DH 0f = éë( 6 mol ´ -412.92 kJ/mol ) + ( 3 mol ´ -285.80 kJ/mol )ùû
- éë(1 mol ´ 48.95 kJ/mol ) + ( 7.5 mol ´ -11.71 kJ/mol )ùû
= -3296.04 kJ
The standard change in enthalpy (DH 0f ) for the mineraliza-
tion of benzene (C6H6) to carbon dioxide (CO2) is equal to
−3296.04  kJ. The negative standard change in enthalpy
(DH 0f ) indicates a reaction that generates heat and is therefore
referred to as exothermic and will proceed spontaneously.
Had the standard change in enthalpy (DH 0f ) been positive, the
reaction would be observed to absorb heat, and it would have
been endothermic. The difference between endothermic and
exothermic reactions is similar to the Gibbs free energy dif-
ference and describes the spontaneity (i.e., required energy
to proceed) of the reaction. The largely negative change in
enthalpy (ΔH) does not mean to imply Equation 6.53 pro-
ceeds at a rapid rate.
6.3.1.2.2.2  Entropy Consideration  The Gibbs free
energy equation defined in Equation 6.49 includes both
enthalpy (H) and entropy (S). Entropy (S) is an abstract
topic that generally describes the spontaneity of a reaction
to trend toward equilibrium and is related to the second law
of thermodynamics. Briefly, the second law of thermody-
namics states that entropy will increase over time. When
a spontaneous reaction occurs, the change in entropy (ΔS)
is always found to be positive.170 Therefore, if all entropy
(S) increases over time, all reactions are slowly progressing
toward equilibrium. If the change in entropy (ΔS) is zero,
this implies the reaction is already at equilibrium. Typically,
in most reactions relevant to in  situ chemical remediation,
rapid rate kinetics progress to equilibrium quickly, and in
most instances the contribution of entropy (S) to the free
energy in Equation 6.49 is negligible.
6.3.1.2.3 Nonstandard Conditions: The
Nernst Equation
The Gibbs free energy for a reaction at nonstandard conditions
is described by the Nernst equation. The free energy change
is determined by the standard free energy of the reaction, the
reaction temperature, reaction stoichiometries, and the con-
centrations of products and reactants, as shown in Equation
6.56, where A and B are reactants and C and D are products,
as shown in Equation 6.55:
aA + bB ® cC + dD (6.55)
é [C ]c D d ¼ ù
DGrxn = DGrxn
0
+ RT ln ê a b ú (6.56)
ë [ A] [ B] ¼ û
263
where A and B indicate reactants and C and D indicate prod-
ucts. The “…” in Equation 6.56 is included to imply that all
products and reactants are included in Equation 6.56.
The free energy for a compound at nonstandard condi-
tions can be determined by the partial molar free energy cal-
culation, shown in Equation 6.57. The bar above the Gibbs
energy symbol, G, indicates a molar quantity for compound
A, in contrast to the Gibbs energy for a reaction, shown in
Equations 6.50 and 6.56:
G A = G A0 + RT ln[ A] (6.57)
6.3.1.2.4  Kinetic Control of Reaction Rates
Thermodynamic analysis tells us the energy yield (ΔGrxn)
when a reaction occurs, but it does not give us information
on the probability that the reaction will actually happen. The
rate at which a reaction occurs, measured as moles per liter
per second (mol/L/s or M/s), is a reflection of the probability
of the reaction. There are two major factors that determine
the probability of completing a particular irreversible reaction
in aqueous solution*:
1.
Frequency of collisions between reactants. For a
reaction to occur, the reactants must make contact.
The frequency of contact events is controlled by two
variables: the concentration of reactants and their
effective velocities in solution. Reactions are more
likely to occur at high reactant concentrations and at
higher molecular velocities (i.e., higher temperatures).
Molecules that rapidly diffuse in aqueous solution
would also be expected to achieve more contact events
than reactants that migrate slowly in solution.
2.
Likelihood that a contact event will result in a com-
pleted reaction. Many collisions occur between
reactants, which do not result in a completed reac-
tion. The rate at which contact events generate reac-
tions is determined by the steric interaction of  the
reactants (the “fit” of the reacting molecules),
the velocity (energy) at which the contact occurs, and
the free energy of formation of the reaction interme-
diate (activated complex), ΔG ‡.
The effects of contact frequency, likelihood of reaction, and
other variables are lumped into a kinetic constant that can
be used to estimate the rate that a reaction occurs under
specified conditions. Kinetic analysis of possible reactions is
important in the development of in situ chemical remediation
because many reactions that are thermodynamically feasible
occur at rates that are too slow or too fast to achieve remedial
objectives. Kinetic analysis of reactions can also be used to
determine when competition for reactants will affect in situ
chemical reactive zone operation. This allows practitioners to
engineer the aquifer chemistry to minimize competitive limi-
tations on reaction effectiveness.
* This treatment of kinetics is not intended to be a comprehensive treatment
of the subject but rather a summarization offered to assist the nonchemist
in understanding the major factors that underlie reaction kinetics.
264 Remediation Engineering

6.3.1.2.4.1  Reaction Order and Rate Equations  There 1.0

are four basic kinetic classifications for reactions that are rel-
evant to in situ chemical remediation: zero-order, first-order, 0.8

Reaction concentration (M)

second-order, and a special case of second-order reactions
called pseudo-first-order reactions. In the sections that follow,
reaction mechanisms and associated mathematical descrip- 0.6
tions are provided for each of the reaction classifications. For
in  situ chemical remediation purposes, the value of kinetic 0.4
analysis lies in the ability to calculate the rate of reaction as a a b
function of a target compound and the injected reagent con-
0.2
centrations and to estimate the rate of loss of injected reagents
to competing, unproductive reactions.
In the simplest reactions, there is one reactant that is changed 0.0
0 200 400 600 800 1000
to make one or more products, as shown in Equation 6.58. This
Time (s)
reaction may follow either zero- or first-order kinetics:

A ® products (6.58)
6.3.1.2.4.2  Zero Order  Zero-order reactions proceed at a
constant rate over time. This may occur in a catalytic reaction
with a single reactant, when the reactant is present in large
quantities. The zero-order rate equation in differential form is
presented as Equation 6.59:
dA
= k (6.59)
dt
Integrating to find a formula for the concentration of A as a
function of time,
[ A] = [ A]0 - k ´ t (6.60)
where
k is the kinetic rate constant (M/s)
[A]0 is the concentration of A when time = 0
A zero-order reaction generates a linear decrease of the reac-
tant over time, as shown in Figure 6.69. Zero-order reactions
are unlikely to be encountered in reactive zone applications.
6.3.1.2.4.3  First Order  First-order reactions also follow
Equation 6.58, and they proceed at a rate that declines over
time. The reaction rate (k) at any time is determined by the
concentration of a single reactant. Radioactive decay and
many enzyme reactions follow first-order reaction kinetics:
dA
= k ´[ A] (6.61)
dt
where
k is the kinetic rate constant of the reaction (s−1)
[A] is the molar concentration of the reactant, A, at any
time, t
FIGURE 6.69  Concentration versus time with zero-order (a) and
first-order (b) kinetic rate constants. For these reactions, the initial
reaction rates are identical. With zero-order kinetics, the reaction
rate remains constant as the concentration of the reactant decreases.
With first-order kinetics, the reaction rate declines as the reactant
concentration decreases.
where [A]0 is the concentration of A when time = 0. A first-
order reaction generates a log-linear decrease of concentration
over time, as shown in Figure 6.69. True first-order reactions
are unlikely to be encountered in reactive zone applications,
although pseudo-first-order reactions are quite common.
Pseudo-first-order reactions are a special case of second-order
reactions and are discussed later.
6.3.1.2.4.4  Second Order  Second-order reactions pro-
ceed at a rate that is determined by the concentrations of two
reactants. The rates of most reactions of interest in chemical
reactive zones are described by second-order reaction kinet-
ics. For the reaction
A + B ® products (6.63)
the rate of reaction is described by the following equation:
d[ A] d[ B]
= = k ´ [ A] ´ [ B] (6.64)
dt dt
where the units for k are M/s.
Notice that the rate of reaction (k) for A and B is the same,
because for each molecule of A reacted, a molecule of B also
reacts. For simple reaction systems, solutions to Equation 6.64
are provided by numerous authors. The following solution,
given by Barrow,178 is useful because it expresses the moles
reacted per liter after time (t) in seconds as “x,” which can be
isolated algebraically:

Integrating, we obtain
kt =
1
ln
éë B ùû 0 ( éë Aùû 0
-x ) (6.65)
[ A] = [ A]0 ´ e - kt (6.62)
éë B ùû 0 - éë A ùû 0 éë A ùû
0 ( éë Bùû 0
- x)
Injected Reagent–Based Remedies 265

where x is the number of moles reacted per liter in time t. concentration relative to the concentration of B, the terms
Solving for x (using the equation-solving facility of MathCad*) are lumped as follows:
at a specified time, t,
k¢ = k éë A ùû (s-1 ) (6.69)
e
( kt éë Aùû0 - kt éë Bùû0 ) - 1
x = éë A ùû 0 éë B ùû 0 ; éë A ùû 0 ¹ éë B ùû 0
éë A ùû 0 e
( kt éë Aùû0 - kt éë Bùû0 ) - é B ù where k′ is the pseudo-first-order kinetic rate constant for the
 ë û0 reaction.
(6.66) The reaction can then be expressed in the same manner as
a first-order reaction, as in Equation 6.62 (with A at a constant
The concentration of each reactant remaining after t seconds is concentration):

éë A ùû = éë A ùû 0 - x (mol/L) (6.67) éë B ùû = éë B ùû 0 ´ e - kt (6.70)

éë B ùû = éë B ùû 0 - x (mol/L) (mol/L) (6.68) The half-life (t1/2) of a reactant can be calculated for both first-
order and pseudo-first-order reaction kinetics. The half-life
Most reactions used for destruction of organic contami- (t1/2) is the time at which half of the reactant remains:
nant in chemical reactive zones are second order. The reac-
tion rate (k) depends on the concentration of the targeted éë B ùû
= 0.5 = e - k ¢t (6.71)
contaminant as well as the injected reagent. Simplifying éë B ùû 0
assumptions are sometimes used to collapse the second-
order kinetics into a pseudo-first-order kinetic analysis, as
Rearranging equation 6.71,
described in the following section. These assumptions must
be made with care to avoid overestimation of the expected
ln ( 0.5 ) = -k¢t (6.72)
reaction rates.
and setting t equivalant to the half-life (t1/2),
6.3.1.2.4.5  Pseudo-First Order  Pseudo-first-order reac-
tion kinetics are a special case of second-order kinetics, in ln ( 0.5 )
which three conditions are met: t1/ 2 = - (6.73)
k¢
1. The reaction is first order relative to both the targeted The above equations can be simplified to 6.74 or 6.75,
contaminant and the injected reagent.
2. The injected reagent concentration is significantly
t1/ 2 = -
( -0.69 ) (6.74)
higher than the targeted contaminant concentration.
k¢
3. The injected reagent is not significantly reactive with
any other chemical species in the reactive zone. 0.69
t1/ 2 = (6.75)
k¢
These conditions are not always met, and the conservative
approach is to use full second-order kinetic analysis of the The error that would be induced by the assumption of a
expected reactions. In chemical reactive zone applications, pseudo-first-order analysis in a true second-order reaction is
pseudo-first-order reaction assumptions may be met at the presented in the example in Figure 6.70, when reactant “B” is
point of injection; however, dilution of injected reagents by initially present at double the concentration of reactant “A”.
groundwater may invalidate the assumptions within a short The assumption of a constant concentration of reactant “B”
distance of the injection point. (the pseudo-first-order assumption) overstates the rate of reac-
Cases in which the conditions are met allow a simpli- tion, giving a lower concentration for reactant “A” than would
fying assumption: the concentration of the higher-con- actually be observed. As shown in Figure 6.70, the error is
centration reactant is effectively constant relative to the minimal during early stages of the reaction and leads to the
lower-concentration contaminant, which allows us to col- greatest error when the reaction is more than 50% complete.
lapse the kinetic rate equation to a pseudo-first-order cal- The magnitude of the error becomes quite large when the two
culation. This is accomplished by lumping the kinetic rate reactants are at similar concentrations.
constant (k) and the concentration of the excess reactant A summary of the reaction kinetic equations for zero-,
into a pseudo-first-order rate constant (k′). For the reac- first-, second-, and pseudo-second-order kinetics is presented
tion described in Equation 6.63, if A is present at a large in Table 6.22.

6.3.1.2.4.6  Kinetic Feasibility  Thermodynamic analysis

* Expansion of the natural log term was required for MathCad to achieve a
determines whether a reaction is energy yielding (exother-
solution. mic) or energy consuming (endothermic). Energy-yielding
266 Remediation Engineering

1.0 the reaction. The principle of kinetic feasibility can be stated

as follows: a reaction is kinetically feasible if it proceeds at a
0.8
rate and at concentrations that achieve remedial objectives in
Reaction concentration (M)

a cost-effective manner.
There are several potential kinetic limitations on the feasi-
0.6 bility of an in situ chemical reactive zone strategy:

0.4
a b
0.2
0.0
0 200 400
Time (s)
FIGURE 6.70  Comparison of second-order and pseudo-first-order
kinetics for the reaction A + B → products. Curve (a) shows the
concentration of reactant A, when the concentration of reactant B
is assumed to remain constant (pseudo-first-order kinetics). Curve
(b) shows the slower rate of reaction when the concentration of B
declines through the reaction process. As the initial concentration
of B is increased, the curve (b) converged to match curve (a). See
additional explanation in the text.
reactions meet the criterion of spontaneity and are thus ther-
modynamically feasible. However, many reactions that are
thermodynamically feasible do not occur at a rate that can be
used cost-effectively in a remedial system. This leads to the
second determination that must be made for candidate reac-
tion systems: kinetic feasibility.
The determination of kinetic feasibility is more subjective
than the determination of thermodynamic feasibility because
a judgment must be made on the economic viability of
1.
It is possible for a reaction to occur too quickly. Many
aquifer contaminants are present in two or more
distinct phases. It is the aqueous-phase fraction of
aquifer contamination that is typically quantified
and that is the phase in which most chemical reac-
tive zone reactions occur. For hydrophobic organic
600 800 1000 contaminants, the nonaqueous fractions constitute a
majority of the contaminant mass in many aquifers.
During a reactive zone treatment for hydrophobic
contaminants, the loss of the target compound from
aqueous phase is balanced by desorption of contami-
nant from nonaqueous phase. The half-life (t1/2) of
highly reactive treatment reagents, such as hydroxyl
radical (OH•), is so short that the reagent may be
spent before the desorption process is completed.
This causes rebound of nonaqueous-phase contami-
nant concentrations, and under these conditions, a
slower-acting reagent may be favored.
2.
It is possible for a reaction to occur too slowly. A
reagent that acts too slowly may be washed out of
the treatment area by groundwater movement, before
reactions occur.
3.
It is possible for a reactant to be consumed by com-
peting chemical processes. Most reagents used in
chemical reactive zones can react with at least sev-
eral chemical species present in the aquifer. It is

TABLE 6.22
Summary of Equations Describing Reaction Kinetics
Reaction Order Differential Solution to Differential Units for k
A → products
dA
Zero order =k [A] = [A]0 − k × t M * s−1
dt
dA
First order = k ´ éë A ùû [A] = [A]0e−k × t s−1
dt
A + B → products

Second order
dA dB
= = k ´ éë A ùû ´ éë B ùû k´t =
1
ln
éë B ùû 0 ( éë Aùû 0
-x ) M−1 * s−1
dt dt A -
éë ùû 0 éë ùû 0 é A ù
B
ë û0 ( éë Bùû 0
- x)

[A]0 ≠ [B]0 Solving for x, the amount of A and B

reacted after t seconds:

e
( kt éë Aùû0 -kt éë Bùû0 ) - 1
x = éë B ùû 0 éë A ùû 0
( kt éë Aùû0 -kt éë Bùû0 ) - é B ù
ëé A ùû 0 ´ e ë û0
dB
Pseudo-first order = k ¢´ éë B ùû éë B ùû = éë B ùû 0 ´ e - k¢t s−1
dt
[A]0 ≫ [B]0
Injected Reagent–Based Remedies
not uncommon to observe significant reagent loss
to reactions that have low kinetic rate constants (k).
This occurs when the concentration of the compet-
ing reactant is high. The bicarbonate ion (HCO3−)
is an example of a reactant that is only moderately
reactive with the hydroxyl radical (OH•). Its second-
order kinetic rate constant is approximately 1000-
fold lower than the rate constant for hydroxyl radical
(OH•) reaction with trichloroethene (TCE). However,
when the pH exceeds 7.0, a significant fraction of
the dissolved-phase inorganic carbon is in the bicar-
bonate ion (HCO3−) form. If the magnitude of the
inorganic carbon pool is large, the molarity of the
bicarbonate ion (HCO3−) will be high, relative to the
trichloroethene (TCE) concentration. As the oxida-
tion reaction proceeds and trichloroethene (TCE)
concentrations decline, an increasing portion of
the hydroxyl radicals (OH•) react with bicarbonate
(HCO3−) rather than with the targeted trichloroeth-
ene (TCE). The effect of carbonate (CO32−) competi-
tion on trichloroethene (TCE) oxidation is quantified
in Section 6.3.2.1.3.3.
4.
The reactant concentration that must be sustained
to fully treat a target contaminant can be uneco-
nomical.  There are many cases in which the aquifer
matrix consumption of a reagent is large, and chemi-
cal reagent mass that must be supplied to achieve
contaminant removal is economically unattractive.
All of these potential pitfalls should be examined in the deter-
mination of kinetic feasibility for a reaction strategy.
Kinetic feasibility generally must be determined on a site-
specific basis. Here are elements of the kinetic analysis that
should be considered for each in situ reaction scenario:
1. Kinetic rate constants for the primary reactions.
2. Kinetic rate constants for competing reactions that
are reasonably anticipated. Examples of these are
a. Decomposition reactions of the injected reagents
b. Reaction with dissolved inorganic species such
as carbonates (CO32−)
c. Reaction with nontarget organic compounds
3. Concentration patterns that will be achieved for the
injected reagents. Reagents are normally injected at
a high concentration, in anticipation of dilution by
groundwater. The injected reagent concentration is
likely to range several orders of magnitude from a
single injection point out to a dose-response moni-
toring well. The effectiveness of the planned reaction
and the production of by-products will be dramati-
cally different over the area of injection influence.
4. Groundwater flushing rate. Will the injected reagent
be swept out of the treatment area before the intended
reactions have been completed?
5. By-products review. Reagents that are poorly
matched to a target contaminant (slow reaction rates)
require high reagent concentrations to achieve needed
267
reductions in an acceptable time frame. With the
high reagent strength comes an increased rate of by-
product-forming reactions. Examples of by-product
formation are given throughout Section 6.3.2.
6.3.1.3  Reaction Mechanisms
Most of the reaction systems considered for use in aquifer reme-
dies were developed and tested in wastewater applications (e.g.,
ozonation) or industrial chemical synthesis (e.g., the Fenton’s
oxidation process). Useful remediation reactions have been
drawn from four classes: electron transfers, nucleophilic sub-
stitutions and eliminations, precipitation reactions, and hetero-
geneous (liquid–solid) reactions. The general mode of action
for each of these reaction classes is introduced in this section,
and detailed discussions of the most effective examples of each
class of reactions are provided in the subsequent section.
6.3.1.3.1  Electron Transfer Reactions
Electron transfer reactions, also known as oxidation–
reduction or “redox” reactions, are the most common of the
chemical reactive zone mechanisms. Both ISCO and ISCR
take advantage of electron transfer reactions in the destruc-
tion of contaminants. Biological reactions are predominantly
electron transfer reactions as well (Chapter 2). The most sig-
nificant distinction between bacterial and chemical reactive
zone chemistries is the use of catalysts (i.e., enzymes) by the
bacteria. Lacking the benefit of catalysts, chemical reactive
zones rely on much higher reactant concentrations to over-
come activation energy limitations.
There are two chemical roles fulfilled in each electron
transfer reaction: an electron donor (donor) and an electron
acceptor (acceptor). A compound or an element may serve
as a donor in some reactions and as an acceptor in others.
As detailed earlier in this chapter, an electron migrates from
the donor to the acceptor during the reaction process, signifi-
cantly changing the chemical behavior of both reactants. The
reactants and products when two compounds, A and B, par-
ticipate in a redox reaction are illustrated in Equation 6.76:
Areduced + Boxidized ® Aoxidized + Breduced (6.76)
For each electron transferred in the reaction of Equation 6.76,
the oxidation number of molecule A is increased by 1, and the
oxidation number of molecule B is reduced by 1. Compound
or element A is referred to as the reductant or reducing agent,
and compound or element B is the oxidant or oxidizing agent.
The oxidation of methane (CH4) by oxygen (O2), shown in
Equation 6.77, is an example of an electron transfer reaction:
CH 4 + 2O2 ® CO2 + 2H 2O (6.77)
The oxidation potential of the carbon in methane (CH4) was −4
and in carbon dioxide (CO2) its oxidation potential increased
to +4, which occurred through donation of electrons to the
oxygen (O2) atoms of the carbon dioxide (CO2) and water
(H2O) molecules. The oxidation potential of the diatomic
oxygen (O2) molecule was 0, which decreased to −2 in each of
four oxygen atoms in the products. The hydrogen (H+) atoms
268
had an oxidation state of +1 in both the methane (CH4) reac-
tant and water (H2O) product. In this reaction, the carbon
atom in methane (CH4) served as the donor (reductant) and
oxygen (O2) served as the acceptor (oxidant).
Electron transfers utilized for in  situ chemical remedia-
tion include homogeneous aqueous-phase reactions (both
reactants are aqueous phase) and heterogeneous reactions, in
which one of the reactants is in the solid (or sorbed) phase
and the other is in the aqueous phase. The gaseous reagents
that might be used for in situ chemical remediation (e.g., the
oxidant ozone [Section 6.3.2.2.4]) react in the dissolved phase.
6.3.1.3.2 Nucleophilic Substitution and
Elimination Reactions
Most of the reactions used in chemical treatment strategies
are highly energetic, with reaction half-lives (t1/2) measured
in minutes to hours. In this section, we introduce nucleophilic
substitutions and elimination reactions, which comprise a
much quieter class of reactions, with half-lives (t1/2) measured
in days to years in aquifers. With their low reaction rates, sub-
stitution and elimination reactions are most often associated
with MNA processes (e.g., hydrolysis for 1,1,1-trichloroethane
[1,1,1-TCA; C2H3Cl3]). It may be possible to accelerate hydro-
lysis reactions through temperature increase or pH change. It
is also possible to generate substitution reactions with other
nucleophiles. That is the reason why this relatively low-
intensity reaction mechanism has become a subject of study
for chemical reactive zone design.179–181
Hydrolysis is an example of a ubiquitous nucleophilic
substitution reaction, in which a water molecule (H2O) or
hydroxyl ion (OH−) is a reactant. The reaction is slow but sus-
tainable. Hydrolysis is likely to be considered a mechanism
supporting the natural attenuation of contamination, but most
of the reactions are too slow to be deployed in a reactive zone
strategy. However, the literature shows that other nucleophilic
reactions can be used effectively for treatment of some of the
halogenated alkanes and can be considered for deployment
in in  situ chemical reactive zones.179–181 These studies cen-
tered on treatment of fumigants, including methyl bromide
(CH3Br) and 1,3-dichloropropene (C3H4Cl2). In this section,
we describe the nucleophilic substitution mechanism and pro-
vide a basis for estimating rates of proposed nucleophilic sub-
stitution reactions from known hydrolysis rates.
The substitution reaction we consider in greatest detail is
termed a concerted reaction, because the substitution of one
functional group for another occurs in a single action. The
substituting group (the nucleophile) approaches the target car-
bon atom in the molecule from a position opposite the atom
or group of atoms that will be displaced (the leaving group).
In a single concerted reaction, electrons from the nucleophile
begin migration into a bond with the target carbon atom,
while electrons of the existing bond migrate to the leaving
group. These reactions are also known by the acronym SN2,
denoting “substitution (S), nucleophilic (N), bimolecular (2).”
Other important modes of nucleophilic substitution are the
SN1 reaction, a unimolecular nucleophilic substitution, and
the E2 reaction, a bimolecular elimination (E) that generates
Remediation Engineering
an alkene. For further readings on SN1, SN2, and E2 reactions,
see Schwarzenbach et al.165
Target sites for nucleophilic substitution reactions are elec-
tron depleted due to a more electronegative bonding partner.
Electrons in carbon atoms that are bonded to halogens or
other strongly electronegative atoms are drawn away from the
carbon, and this electron depletion endows the carbon atom
with a slightly positive charge. An electron-depleted atom is
a target for reaction with anions and molecules with electron-
rich atoms that can be donated to a covalent bond. Because
the substituting molecules are attracted to the positive charge
centered in an atom’s nucleus, they are termed nucleophiles.
Stated more formally, a nucleophile is an electron-rich mol-
ecule or ion that can react with a locus of electron depletion in
an organic molecule.*
Two nucleophilic substitution reactions with chloroethane
(C2H5Cl) are presented in Figure 6.71—base-mediated elimi-
nation (E2) and neutral-pH hydrolysis (SN2):
• In the base-mediated elimination reaction (E2), the
hydroxyl ion (OH−) is the nucleophile, capturing a
hydrogen nucleus (a proton; H+) from the methyl
group (CH3) end of the chloroethane molecule. The
electron of the C2–H bond migrates to form a dou-
ble bond with the other carbon atom (C1), while the
electrons of the C1–Cl bond migrate to the chlorine
atom, generating ethene (C2H4), water (H2O), and a
chloride ion (Cl−).
• In the neutral-pH hydrolysis (SN2) reaction, the elec-
tron-rich oxygen atom of the water molecule (H2O)
attacks the chlorine-bearing carbon atom (C1) from
a position opposite the chlorine atom. An electron
from one of the water’s hydrogen bonds migrates to
form an O–C1 bond, releasing the proton (H+). At the
same time, the electrons in the C1–Cl bond migrate to
the chlorine atom, releasing a chloride ion (Cl−). The
resulting products of the neutral-pH hydrolysis are eth-
anol (C2H6O), chloride (Cl−), and hydrogen ions (H+).
Activation energies for nucleophilic substitution reactions are
typically high, so they are temperature sensitive. For hydroly-
sis of chlorinated ethanes and methanes, the activation ener-
gies (EA) generally were estimated near 110 kJ/mol, with a
minimum 92.4 kJ/mol for 1,1,2,2-tetrachloroethane (C2H2Cl4)
and a maximum value of 122.9 kJ/mol for chloroform
(CHCl3).182 As an example, the neutral-pH hydrolysis (SN2)
half-life (t1/2) for 1,1,1-trichloroethane (1,1,1-TCA; C2H3Cl3)
* Electrons shared by atoms of different elements in covalent bonds are not
evenly distributed between the atomic nuclei. The elements vary in their
affinity for electrons, and the density distribution of the electron bonding
cloud is tipped toward the more electronegative atom. Carbon atoms lie in
the middle of the range between electronegative and electropositive atoms.
The halogens, such as chloride and fluoride, are strongly electronegative
elements. When these elements form a bond with other elements, the bond-
ing electrons are drawn strongly toward the halogens nucleus. The alkalis,
such as hydrogen and sodium, are strongly electropositive. Atoms of these
elements readily release their bonding electrons, and a positive charge
accumulates at these atoms.
Injected Reagent–Based Remedies 269

Base-mediated elimination (E2) reaction

OH–
H H H H H H
Cl Cl H H H
–
C C + OH C C C C + Cl– + H2O
H H H H H H

Neutral‐pH nucleophilic (SN2) hydrolysis reaction

H H H Cl H H H H H H
H Cl H
O + C C O C C HO C C + Cl– + H+
H H H H H H
H H

FIGURE 6.71  Potential reaction pathways for base-mediated elimination and nucleophilic substitution (water hydrolysis) of chloroethane.
Curved arrows show electron migrations.

TABLE 6.23
Kinetic Rate Constants and Arrhenius Parameters for Base-Mediated (KB) and Neutral-pH (KN) Hydrolysis
Neutral-pH Reaction Base-Mediated Action
Target Compound Product A (per min) EA (kJ/mol) A (L/mol/min) EA (kJ/mol) kobs (per min) Half-Life (Years)
Carbon tetrachloride CO2 + H2O 4.07 × 1012 114.5 3.46 × 10−8 38.1
Chloroethane Ethene + HCl 1.37 ×1013 110.8 3.72 × 1013 101.2 5.18 × 10−7 2.54
Acetaldehyde + HCl
1,1-Dichloroethane Chloroethene + HCl 3.54 × 1011 109.5 9.95 × 1013 114.8 2.26 × 10−8 58.2
Acetaldehyde + HCl
1,2-Dichloroethane Chloroethene + HCl 2.83 × 1010 103.7 1.75 × 1013 97.4 1.88 × 10−8 70
2-Chloroethanol
1,2-Dichloropropane 1-Chloropropene + HCl 1.6 × 1012 110.1 1.4 × 1014 110.1 7.93 × 10−8 16.6
2-Chloropropanol
1,1,1-Trichloroethane Acetic acid 4.06 × 1014 117.2 1.6 × 10−6 0.826
1,1-Dichloroethene 3.7 × 1014 119.4

Source: Washington, J.W., Groundwater, 333, 415, 1995.

Note: All values are for reactions at 25°C and pH = 7.0.

increased from 0.86 to 10.3 years, as the reaction temperature 6.3.1.3.3 Nucleophilicity

decreased from 25°C to 10°C. The hydrolysis reaction activa-
tion energy for 1,1,1-trichloroethane (1,1,1-TCA; C2H3Cl3) is
119.4 kJ/mol.182 A discussion of temperature effects on reac-
tion rates, along with methods for kinetic rate calculation, is
presented in Section 6.3.1.4.1.
There are three categories of hydrolysis that can occur:
acid mediated, neutral pH, and base mediated. The observed
hydrolysis rate for any compound is the sum of the rates of the
three categories:
kobs = K A + K N + K B (6.78)
Washington182 summarized rate constant and Arrhenius
parameters for the neutral-pH and base-mediated reaction
mechanisms, pointing out that natural aquifers are normally
buffered into pH ranges that do not support acid-mediated
hydrolysis.182 Data excerpted and converted from Washington
are presented in Table 6.23.
Nucleophilic substitution reactions can be driven by com-
pounds other than water (H2O) and the hydroxyl anion (OH−).
A list of common aqueous-phase nucleophiles is presented
in Table 6.24. The strength of each compound’s reactiv-
ity in nucleophilic substitution reactions, or nucleophilicity,
is also provided in Table 6.24. The nucleophilicity values
given are for each nucleophile’s reaction with methyl bromide
(CH3Br), scaled relative to the neutral-pH hydrolysis reaction
for methyl bromide (CH3Br). Schwarzenbach et al.165 provide
Equation  6.79 developed by Swain and Scott (published in
1953) for the extrapolation of nucleophilic substitution reac-
tion kinetics for methyl bromide (CH3Br), from its neutral-pH
hydrolysis rate constant, k H2O:
æk ö
log ç nuc ÷ = s ´ nnuc,CH3 Br (6.79)
è kH2 O ø
270 Remediation Engineering

From experimental studies reported by Wang et  al.,181 the

TABLE 6.24 rate constant for overall hydrolysis, k obs, was reported as
Nucleophilicity of Selected Ions, nnuc ,CH3Br , Based on 9.19 × 10 −4 h−1 (2.6 × 10 −7 s−1) at 20°C. This indicates good
Reaction with Methyl Bromide agreement between theoretical and experimental observa-
tions of hydrolysis for methyl bromide (CH3Br). Larger dif-
Nucleophile Compound Name Chemical Formula nnuc ,CH3Br ferences are likely to arise for nucleophilic reactions with
Water H2O 0.0 target compounds other than methyl bromide (CH3Br),
Nitrate ion NO3− 1.0 however. Some of these differences will be related to the
Fluoride ion F− 2.0 susceptibility factor (s) in Equation 6.79, and in other
Sulfate ion SO42− 2.5 cases, unrecognized nucleophiles may be present in reac-
Acetate ion CH3COO− 2.7 tion solutions (e.g., phosphate [PO 43−] buffers have nucleo-
Chloride ion Cl− 3.0 philic potential). Pagan et al.183 noted significant differences
Bicarbonate ion HCO3− 3.8 among reported hydrolysis rate constants for chlorinated
Phosphate ion HPO42− 3.8 ethanes and propanes.
Bromide ion Br− 3.9 There are many potential nucleophilic reaction pathways
Hydroxyl ion OH− 4.2
and a large number of potential nucleophiles that could be
Iodide ion I− 5.0
used to support destruction of aqueous-phase contaminants.
Cyanide ion CN− 5.1
Most of the reactions are slow at aquifer temperatures but
Bisulfite ion HS− 5.1
do contribute to the broader natural attenuation mechanisms
Thiosulfate ion S2O32− 6.1
for select contaminants. Due to the increased susceptibil-
Source: Schwarzenbach, R.P. et al.: Environmental Organic Chemistry, ity of the chlorinated alkanes to hydrolysis mechanisms at
2nd  ed., John Wiley & Sons, New York, 2003. Copyright Wiley- increased temperatures, these reactions can be levered suc-
VCH Verlag GmbH & Co. KGaA. Reproduced with permission. cessfully as part of heated oxidation applications. Candidate
Note: Values for nnuc,CH3Br can be used in Equation 6.80 to estimate kinetic reaction systems should be tested at the bench scale, with
rate constants for nucleophilic substitution reactions. great care taken to run the tests at expected aquifer tempera-
tures, due to the temperature sensitivity of the nucleophilic
reactions.
Simplifying,
knuc 6.3.1.4  Geochemical Considerations
= 10 s´nnuc ,CH3Br (6.80)
kH2 O This section provides a brief discussion of three important

geochemical considerations for chemical reactions: tempera-
Using Equation 6.80 and Table 6.24, the second-order kinetic ture, pH, and ionic strength. The importance of geochemistry
rate constant for the reaction of methyl bromide (CH3Br) when implementing in situ chemical remediation is exempli-
with other nucleophiles can also be estimated. For example, fied by the influence on reaction rates, feasibility of targeted
the nucleophilicity of the hydroxyl anion (OH−) is 4.2. That reactions, secondary by-product formation, and the cost of
value can be substituted into Equation 6.80 to determine the implementation.
second-order reaction rate constant for base-mediated hydro-
lysis of methyl bromide (CH3Br): 6.3.1.4.1  Effect of Temperature on Reactions
The temperature of a reaction solution is one of the variables
kOH,CH3 Br = kH2 O,CH3 Br ´10 nOH,CH3Br (6.81) controlling the frequency of contact events between reactants
(another is the concentration of the reactants). Temperature also
Schwarzenbach et  al. (2003) indicate that the value for
determines the energy at which contact occurs. Consequently,
k H2O, CH3Br is approximately 5 × 10 −9 L/(mol s) at 25°C (298 K).
temperature can have a significant impact on reaction rates.
That value can be used to project a value for kobs, the combined
The Arrhenius equation (Equation 6.83) describes the rela-
rate constant for K N and KB. Using Equations 6.78 and 6.81,
tionship between the temperature and the kinetic rate constant
we can estimate kobs as a function of hydroxyl anion (OH−)
for a reaction as follows:
concentration (note that kobs is typically shown as a pseudo-
first-order rate constant): - EA

( ) (
kobs = kH2 O ´ éëH 2O ùû + kOH,CH3 Br ´ 10 4.2
)
´ éëOH ùû (6.82)
- k = A ´ e RT (6.83)

where A is the preexponential factor that describes the fre-

Solving (at neutral pH),
quency of collisions with the correct geometry for a reaction

(
kobs = 2.8 ´ 10 -7 + 5 ´ 10 -9 ´ 10 4.2 ´ 10 -7
kobs = 2.8 ´ 10 -7 + 4.4 ´ 10 -10
kobs = 2.8 ´ 10 -7
) to occur (L/[mol * S]) and the exponential term quantifies the
fraction of collisions that occur with sufficient energy to com-
plete a reaction. EA is the activation energy, and R and T are
the universal gas constant (8.3145 J/[mol * K]) and the reac-
tion temperature (K), respectively.
Injected Reagent–Based Remedies 271

In many cases, a kinetic rate constant (k) for a reaction

is available at a generic temperature (T1), and a calculation TABLE 6.25
is required to determine the kinetic rate constant (k) for a Ionization Constants for Pure Water
site-specific temperature (T2). If the activation energy (EA) is
Temperature (°C) K wa = éëH+ ùû ´ éëOH- ùû
known for the reaction of interest, the kinetic rate constant (k)
can be calculated for the reaction at an alternative tempera- 10 0.29 × 10−14
ture using Equation 6.84: 15 0.45 × 10−14
20 0.68 × 10−14
æk ö E æ 1 1ö 25 1.01 × 10−14
ln ç T1 ÷ = A ç - ÷ (6.84) 30 1.47 × 10−14
è kT2 ø R è T2 T1 ø
Source: Kotz, J.C. et al., Chemistry and Chemical Reactivity, 5th ed.,
Many reactions that can be considered for in  situ chemical Thomson-Brooks/Cole, 2003.
a The units for K are mol2/L.
remediation are temperature sensitive, and it is important w

to consider the expected reaction temperature when evalu-

ating the use of these reactions. Nucleophilic substitutions
and persulfate (S2O82−) oxidation are among the especially
temperature-sensitive reactions.
6.3.1.4.2  Effect of pH on Reactions
Changes in the solution pH for reactions that involve a hydro-
gen ion (H+) or hydroxyl anion (OH−) directly affect the reac-
tion rate. The effect can be assessed by supplying alternative
values for the hydrogen ion (H+) or hydroxyl anion (OH−), as
appropriate for the reaction. The hydrogen ion (H+) concen-
tration is calculated as the negative log of the pH, and the
hydroxyl anion (OH−) concentration for a specified pH value
can be calculated from the dissociation of water, which is
expressed by Equation 6.85:
kw
H 2O « H + + OH - (6.85)
The activity of a pure substance (a solid or a liquid) is typi-
cally approximated to be unity in equilibrium expressions due
to the relative insensitivity to dilute species.166 In other words,
water (H2O) is present at a high concentration compared to
the dissolved contaminant concentrations that the concen-
tration of water (H2O) remains unchanged during reactions.
This is an appropriate universal assumption that is applied to
pure liquids and solids relevant to discussions in this book.
Therefore, the dissociation rate for Equation 6.85 is defined
by Equation 6.86:
K w = éëH + ùû ´ éëOH - ùû (mol 2 /L or M2 ) (6.86)
Applicable dissociation constants for water (Kw) as a function
of temperatures ranging from 10°C to 30°C are presented in
Table 6.25. The hydroxyl anion (OH−) concentration is defined
as a function of pH and the dissociation constant for water
(Kw) in Equation 6.87:
sometimes referred to as the proton concentration. For exam-
ple, at pH 11 and 20°C, Kw = 0.68 × 10 −14 (Table  6.25) and
(using Equation 6.87)
éOH - ù = 0.68 ´ 10 -14 ´ 1011 = 6.8 ´ 10 -4 (M)
ë û
The ionic strength that results from the hydroxyl anion (OH−)
concentration at pH 11 can reduce the activity of other ions
in solution.
6.3.1.4.3  Effect of Ionic Strength on Reactions
Aqueous-phase molar concentrations are utilized in cal-
culations as an estimate of chemical activity. The activity
of a chemical species, {A}, is related to its aqueous-phase
concentration [A] by its activity coefficient (γA), as shown in
Equation 6.88:
{ A} = g A éë Aùû (6.88)
The value of the activity coefficient (γA) approaches unity in
very dilute aqueous solutions, and under these conditions,
the concentration ([A]) provides an accurate representation
of chemical activity. However, as dissolved ionic solids’ con-
centrations increase, the value of the activity coefficient (γA)
decreases significantly. Ionic solids’ concentrations in many
chemical reactive zone applications are high, and calculations
that use molar concentrations, in lieu of chemical activities,
may overestimate reaction rates.
The calculation of ionic strength (I) is a function of the
concentration (Ci) and the ionic charge (zi) of the dissolved
constituents (Equation 6.89):
åC z (6.89)
1
I= 2
i i
2

éOH - ù = K w ´10 pH (6.87)
ë û
Further, pH also affects reactions through the contribution to
ionic strength from hydroxyl anion (OH−) or hydrogen ion (H+)
concentration at extreme pH values. The hydrogen ion (H+) is
For solutions with relatively low ionic strength (I < 10 −2.3), the
Debye–Huckel equation provides an estimate of the activity
coefficient at 25°C (Equation 6.90):
log ( g ) = -0.5z 2 I (6.90)
272 Remediation Engineering

TABLE 6.26
Summary of Available Oxidants, Characteristics, and Resultant Reactive Species
Oxidant Chemical Formula Available Form Initiator/Activator Resultant Reactive Species
Permanganate MnO4 − Powder or liquid None MnO4−
Hydrogen peroxide H2O2 Liquid None, Fe2+, Fe3+ OH•, O2•−, HO2•, HO2−
Ozone O3 Gas None, H2O2 O3, OH•
Persulfate S2O82− Powder None, Fe2+, Fe3+, heat, H2O2, high pH S2O82−, SO4•−
Percarbonate Na2CO3 · 1.5H2O2 Powder Fe2+ OH•
Calcium peroxide CaO2 Powder None H2O2, HO2−

Source: Huling, S.G. and Pivetz, B.E., Engineering issue paper: In-situ chemical oxidation. EPA 600-R-06-072. U.S. Environmental
Protection Agency (USEPA) Office of Research and Development, National Risk Management Research Laboratory, Cincinnati,
OH, 60 p, 2006. http://www.epa.gov/tio/tsp/issue.htm#EF.

The extended Debye–Huckel equation adds a correction factor
(a) that accounts for the effects of the ionic radius of each spe-
cies and is valid for ionic strengths up to 0.1 M (Equation 6.91):
æ I ö Table 6.27. Each of the ISCO reagents has limitations related
log ( g ) = -0.5z 2 ç (6.91)
ç 1 + 0.33a I ÷÷
è ø
Values for the correction factor (a) are given by Stumm and
Morgan.164
An example of interest is the ionic strength (I) of reagents
at the solution “working strength” commonly used in in situ
chemical reactive zones. For example, the persulfate anion
(S2O82−) is likely to be applied in aquifers at a strength of
1% by weight (10 g/L) or greater. The molecular weight of
sodium persulfate (Na2S2O8), which is often used to gener-
ate the oxidant solution, is 238 g/mol. Therefore, a 10 g/L
sodium persulfate (Na2S2O8) solution is equivalent to a molar
concentration of 0.042 mol/L. Because the chemical formula
for sodium persulfate (Na2S2O8) shows the sodium (Na+) to
persulfate (S2O82−) mole ratio is 2:1, the sodium cation (z = +1)
concentration is twice that of the persulfate anion (z = −2)
concentration. Using Equation 6.89,
are the most common oxidant sources for ISCO treatments.184
A collection of characteristics of available chemical oxidants
is presented in Table 6.26, and the standard reduction poten-
tial of commonly resultant reactive species is presented in
to its reactivity, stability, and transport. CHP has the poten-
tial to degrade a wide range of organic contaminants and has
been shown to treat sorbed contaminants and DNAPL.185–
187 However, the CHP oxidant source, hydrogen peroxide
(H2O2), is unstable and short-lived in the subsurface. Ozone
(O3)-based ISCO processes have the potential for treating
groundwater contaminants but are limited by mass transport
and stability. In contrast, permanganate (MnO4−) is stable in
the subsurface but is reactive with a narrow range of contami-
nants.188 Persulfate (S2O82−) is the newest ISCO reagent and is
more stable than CHP and more reactive than permanganate
TABLE 6.27
Summary of the Standard Reduction Potential of
Common Resultant Reactive Species and Parent
Compounds

å ( 0.084 ´ ( +1) + 0.042 ´ ( -2 ) )

1 2 2
Standard Reduction
I=
2 Resultant Reactive Species Formula Potential (V)
Hydroxyl radical OH• +2.8
and
Sulfate radical SO4•− +2.6
I = 0.126 M Ozone O3 +2.1
Persulfate anion S2O82− +2.1
This result exceeds the application of the extended Debye– Hydrogen peroxide H2O2 +1.77
Huckel equation (Equation 6.91). It is clear that this ionic Permanganate anion MnO4− +1.7
strength (I) would have an influence on the assumption that all Perhydroxyl radical HO2• +1.7
Oxygen O2 +1.23
activity coefficients are unity and underscores the importance
Hydroperoxide anion HO2− −0.88
of understanding the assumptions upon which rate calcula-
Superoxide radical O2•− −2.4
tions are built.
Source: Huling, S.G. and Pivetz, B.E., Engineering issue paper: In-situ
6.3.2 Chemical Oxidation chemical oxidation. EPA 600-R-06-072. U.S. Environmental
Protection Agency (USEPA) Office of Research and Development,
ISCO involves the injection of strong chemical oxidants into National Risk Management Research Laboratory, Cincinnati, OH,
the subsurface. CHP (modified Fenton’s reagent), permanga- 60 p, 2006. http://www.epa.gov/tio/tsp/issue.htm#EF.
nate (MnO4−), ozone (O3), and activated persulfate (S2O82−)
Injected Reagent–Based Remedies
(MnO4−)189; however, persulfate (S2O82−) requires activation
for efficient degradation of contaminants.
This section comprises several fundamental principles
of ISCO, combined with some example demonstrations and
bench-scale and field-scale case studies. The chemical oxida-
tion field of study has a lengthy publication history, and some
key references that the reader is referred to are Siegrist et al.,184
Osgerby,159 ITRC Guidance Document,160 the Petroleum
Environmental Research Forum Project in 2013,161 and the
U.S. Environmental Protection Agency review in 2006.162
6.3.2.1  Radical Reactions
The most aggressive of the chemical reactive zone mecha-
nisms is the radical chain reaction. It is the basis for CHP
reagent, the basis of engineered flexibility for persulfate
(S2O82−) chemistry, and much of the functionality of ozona-
tion (i.e., ozone [O3] can act directly as an oxidant or serve as
a feedstock reagent for hydroxyl radical [OH•] formation). The
kinetic rate constants (k) of radical reactions are the highest
of any of the chemical reactive zone mechanisms, with many
of the reaction rates exceeding 1010 M−1 s−1. Because radical
reactions used in chemical reactive zones occur quickly, con-
centrations of radicals in solution never reach high levels. The
hydroxyl radical (OH•), for example, is expected to range from
1 × 10 −13 to 1 × 10 −11 M.190,191
A summary of second-order kinetic rate constants (k) for
reactions of the hydroxyl radical (OH•), ozone (O3), perman-
ganate (MnO4−), and persulfate (S2O82−) with typical organic
contaminant compounds, along with reaction rates for com-
pounds that may act as scavengers, is provided in Table 6.28.
Scavengers are defined as those competitive inhibiting com-
pounds that consume oxidant capacity yet are not targeted
contaminants. Additionally, estimates of molarities that can
be achieved in reactive zone applications for each oxidant are
provided (Table 6.28). These values can be used in conjunc-
tion with kinetic rate constants (k) and target contaminant
concentrations to estimate treatment rates and competitive
interactions that are likely to be observed in field applications.
6.3.2.1.1  Radical Chemistry
Radicals are atoms or compounds that have unpaired electrons
and are typically extremely reactive. Many chemical reac-
tion mechanisms include formation and instantaneous reac-
tion of radicals to form new compounds. To harness radical
reactions during in situ chemical remediation, it is necessary
to generate useable radicals from a feedstock reagent in situ.
The most sought-after of these highly reactive agents is the
hydroxyl radical (OH•). Reflecting its high level of reactivity,
the Notre Dame Radiation Laboratory/National Institute of
Standards and Technology (NDRL/NIST) solution kinetics
database characterizes 1787 reactions in which the hydroxyl
radical (OH•) is a reactant, while it is a product of only 54
listed reactions.196
The creation of a hydroxyl radical (OH•) from hydrogen
peroxide (H2O2) through reaction with a ferrous iron (Fe2+) is
presented in Figure 6.72. The ferrous iron (Fe2+) donates an
electron to the hydrogen peroxide (H2O2) molecule, causing
273
it to split into a hydroxyl anion (OH−) and a hydroxyl radi-
cal (OH•). Notice that the oxygen atom in the hydroxyl anion
(OH−) has a total of eight valence electrons, including the pair
shared in the covalent bond with a hydrogen atom. Hydrogen
and oxygen in the hydroxyl anion (OH−) together bring
seven valence electrons. The eighth, donated by the ferrous
iron (Fe2+) atom, is an “extra,” conferring a negative charge
on the molecule. The fact that the electrons are all “paired”
decreases their reactivity, relative to the unpaired electron of
the hydroxyl radical (OH•).
The hydroxyl radical (OH•) is electrically neutral, because
there are seven valence electrons in the molecule (six from the
oxygen and one from the hydrogen) so the protons and elec-
trons are equal in number. Although the molecule is electri-
cally neutral, the unpaired electron associated with the oxygen
atom is highly reactive, readily capturing electrons from other
atoms and molecules. The aggressive capture of electrons
makes the hydroxyl radical (OH•) a strong oxidant. Many of its
reactions are so fast that they are limited by the aqueous dif-
fusion rates of its reactants (hence the term ­“diffusion-limited
reaction rate”). There are many mechanisms of hydroxyl radi-
cal (OH•) formation, but for in situ chemical reactive zones,
the primary sources of hydroxyl radical (OH•) are reactions
with hydrogen peroxide (H2O2), as in the Fenton’s reagent
reactions, alkaline activation of the persulfate anion (S2O82−),
and sparingly through radical initiation reactions with the
ozone (O3) molecule.
6.3.2.1.2  Chain Reactions
As a result of their high reactivity, radicals can enter into
many reactions in any natural groundwater system. Hassan
et al.197 incorporated the kinetics of 72 reactions to effectively
model the hydroxyl radical (OH•) reaction network with ozone
(O3) and hydrogen peroxide (H2O2) feedstock, in the presence
of bromide (Br−), phosphate (PO43−), and carbonate (CO32−)/
bicarbonate (HCO3−) ions.
Many of the potential reaction products are radicals, and
the formation of a radical chain reaction network is a fea-
ture of efficient use of radicals in chemical reactive zones.
There are three basic processes occurring in a radical reaction
network—initiation, promotion, and termination:
• Initiation. The first step in a radical chain reac-
tion is the formation of a radical through reaction
between an initiator and a feedstock reagent. A
practical way to envision a radical-based chemical
reactive zone is the injection of a compound that
carries energy that can be used to drive reactions,
but which is not sufficiently reactive to drive the
process directly. Reaction with an initiator acti-
vates the feedstock reagent, forming a radical and
thereby concentrating the available energy in the
unpaired valence electron.
• Promotion. Many of the possible reactions of the first
radical formed generate radicals as products. The
secondary radicals may react with target compounds
in termination reactions, form other radicals that
274 Remediation Engineering

TABLE 6.28
Summary of Kinetic Rate Constants for Oxidation Reactions
with Common Organic Contaminant Compounds
Second-Order Kinetic Constants (M/s)
Sulfate
Hydroxyl Radical Permanganate
Compound Ozone (O3) Radical (OH•) (SO4•−) (MnO4−)
PCE <1 × 10−1 3 × 109 4.5 × 10−2
6.5 × 10−1
TCE 1.7 × 101 4 × 109 6.6 × 10−1
8.9 × 10−1
cis-DCE <8 × 102 9.2 × 10−1
1,1-DCE 1.1 × 102 7 × 109 2.4 × 100
1,1,1-TCA <1.2 × 10−2 1 × 108
1,2-DCP <4.0 × 10−3 3.8 × 108
MTBE 0.14 [192] 1.6 × 109 3.1 × 107 [195] 3.5 × 10−5 [193]
1,4-Dioxane 3.2 × 10−1 2.4 × 109 Not reactive [194]
Tetrahydrofuran 4.0 × 109 [191] 1.1 × 108 [195]
NDMA 10 3.3 × 108
tert-Butyl alcohol 3 × 10−3 2.4 × 109
Methanol 2.4 × 10−2 3.3 × 108
Ethanol 1.6 × 109 [191] 7.8 × 105 [195]
Phenol 1.4 × 102 5.9 × 108
Acetate 3 × 10−5 9.7 × 108
Benzene 2 × 100 7.8 × 109
Fluorene 1.8 × 1010
Phenanthrene 1.5 × 104 2.3 × 1010
Naphthalene 3 × 103 9.4 × 109
Nitrobenzene 4.0 × 109
HCO3− 8.5 × 106 6.1 × 106 [195]
CO32− 4.0 × 108 1.6 × 106 [195]
Cl− 4.3 × 109 [191] 2.5 × 108 [195]
Fe2+ 5 × 105 1.7 × 1010
Formic acid 5 × 100 3.5 × 10−1
Glyoxylic acid 1.7 × 10−1 3.7 × 10−1
Oxalic acid 1.1 × 10−1
H2O2 (HO2−) (5.5 × 106)
Oxidant Feasible oxidant molarities (mol/L)
Ozone 1 × 10−3 (6% O3 gas phase)
(O3)
Hydroxyl radical 1 × 10−13 to 1 × 10−11
(OH•)
Sulfate radical
(SO4•−)
Permanganate 2.5 × 10−1 to 2.8 × 100 (4% KMnO4 to 40% NaMnO4)
(MnO4−)

Source: Ross, A.B. et al., NDRL-NIST solution kinetics database—Version 3, Notre Dame Radiation
Laboratory, Notre Dame, IN, and NIST Standard Reference Data, Gaithersburg, MD, 1998.

propagate the chain reaction, or serve as initiators.
The secondary radicals might be more reactive with
the target compound than the first radical formed.
An example of radical promotion is the generation
of the superoxide (O2•; moderate reductant) radical
during alkaline activation of persulfate (S2O82−) (or
activation through trace aquifer minerals), which
subsequently reduces geogenic ferric iron (Fe3+) to
ferrous iron (Fe2+), which serves to initiate more per-
sulfate radicals (S2O8•).198–200
Injected Reagent–Based Remedies 275

Fe2+ Fe3+ scavengers in chemical reactive zones are carbonate (CO32−)

and bicarbonate (HCO3−) ions.
A conceptual radical chain reaction network, which is fed
by either hydrogen peroxide (H2O2) or ozone (O3) as a feed-
stock reagent, is presented in Figure 6.73. Ferrous iron (Fe2+)
•• •• serves as an initiator, generating the first radical, a hydroxyl
H •• O •• O •• H
•• •• radical (OH•). The hydroxyl radical (OH•) can then enter a pro-
motion reaction, enter a target compound termination reaction
sequence, or succumb unproductively to a scavenger reaction
•• •• such as shown with the bicarbonate (HCO3−) ion.
H •• O • ••O •• H
•• ••
6.3.2.2  Reagent Loading and Geochemistry
(OH•) (OH–) Not surprisingly, the two main drivers for chemical reagent
Hydroxyl Hydroxyl
loading to an in situ chemical reactive zone are the contami-
radical anion
nant concentrations (or the contaminant oxidant demand) and
FIGURE 6.72  Creation of hydroxyl radical (OH•) from hydrogen the amount of oxidant that is scavenged by the aquifer (or
peroxide (H2O2), showing Lewis structures. Ferrous iron (Fe2+) is the matrix oxidant demand). These important ISCO design
the initiator and is reduced to ferric iron (Fe3+) by the donation of an parameters are site specific, and it is best to conduct bench-
electron to the hydrogen peroxide (H2O2) molecule. scale treatability testing prior to a field implementation to
fully understand them.
• Termination. The final step in the radical chain The nontarget demand is termed the matrix oxidant
reaction is termination of the radical. When radi- demand (commonly referred to as the natural oxidant demand
cal chemistry is employed for oxidation of dissolved (NOD) as well). The matrix oxidant demand dictates how
organic compounds in a chemical reactive zone, the much oxidant can be distributed throughout the treatment ROI
radical propagation sequence generates a carbon to completely destroy the appropriate quantity of contaminant
radical (R•). The carbon radical (R•) acts as a donor, mass. Matrix oxidant demand is a function of the aquifer soil
reducing a susceptible molecule. Then, the organic type and the oxidation–reduction status. It represents all of
molecule bearing the carbon radical (R•) cracks and the reduced species likely to exert scavenging or competitive
releases carbon dioxide (CO2). In an ideal radical inhibition on the in situ engineered chemistry. Lower matrix
chain reaction, the carbon radical (R•) reduces an oxidant demand is expected from coarse-grained sands and
oxidized initiator, recycling it to rejoin the radical gravels, while relatively higher demands are expected for
chain reaction network. fine-grained soils such as silts and clays. The results of matrix
oxidant demand testing for a range of soil types collected at a
Unproductive termination reactions also occur in reactions Midwestern site are presented in Table 6.29. The permanga-
that are often referred to as scavenging. Two of the prominent nate (MnO4−) demand ranged from 6.3 to 18.5 g of oxidant per

Productive
Precursor termination pathways
(H2O2, O3) (CO2(g))
Reduced
Reduced initiator
initiator (Fe2+)
(Fe2+)
Radical propagation pathways
(O•3–, HO•2, O•2–, O•–)
Oxidized Carbon
radical Oxidized
initiator
(•C---R) initiator
(Fe3+)
(Fe3+)

Radical Smaller
(OH•) organic
molecule

Scavengers Dissolved
(HCO3–) organic
Unproductive termination pathways carbon
(HCO3• , OH–) (C---R)

FIGURE 6.73  Radical chain reaction network (simplified), showing the network or reactions that develop when hydrogen peroxide (H2O2)
or ozone (O3) is injected into an aqueous-phase solution containing dissolved organic carbon.
276 Remediation Engineering

oxidant demand (ODM) is based on the mass of the soil (Ms)

TABLE 6.29
Permanganate Matrix Demand Results for Aquifer
Soils at a Midwestern Site
Sample Soil Description
1 Sand, gravel
1-rep Sand, gravel (replicate)
2 Sand, gravel, rock
3 Clay
4 Clay loam (wet)
5 Sand, clay
(hydrocarbon odor)
in the treatment ROI, which is calculated to be 1.3 × 105 kg.
Therefore, the conceptualized matrix oxidant demand (ODM)
for this example treatment ROI is approximately 1 × 103 kg of
oxidant. The four order of magnitude difference between the
Observed Permanganate
Demand(g KMnO4/kg dry wt)
matrix oxidant demand (ODM) and the contaminant oxidant
demand (ODC) demonstrates the significance of the matrix
7.53
oxidant demand in ISCO design and implementation and
9.84
highlights the importance of pretreatment bench-scale treat-
6.34
ability testing. The calculations discussed in this paragraph
18.53
are illustrated in the following:
7.91
8.21
Vgw = p ´ ROI 2 ´ h ´ qT = 31 m 3

Note: Batch testing was conducted over a 4-day exposure period on soil M c = Vgw ´ Cgw = 3.1 ´ 10 -2 kg
samples collected from an aquifer contaminated by trichloroeth-
ene. Total organic carbon concentrations were 550–580 mg/kg in
two samples that were analyzed for that parameter. ODc = MR ´ M c = 1 ´ 10 -1 kg

M s = p ´ ROI 2 ´ h ´ rb = 1.3 ´ 105 kg

kilogram of soil gox/kgs. For an aquifer with a bulk density of
1500 kg of soil per cubic meter of soil kgs/m3s, that translates
to 9.5 to 27.8 kg of oxidant per cubic meter of soil kgox/m3s
( )
or 16 - 47 lbox /yd 3ox . Typical matrix oxidant demand values
range from less than 0.1–20 g of oxidant per kilogram of soil
gox/kgs.201 For conceptual budget preparation (prior to bench-
scale treatability testing), most sites can be expected to fall
within the range of 1–20 gox/kgs.
To demonstrate the significance of the matrix oxidant
demand, consider a site that has a measured matrix oxidant
demand (ODm) of 8 gox/kgs. The total benzene (C6H6), tolu-
ene (C7H8), ethylbenzene (C8H10), and xylene (C8H10; BTEX)
concentration in groundwater (Cgw) at this site is 1000 µg/L,
and numerous soil samples indicate that minimal adsorbed
BTEX is present. There are no observations of drainable or
nondrainable LNAPL, and the injection hydraulics are ame-
nable to the ISCO technology. The targeted ROI is 3 meters
over a 3 meter thickness (h), and the total porosity (θT) and
bulk density (ρb) of the soil are 36% and 1500 kgs/m3s, respec-
tively (as confirmed through geotechnical testing). The antici-
pated groundwater volume (Vgw) in the treatment ROI is 31 m3.
Therefore, the estimated dissolved-phase mass of BTEX in
the groundwater (MC) is 3.1 × 10 −2 kg. For the sake of this
example, it is assumed that oxygen is the oxidant and the reac-
tion between BTEX and oxygen is a direct electron transfer
that follows ideal stoichiometry. From Equation 6.53, the stoi-
chiometric ratio of oxygen and benzene (C6H6) is 7.5:1, and
the resultant mass ratio (MR) is 3.1 kg of oxygen per kg of
benzene.* Therefore, the conceptualized contaminant oxidant
demand (ODC) for 1000 µg/L BTEX over this example treat-
ment ROI is approximately 1 × 10 −1 kg of oxygen. The matrix
* In this example, BTEX is conceptualized to be represented by benzene
(C6H6). It can be shown through stoichiometry of balanced chemical reac-
tions that the approximation of 3.1  kg oxygen per kg of benzene (C6H6)
is sufficiently representative of toluene (C7H8), ethylbenzene (C8H10), and
total xylenes (C8H10), which have oxygen to contaminant ratios of 3.1, 3.2,
and 3.2 kg oxygen per kg contaminant, respectively.
ODM = M s ´ ODm = 1 ´ 103 kg
A potential strategy to dealing with the matrix oxidant demand
is to recognize the total matrix oxidant demand and divide
it equally among multiple injection events. This reduces the
oxidant injection concentration and allows for field-scale data
analysis to dictate the actual level of matrix oxidant demand.
Additionally, matrix oxidant demand may be realized over
time as reactions with aquifer minerals occur, and front-load-
ing all of the matrix oxidant demand may result in excessive
wasted oxidant load. A general equation that integrates the
total injection volume, the aquifer pore space through which
the reagent travels, and the matrix oxidant demand deter-
mined in a laboratory (ODm) is included in Equation 6.92.
This calculation also includes the soil bulk density (ρb) and
the anticipated injection concentration (Cox):
(
ODm ( gox /kgs ) ´ rb kgs /m 3s )
( )
Injection volume L ox soln /m 3s =
Cox ( gox /L ox sol )
(6.92)
This highlights a significant issue of any chemical reactive
zone application—aqueous-phase liquid injections are lim-
ited in the reagent mass that can be delivered per unit vol-
ume, and multiple aquifer pore volumes of fluid injection are
often required to deliver the specified reagent mass. Multiple
injection episodes or days-long, slow-paced injections may be
required to deliver oxidant at a rate that matches the rate at
which the reactions occur in the aquifer. Dilution that occurs
when the injected fluid reaches the formation and travels along
preferred flow paths further complicates the delivery process.
The hydraulic challenges associated with multiple
pore volume chemical floods are evaluated by Ibaraki
and Schwartz.202 They concluded that contact efficiencies
of chemical floods will be low in heterogeneous media.
Because their study did not include consideration of carbon
Injected Reagent–Based Remedies
dioxide (CO2) gas production associated with oxidation (and
the associated localized reduction of hydraulic conductivity),
chemical flood efficiencies are likely to be even lower than
their modeling projected.
The contaminant oxidant demand is not always insignifi-
cant. If considerable adsorbed contaminant mass or drainable/
nondrainable NAPL exists (adsorbed/NAPL mass), the con-
taminant oxidant demand can be considerable and may even
preclude ISCO as a remedial alternative. As will be discussed
in this chapter, the reaction rate associated with most ISCO is
extremely rapid compared to biological reactions. Additionally,
the scavenging rate of oxidants is a considerable competitive
inhibitor. In Section 6.3.2.1.1, this was referred to as diffusion-
limited reaction rates, implying that the rate of oxidation is
actually limited by aqueous-phase diffusion-facilitated con-
tact between the oxidant and contaminant molecules. As the
contaminant in groundwater is destroyed, the concentration
gradient between the contaminant in the groundwater and the
adsorbed/NAPL mass increases, and this drives dissolution
and desorption of the adsorbed/NAPL mass into the ground-
water. Considering that the rate of oxidation is so fast that con-
tact within the same phase is rate limiting, it is unrealistic to
assume that the residence time of the oxidant in situ will match
the dissolution and desorption rate. With the advanced under-
standing of remediation hydraulics203 and the complexities of
adsorbed/NAPL mass in heterogeneous stratigraphic porous
media, it should be expected that ISCO implementation for
significant adsorbed/NAPL mass will require numerous injec-
tions over an extended time frame. This reality should be con-
sidered against preliminary remedial strategies that physically
remove adsorbed/NAPL mass. While treatment of contami-
nant source zones and adsorbed/NAPL with various forms
of ISCO is possible, the practical implementation should be
expected to be lengthy with numerous injection events, and
the cost of such effort and reagent loading may be impractical.
6.3.2.2.1  Importance of Bench Testing
Considering the importance of matrix and contaminant oxi-
dant demand, pretreatment bench-scale treatability testing
should be strongly considered as a requirement for ISCO.
Typical costs of bench-scale treatability testing range from
$10,000 to $40,000 depending on the scale and are inclusive
of sample collection and shipment, treatability testing, and
analytical laboratory costs. Common objectives of an ISCO
treatability test include
1. Understanding the matrix oxidant demand
2. Evaluating the potential for secondary water quality
concerns
3. A comparison of different oxidants, oxidant concen-
trations, and/or activator efficacies
4. Proof of concept, whereby the destruction of a par-
ticular contaminant is demonstrated to be feasible (if
necessary)
Bench-scale treatability testing may be a regulatory require-
ment to understand the potential for secondary water quality
277
concerns. If ISCO is the preferred remedy at a site, oftentimes
effective bench-scale treatability testing can garner support.
Sample collection for bench-scale treatability testing is
important, as extreme deviations from the natural aquifer
reduce the relevance of the testing. Previous experience with
more than 100 ISCO bench-scale treatability tests indicates
that variance for pretreatment contaminant concentrations in
source areas is typically high. The variance is typically also
quite high for other characteristics affecting remedy perfor-
mance, such as TOC. Samples collected in parallel from a
contamination source zone are often too variable to be rep-
resented by a sample mean (the standard error may exceed
the mean estimate). If multiple samples are collected and
some are sacrificed for pretreatment analysis while others
are treated and then analyzed, the high variance may prevent
comparison of pre- and posttreatment sample means. To gain
the benefit of uniform pretreatment test material and to obtain
useable replication in the bench-scale treatability testing, a
sample homogenization protocol is recommended.
The scale and procedure of the bench-scale treatability
testing should be matched to the specific objectives at a par-
ticular site. For example, if anoxic sample collection is neces-
sary due to high anticipated ferrous iron (Fe2+) and sulfide
(S2−) concentrations, nitrogen gas purged anoxic sample con-
tainers may be used to reduce sample exposure to atmospheric
oxygen. Sample processing may be conducted in an anaerobic
chamber to further minimize exposure to atmospheric oxy-
gen. If pretreatment laboratory analysis indicates consider-
able contaminant concentration variability or contaminant
concentrations below field observed contaminant concentra-
tions, a laboratory-grade form of the contaminant may be
“spiked” into the sample homogenate. It should be noted that
each added consideration may incrementally increase the cost
of the bench-scale treatability test.
6.3.2.2.2  Secondary Water Quality Concerns
The concern of secondary water quality following an ISCO
implementation is universal to all ISCO reagents. Typically,
the focus is on metal mobility, but there are other forms of
secondary water quality that may cause site-specific con-
cerns, such as associated anions from the oxidant or contami-
nant intermediaries. In reality, any result of ISCO that creates
an exceedance of a primary or secondary MCL may be scru-
tinized by a regulatory agency. It is industry experience that
secondary water quality concerns are temporary and spatially
limited to the ISCO treatment area, but these concerns should
be acknowledged before ISCO implementation. If necessary,
sentinel monitoring plans may be devised with contingency
action.
The influence on geogenic metals by altering the pH,
through acidity or alkalinity generation, is intuitive and dis-
cussed at length in Chapter 7. Some metals (arsenic, chromium,
iron, molybdenum, selenium, vanadium, etc.) are oxidation–
reduction potential sensitive, and the oxidizing conditions
imposed by the presence of a powerful oxidant will influence
the solubility of these metals. An example of the spatial limits
of metal mobility related to ISCO is presented in Figure 6.74.
278 Remediation Engineering

Sulfate
Sodium
Aluminum
Arsenic
Cadmium Aluminum
Copper Arsenic
1.0 Iron
Iron
Normalized increase in metal concentration

Manganese

Normalized increase in metal concentration

Manganese 1.0
Nickel Nickel
0.8 Zinc Zinc
0.8

0.6
0.6

0.4
0.4

0.2 0.2

0.0 0.0
4 7 10 12 4 7 10 12
(a) Distance from injection well (b) Distance from injection well

1.E+07 8.0
1.E+07 8.0 7 ft from IW
4 ft from IW 1.E+06
1.E+06
Metal concentration (mg/L)

Sulfate
Metal concentration (mg/L)

Sulfate 1.E+05 7.0 Al

1.E+05 Injection 7.0 Al Injection As
As 1.E+04
1.E+04 Cr
Cr Fe
Fe 1.E+03 6.0
1.E+03 6.0 Mn
Mn Ni
Ni 1.E+02
1.E+02 Na
Na Zn
Zn 1.E+01 5.0
1.E+01 5.0 pH
pH
1.E+00
1.E+00
1.E–01 4.0
1.E–01 4.0
3/3/08 4/2/08 5/2/08 6/1/08 3/3/08 4/2/08 5/2/08 6/1/08

1.E+07 8.0 1.E+07 8.0

10 ft from IW 12 ft from IW
1.E+06 1.E+06
Metal concentration (mg/L)
Metal concentration (mg/L)

Injection Sulfate Injection

1.E+05 7.0 Al 1.E+05 7.0 Sulfate
As Al
1.E+04 Cr 1.E+04 As
Fe Cr
1.E+03 6.0 Mn 1.E+03 6.0 Fe
Ni Mn
1.E+02 1.E+02 Ni
Na
Zn Na
1.E+01 5.0 1.E+01 5.0 Zn
pH
pH
1.E+00 1.E+00

1.E–01 4.0 1.E–01 4.0

3/3/08 4/2/08 5/2/08 6/1/08 3/3/08 4/2/08 5/2/08 6/1/08
(c)

FIGURE 6.74  Total metals analysis from 4, 7, 10, and 12 feet downgradient of an injection well one month after a sodium persulfate
(Na2S2O8) injection. The results suggest considerable metal mobility 4 and 7 feet from the injection well, but spatial attenuation within a
relatively short distance considerably limits the mobilization at 12 feet downgradient. The total normalized percent increase of all metals is
shown in (a). A subset of metals typically associated with secondary water quality concerns is shown in (b). The four plots in (c) show the
actual analytical concentrations of the metals with respect to 4, 7, 10, and 12 feet from the injection well. (Continued)
Injected Reagent–Based Remedies 279

1.E+07 8.0 1.E+07 8.0

4 ft from IW 7 ft from IW
1.E+06 1.E+06 Injection
Injection
Metal concentration (mg/L)

Metal concentration (mg/L)

1.E+05 7.0 1.E+05 7.0
Al Al
1.E+04 As 1.E+04 As
Fe Fe
1.E+03 6.0 Mn 1.E+03 6.0 Mn
Ni Ni
1.E+02 Zn 1.E+02 Zn
pH pH
1.E+01 5.0 1.E+01 5.0

1.E+00 1.E+00

1.E–01 4.0 1.E–01 4.0

3/3/08 4/2/08 5/2/08 6/1/08 3/3/08 4/2/08 5/2/08 6/1/08

1.E+07 8.0 1.E+07 8.0

10 ft from IW 12 ft from IW
1.E+06 Injection 1.E+06 Injection

Metal concentration (mg/L)

Metal concentration (mg/L)

1.E+05 7.0 1.E+05 7.0

Al
Al
1.E+04 As 1.E+04 As
Fe
6.0 Fe
1.E+03 6.0 Mn 1.E+03
Mn
Ni
1.E+02 1.E+02 Ni
Zn
Zn
pH
1.E+01 5.0 1.E+01 5.0 pH

1.E+00 1.E+00

1.E–01 4.0 1.E–01 4.0

3/3/08 4/2/08 5/2/08 6/1/08 3/3/08 4/2/08 5/2/08 6/1/08
(d)

FIGURE 6.74 (Continued)  Total metals analysis from 4, 7, 10, and 12 feet downgradient of an injection well one month after a sodium
persulfate (Na2S2O8) injection. The results suggest considerable metal mobility 4 and 7 feet from the injection well, but spatial attenuation
within a relatively short distance considerably limits the mobilization at 12 feet downgradient. The four plots in (d) shows a subset of metals
typically associated with secondary water quality concerns.

The distance progression presented in Figure 6.74 represents
4, 7, 10, and 12 ft downgradient from an injection well where
4350 gal of a 1% by weight solution of sodium persulfate
(Na2S2O8) was injected. There was no engineered activation
as it was anticipated from baseline geochemistry that the
ambient dissolved-phase metal concentrations would be suf-
ficient for ambient persulfate (S2O82−) activation. Monitoring
wells located at 4 and 7 ft observed persulfate (S2O82−) break-
through of 88% and 30%, respectively. Only one month of
postinjection performance monitoring data is available; how-
ever, persulfate (S2O82−) was observed to be consumed within
this time period. The data presented in Figure 6.74 provide
a snapshot one month after an ISCO injection and demon-
strate orders of magnitude reduction of metal mobility within
a few feet. This demonstrates that the extreme geochemistry
engineered for ISCO implementation influences the treatment
ROI and will mobilize metals, but this influence is limited to
the treatment ROI and considerable attenuation is expected
further downgradient.
The engineered pH, already mentioned to influence metal
mobility, may also accelerate source mass dissolution and
desorption. This has been observed in numerous persulfate
(S2O82−)-based PHC implementations and has been attributed
to extremely acidic or alkaline pH. This result is typically
observed through either an increase in dissolved concen-
trations postinjection or reduced viscosity of LNAPL with
observations of sheens or LNAPL thickness not previously
reported. An example of increased aqueous concentrations
following an approximate 3000 gal injection of a 5% by
weight sodium persulfate (Na2S2O8) injection with chelated
iron activation in the eastern United States is presented in
Figure 6.75. ISCO was selected as a remedial technology to
address residual dissolved-phase concentrations primarily
of benzene (C6H6) that appeared to follow a seasonal pattern
Postinjection concentrations are observed to increase above
baseline concentrations, most notably for toluene (C7H8) and
xylenes (C8H10). The precise mechanism for this observation
is not well understood and could be either a combination or
directly attributable to one of the following:
• Higher dissolved-phase concentrations within the
immobile fraction of the porous media that were
flushed during the injection.
• Strongly acidic conditions appear to be main-
tained for several years postinjection and this may
have facilitated reduced interfacial surface tension
between adsorbed/NAPL mass and groundwater
promoting dissolution.
280 Remediation Engineering

4000
Benzene
Toluene
3500 Ethylbenzene
Xylenes
3000 Injection

Concentration (µg/L)
2500

2000

1500

1000

500

0
06/17/07 08/25/09 11/03/11 01/11/14 03/21/16
(a)

9.0 50

8.0 pH 49
Injection
7.0 Groundwater elevation 48

Groundwater elevation (ft)

47
6.0
pH (standard units)

46
5.0
45
4.0
44
3.0
43
2.0 42

1.0 41

0.0 40
6/17/2007 8/25/2009 11/3/2011 1/11/2014 3/21/2016
(b)

FIGURE 6.75  (a) Petroleum hydrocarbon concentrations at an influenced dose-response well after a sodium persulfate (Na2S2O8) injec-
tion. The results, particularly for toluene and xylenes, show considerable increases after the injection suggesting liberated adsorbed mass/
NAPL following the injection. (b) pH and groundwater elevation trends at the influenced dose-response well. The groundwater elevation
fluctuates from 42 to 46 ft. The pH shows considerable acidity sustained more than 3 years postinjection.

• Incomplete oxidized PHCs (CxHy), which are poten-
tially oxidized to alcohols (CxHyOz) or other inter-
mediates, that act as surfactants to dissolve the
adsorbed/NAPL mass.
• Microbial surfactants generated as a result of aerobic
or anaerobic metabolisms using the residual electron
acceptor after the ISCO chemistry is exhausted.
While an increase in contaminant concentrations postinjec-
tion seems counterintuitive and unproductive, accelerating
access to this stored contaminant mass that would otherwise
slowly advect and diffuse into mobile groundwater over an
extended duration is actually beneficial. This is, however,
a good example of the resource commitment of an ISCO
implementation. It underscores the importance of a sound
CSM where the nature and extent of contamination are well
understood. If ISCO is selected with the understanding of the
potential for adsorbed/NAPL mass, repeat injections over an
extended duration should be the expectation, and the second-
ary water quality ramifications of the selected oxidant over
numerous events should be considered.
Other related secondary water quality concerns include
the anions or metals associated with the oxidants (i.e., per-
sulfate [S2O82−] results in high sulfate [SO42−] concentrations
and permanganate [MnO4−] results in high total manganese
concentrations). Examples presented in Sections 6.3.2.2.1.3
and 6.3.2.2.3.3 present the potential for minor trihalometh-
anes (THMs) and chloroethane production. The influenced
ionic strength of salt-based oxidants may create concerns of
high TDS. The type of by-product formation is a trade-off that
Injected Reagent–Based Remedies 281

must be considered for any oxidant injection, and site-specific Taking the negative log of both sides of Equation 6.95 yields
testing is useful in determining the upper acceptable concen- Equation 6.96:
tration. It is important to note that some potential target com-
pK A = pH (6.96)
pounds would require such a high oxidant strength that the
benefit gained by initial target destruction may be outweighed The insinuation of Equation 6.96 is that when the pH is at the
by the formation of more troublesome by-products. same numeric value as the pK A, the concentrations of the acid
(HA) and conjugate base (A−) are equal.
6.3.2.2.3  Carbonate Interference
Inorganic carbon in groundwater reacts readily with hydroxyl 6.3.2.2.3.2  Two-Step Dissociations  Carbonic acid
radicals (OH•) and other compounds in the radical chain reac- (H2CO3) bears two hydrogen atoms (H+; protons) that readily
tions of ozonation, ultraviolet oxidation, and CHP reactions. dissociate in groundwater (Equation 6.97):
In aquifers, the inorganic carbon pool is composed of three
carbonates: the carbonic acid (H2CO3), the bicarbonate ion K A1 KA2

(HCO3−), and the carbonate ion (CO32−). To determine the H 2CO3 « H + + HCO3- « 2H + + CO32 - (6.97)
extent of potential interference, it is first necessary to calcu-
or in the generalized form (Equation 6.98):
late the molarities of the two main interfering compounds,
bicarbonate (HCO3−) and carbonate (CO32−). This is accom- K A1 KA2

plished using alkalinity data, the hydrogen ion (H+) concen- H 2 A « H + + A - « H + + A - (6.98)
tration (from pH), and the acid–base dissociation constants for The mole fraction of each constituent can be calculated by spec-
the two-step dissociation from carbonic acid (H2CO3) to the ifying a pH value and solving the two kinetic equations simulta-
carbonate ion (CO32−). After the carbonate species molarities neously. The first step is to set the sum of mole fractions of the
have been calculated for a particular aquifer, the reaction rates carbonate system constituents equal to 1.0 (Equation 6.99):
between radical and target compound can be compared to the
rates of radical chain termination reactions that will be gener- H 2CO3 + HCO3- + CO32 - = 1.0 (6.99)

ated by dissolved carbonates. From that estimate, it can be
determined whether the expected losses of reagent to carbon- The next step is to express carbonic acid (H2CO3) and carbonate
ate termination will be small or, alternatively, the level of pH (CO32−) in terms of the common ion, bicarbonate (HCO3−), using
adjustment that would be needed to achieve acceptable radical Equation 6.94. The following can be used to evaluate the first
reaction rates with the target compounds. Inorganic carbon dissociation (Equation 6.100):
generally needs to be greater than 100 mg/L in groundwater
to adversely influence hydroxyl radical formation. éH + ù ´ éHCO3- ù
K A1 = ë û ë û (6.100)
éëH 2CO3 ùû
6.3.2.2.3.1  Acid–Base Equilibrium  Aquifer carbonate
concentrations are controlled by the two-step carbonic acid
(H2CO3) dissociation. The general form of the acid–base Rearranging Equation 6.100,
equilibrium is described by Equation 6.93: éH + ù ´ éHCO3- ù
éë 2 = ë û ë û (6.101)
KA H CO 3ù
û
HA « H + + A - (6.93) K A1

where HA is the undissociated acid, H+ is a proton, and A− is From the second dissociation (Equation 6.102):
the conjugate base.* The kinetic rate constant (K A) for the 2
acid dissociation is defined by Equation 6.94: éH + ù ´ éCO32 - ù éH + ù ´ éCO32 - ù
K A2 = ë +û ë û=ë û ë û (6.102)
é H ù ´ éHCO3- ù éHCO3- ù
éH ù ´ é A ù
+ -
ë û ë û ë û
K A = ë û ë û (6.94)
ëéHA ùû Rearranging Equation 6.102,

In the special case when the acid is half dissociated, the K A 2 ´ éëHCO3- ùû
concentrations of the undissociated acid (HA) and the con- éCO32 - ù = (6.103)
ë û é +ù
jugate base (A−) are equal, so Equation 6.94 reduces to ëH û
Equation 6.95:
Substituting Equation 6.101 and Equation 6.103 into Equation
K A = éëH + ùû (6.95) 6.99:

éH + ù ´ éHCO3- ù é -
ù
* The conjugate base of an acid is formed when the acid (HA) donates a ë û ë û + éHCO - ù + K A 2 ´ ëHCO3 û = 1.0
K A1 ë 3 û é +ù
ëH û
proton (H+). For example, the hydroxyl anion (OH−) is the conjugate base
of the acid water (H2O), because water (H2O) donates a hydrogen ion (H+)

to form the hydroxyl anion (OH−). (6.104)
282 Remediation Engineering

Solving Equation 6.104 for the bicarbonate ion (HCO3−): 1

éCO32 - ù =
ë û æ
éH + ù éH + ù ö
2

1 ç1 + ë û+ ë û ÷
éHCO3- ù = (6.105) çç
ë û æ éH ù K ö
+ K A2 K A1K A2 ÷÷
ç1 + ë û A ÷ è ø
+ 2
ç K A1 éH + ù ÷
è ë ûø æ éH + ù éH + ù ö
2

ç
where µ3 = 1 + ë û + ë û ÷ (6.110)
çç K A2 K A1K A2 ÷÷
Solving Equation 6.101 for carbonic acid (H2CO3): è ø

éH + ù 1 Recall that for Equation 6.99 the total concentration of the

éëH 2CO3 ùû = ë û ´ (6.106) example carbonate compounds was arbitrarily set to 1 but
K A1 æ éH + ù K ö
ç1 + ë û + A2 ÷ could be more generically defined as the total concentra-
ç K A1 éH + ù ÷ tion (CT). Therefore, the total concentration (CT) divided by any
è ë ûø
of the alphas (α) presented in Equations 6.108 through 6.110 at
a given pH with known dissociation constants (K A) will provide
Solving Equation 6.103 for the carbonate ion (CO32−): the concentration of the respective compound. In Chapter 7,

K 1 0
éCO32 - ù = A 2 ´ (6.107) pKA1 = 6.3 pKA2 = 10.3
ë û éH + ù æ éH ù K ö
+
–1
ë û ç ë û A2 ÷ [H2CO3] [HCO3 –] [CO32–]
1+ +
ç K A1 éH + ù ÷ –2
è ë ûø
–3
–4
For oxyanions (or negatively charged compounds with oxy-
log[C]

gen) with numerous hydrogen ions (H+), the calculations –5

summarized earlier can be tedious and time intensive. Based –6 [H+]
[OH–]
on Equations 6.105 through 6.107 for each of the carbonate –7
compounds, it is evident that a repetitive pattern of hydrogen
–8
ions (H+) and dissociation constants (K A) occurs for sequen-
tially protonated compounds. Multiplying the leading expres- –9
sions in Equations 6.106 and 6.107 through the rest of the –10
equation results in expressions presented as Equations 6.108 0 2 4 6 8 10 12 14
through 6.110, which can be used to quickly solve for other pH
sequentially protonated compounds. The equations presented
in Equations 6.108 through 6.110 are referred to as alpha (α) FIGURE 6.76  Speciation diagram for carbonate system. Total car-
values, and the user requires only a pH and the compound- bonate concentration = 10 −2 M.
specific dissociation constants (K A) to solve for the desired
compound: 10
Relative reactive rate: TCE/HCO3–

1
éëH 2CO3 ùû = 1
æ ö
ç 1 + K A1 + K A1K A2 ÷
çç éH + ù é + ù 2 ÷÷
H
è ë û ë û ø 0.1

K A11 K A1K A2
where µ1 = 1 + + (6.108)
éH + ù éH + ù 2
ë û ë û 0.01

1 0.001
éHCO3- ù =
ë û æ 1 10 100 1,000 10,000
éH ù K A2 ö÷
+
ç1 + ë û + TCE cleanup goal TCE concentration (µg/L)
ç K A1 éH + ù ÷
è ë ûø
FIGURE 6.77  Relative reaction rates of TCE (C2HCl3) and bicar-
éH + ù K bonate ion (HCO3−) reaction with the hydroxyl radical (OH•), as a
where µ2 = 1 + ë û + A+2 (6.109) function of pH. Total carbonate alkalinity is 100 mM (300 mg/L as
K A11 éH ù
ë û CaCO3).
Injected Reagent–Based Remedies 283

several logarithm of the concentration versus the pH diagrams
(log C–pH diagrams) are presented and discussed for other
sequential deprotonated compounds (i.e., sulfur, arsenic, and
chromium).
The logC–pH diagram for the carbonate compounds is pre-
sented in Figure 6.76. The relevant dissociated constants for the
carbonate compounds are K A1 = 4.467 × 10 −7 and K A2 = 4.677 ×
10−11, and the negative logarithms (or pKA1 and pKA2) are 6.33
and 10.33 respectively. Note that the intersection of the carbon-
ate curves in Figure 6.77 occurs at values equal to the pKA val-
ues, demonstrating equivalent concentrations at equilibrium.
Second, calculate the bicarbonate (HCO3−) molarity using the
total alkalinity and the mole fraction of bicarbonate (HCO3−)
at pH 8.0. From Figure 6.76, it is evident that the bicarbonate
(HCO3−) mole fraction is 0.95 at pH 8.0 (Equation 6.105 could
also be used to make a more exact calculation):
éHCO3- ù = 3 ´ 10 -3 M as
ë û
CaCO3 ´ 0.95 mol HCO3- /mol CaCO3
and

6.3.2.2.3.3   Calculation of Competitive Interaction  The éHCO3- ù = 2.85 ´ 10 -3 M

ë û
loss of the hydroxyl radical (OH•) to carbonate (CO32−)/bicar-
bonate (HCO3−) scavenging can be calculated as a function This is the value that will be used in the kinetic rate calcula-
of target contaminant concentration at a specified aquifer tions that follow.
pH and alkalinity. The calculations summarized in Section Third, develop a formula that expresses the relative rates
6.3.2.1.3.2 are first used to determine the mole fraction of the of reaction with the hydroxyl radical (OH•). To do this, differ-
bicarbonate (HCO3−) and/or carbonate (CO32−) ion for the pH ential equations of the second-order rate constants for the two
of interest. Then, the molarity is calculated by multiplication competing reactions are necessary:
of the mole fraction and total carbonate alkalinity, expressed
in molar concentration. TCE + OH • ® Products
Consider a site where hydroxyl radical (OH•) oxidation is
proposed for in  situ chemical remediation. The subject site
and
has an approximate pH of 8.0 and a carbonate alkalinity of
300 mg/L as CaCO3. The target compound is trichloroeth-
HCO3- + OH • ® H 2O + CO•3-
ene (TCE), and it is necessary to evaluate if pH adjustment is
necessary for a successful oxidation, using a chelating agent*
to maintain iron levels in groundwater. In this circumstance, The first differential equation is based on the TCE oxidation
competition from carbonate (CO32−) ions could be significant. reaction (Equation 6.111):
The calculation strategy is as follows:
dTCE æ mol ö
= kTCE éë TCE ùû éëOH • ùû ç -1 ÷
(6.111)
1. Estimate the mole fraction of bicarbonate (HCO3 ) − dt è L´s ø
and, combined with the carbonate alkalinity data,
calculate the bicarbonate (HCO3−) molarity at the and the second differential equation is calculated for the
specified pH and alkalinity. bicarbonate anion (HCO3−) reaction with the hydroxyl radical
2. Develop a formula that expresses the reaction rate of (OH•) as follows (Equation 6.112):
the hydroxyl radical (OH•) with TCE, divided by the
dHCO3-
rate of reaction between hydroxyl radical (OH•) and
bicarbonate (HCO3−). This gives a value for the frac- dt
( )
= kHCO3 éëHCO3- ùû éëOH • ùû mol/L ´ s-1 (6.112)

tion of productive, relative to total, reactions.

3. Prepare a graphic representation of the results. A ratio is used to establish a comparison of the two reaction
rates (Equation 6.113):
First, calculate the bicarbonate (HCO3−) molarity under the
specified conditions: dTCE
kTCE éë TCE ùû éëOH • ùû
dt = (6.113)
MWCaCO3 = 100 mg/mmol dHCO3- kHCO3 éHCO3- ù éOH • ù
ë ûë û
dt
300 mg/L
= 3 mmol/L as CaCO3
100 mg/mmol Simplifying Equation 6.113,

= 3 ´ 10 -3 M CaCO3 total alkalinity dTCE kTCE éë TCE ùû

-
= (6.114)
dHCO3 kHCO3 éëHCO3- ùû

* A chelating agent is a molecule that can form several weak bonds to a single
metal ion and essentially maintain the metal reactivity at a pH that (in the
absence of the chelating agent) would typically result in metal precipitation.
The bicarbonate (HCO3−) concentration is much larger than the
Another way to describe a chelating agent is as a multidentate ligand, and TCE concentration for the concentrations of interest, so it can
an example is ethylenediaminetetraacetic acid (EDTA; C10H16N2O8). be assumed to be constant (this assumption is also supported
284
by the fact that bicarbonate [HCO3−] will be refreshed by con-
version from carbonate [CO32−] soil minerals):
dTCE kTCE
= ´ é TCE ùû (6.115)
dHCO3- kHCO3 éHCO3- ù ë
ë û
The rate constants for hydroxyl radical (OH•) reaction
with TCE and bicarbonate (HCO3−) can be obtained from
Table 6.28:
æ 1 ö
kTCE = 4 ´ 109 ç ÷
è M ´s ø
æ 1 ö
kHCO3 = 8.5 ´ 106 ç ÷ materials handling of potentially dangerous chemical oxidiz-
è M´s ø
Using the value of bicarbonate (HCO3−) calculated earlier
(2.85 × 10 −3 M), Equation 6.116 is determined:
dTCE 4 ´ 109
= ´ éë TCE ùû (6.116)
dHCO3- ( )(
8.5 ´ 106 2.85 ´ 10 -3 ) lessons learned and potential unsafe outcomes.158,160,162,205
dTCE
= 1.65 ´ 105 ´ éë TCE ùû (6.117)
dHCO3-
The value of the function described by Equation 6.117 can be
graphed as a function of TCE concentration values. The com-
parison of the relative reaction rate of TCE and bicarbonate
(HCO3−) with the hydroxyl radical (OH•) versus TCE concen-
trations ranging from 1 to 10,000 µg/L is presented in Figure
6.77. At high TCE concentrations, the ratio is approximately
10.5, indicating that more than 90% of the radical reactions
occur with TCE. When the TCE concentration decreases
to 1000 µg/L, only a little more than 10% of the reactions
occur with TCE. When the TCE concentration approaches the
typical target value established for drinking water protection
(5 µg/L), fewer than 1 reaction in 100 is occurring between
TCE and the hydroxyl radical (OH•). From this exercise, it is
concluded that bicarbonate ion (HCO3−), when present at a
concentration greater than 100 mg/L, is a significant competi-
tor for TCE in hydroxyl radical (OH•) oxidation, and it may be
necessary to lower the aquifer pH to reduce TCE levels to the
5 µg/L range.
6.3.2.2.4  Oxidant Quenching
If a postinjection sample is collected from within a treatment
ROI of an ISCO injection, there is a potential for residual oxi-
dant to remain in the groundwater. This oxidant, if included
into a performance-based sample, may continue to influence
the chemistry within the sample bottle in transit to the lab-
oratory and especially during laboratory analysis. As such,
depending on the data quality objectives at a particular site,
it may be appropriate to actively quench the residual oxidant
prior to sample collection for laboratory analysis. A procedure
for quenching has been established204 and uses ascorbic acid
(C6H8O6) to actively consume the residual oxidant, without
Remediation Engineering
overly diluting the sample or influencing the performance
monitoring results. Another alternative to oxidant quench-
ing is delaying the collection of performance monitoring data
until the oxidant has been consumed. Oxidant quenching is
typically not necessary for ozone (O3) or hydrogen peroxide
(H2O2) ISCO implementations, may be necessary for persul-
fate (S2O82−) oxidation and is typically required for perman-
ganate (MnO4−) oxidation. Quenching can be performed in
the field with a simple titration from a concentrated ascorbic
acid (C6H8O6) solution and then confirmed with field testing
for residual oxidant.
6.3.2.2.5  Health and Safety Considerations
The implementation of ISCO usually requires some degree of
ers and manipulating oxidation chemistry may lead to unsafe
conditions. A rigorous health and safety plan rooted in practi-
cal experience and a behavioral-based health and safety sys-
tem are cornerstones to mitigating the risk of injuries and/or
fatalities associated with ISCO implementation. The publica-
tion literature is rich with case study examples highlighting
Each chemical oxidant will have its own health and safety
considerations, and the safety data sheet (SDS) should be con-
sulted for safe handling of a particular oxidant. The vendor
producing the oxidant is required to provide the SDS. In gen-
eral, a few ISCO guidelines for health and safety include the
following:
• Implementing engineering controls to avoid field
staff handling of an oxidant is a primary risk miti-
gation strategy. Where it is cost effective and stor-
age logistics allow, small volumes of concentrated
liquid solutions that are diluted in-line for injection
may be preferable as they avoid field dissolution of
solid oxidants. Additionally, it prevents manual lift-
ing of oxidant packages, which typically weigh 50 to
55 pounds.
• Personal protective equipment (PPE) is a require-
ment for all field staff involved in the implementation
of oxidant mixing and dose-response monitor-
ing. At a minimum, full-body chemically resistant
suits, chemically resistant shin-high rubber boots,
chemically resistant elbow-length gloves, and splash
aprons should be worn by those conducting the oxi-
dant mixing. For those oxidants that are salts (potas-
sium permanganate [KMnO4] and sodium persulfate
[Na2S2O8]), a full-face particulate respirator is typi-
cally required. Duct tape is used to seal the boots
and gloves to the chemically resistant suite. This
degree of PPE is referred to as Level C. The rule of
thumb for PPE is that an appropriate level of PPE
should be worn to mitigate all hazards, but not itself
create an unsafe condition. If no solid oxidant is used
(i.e., concentrated liquid is diluted in-line), a full face
respirator may not be required, but face shield with
safety glasses equipped with side splash guards will
Injected Reagent–Based Remedies
still be required. The required degree of PPE should
be determined by a qualified health and safety site
officer and documented in the health and safety plan.
Additionally, the field conditions should be consid-
ered for the working environment for the field staff.
Specifying Level C PPE for extremely hot and humid
conditions may create unsafe conditions.
• Proper ventilation of the mixing area is of critical
importance. While the most commonly used salt-
based oxidants (permanganate [MnO4−] and per-
sulfate [S2O82−]) do not generate inhalation vapors,
the particulates that may accumulate in an enclosed
mixing area may create an unsafe inhalation hazard.
Indoor mixing systems should have Occupational
Safety and Health Administration–approved venti-
lation systems capable of exchange rates that avoid
unsafe inhalation conditions. While outdoor tempo-
rary batch mixing configurations typically provide
sufficient ventilation, field staff awareness of par-
ticulate inhalation is important and full-face res-
pirators while dissolving salt-based oxidants are a
requirement.
• Ozone (O3) sparging and CHP may yield significant
gas generation and temperature change. These poten-
tial observations should be discussed with field staff
prior to implementation, and reasonable response
actions should be documented in the site-specific
health and safety plan. At a minimum, monitoring
should be conducted for the oxygen content of the
off-gas, and provisions for safely venting the vadose
zone to prevent the development of explosive condi-
tions should be considered. Observations of ozone
(O3) discharge through cracks in asphalt parking
lots have been observed. Ozone (O3) air monitoring
around the ozone (O3) generation system is recom-
mended to avoid field staff exposure.
• Some states have Homeland Security limitations on
the storage mass of particular oxidants. This is not
federally mandated and should be confirmed with
the governing fire department in the area where
ISCO is to be implemented. This concern also
relates to burglary or vandalism of stored oxidants
on-site. Appropriate lockout tag-out procedures
should be documented in the site-specific health and
safety plan.
• Chemical compatibility is a major concern for oxi-
dation chemistry. Typically, PVC or high-density
polyethylene are preferred for working with aggres-
sive oxidants, but the exact chemical compatibility
of the aboveground conveyance should be confirmed
with the oxidant prior to specifying a bill of mate-
rials. Temperature considerations when using CHP
and diluting strong acids and bases may preclude
PVC as there have been field observations of melted
PVC wells or malleable injection conveyance equip-
ment from rapid temperature increase. Routine (i.e.,
daily) operation and maintenance of the injection
285
conveyance may be required to inspect and con-
firm the injection equipment remains functional.
Additionally, the chemical compatibility of sub-
surface utilities for shallow ISCO implementations
should be considered as most utilities are some form
of carbon steel that is highly susceptible to reactions
with oxidants. Some methods of utility compatibility
have been implemented (such as cathodic protection
for metallic utilities), but in general avoidance of oxi-
dant and utility contact is recommended.
• Mixed reagents or concentrated bulk reagents need
to be secondarily contained to 110% of the volume
of the storage tank. Oftentimes, space is at a pre-
mium for a temporary batch ISCO implementation,
and sufficient secondary containment cannot be pro-
vided. This forces smaller tanks and more frequent
mixing and should be considered during the design
and health and safety plan development.
These preceding examples are applicable to ISCO implemen-
tations in one way or another, and it is clear that potential
health and safety risks need to be assessed during oxidation
applications. These risks can be managed through proactive
strategies to avoid field staff contact with oxidants and educa-
tion of the potential hazards.
6.3.2.3  Reagent Selection/Types
Available forms of chemical reagents for ISCO and their
reactive species are summarized in Table 6.26, and the resul-
tant standard reduction potential (measured in volts) is sum-
marized in Table 6.27. Of the available forms of chemical
reagents, permanganate (MnO4−), CHP, persulfate (S2O82−),
and ozone (O3) are the four primary forms of oxidants and
will be discussed in detail in this section. A summary of con-
taminant applicability to the four main forms of oxidants is
summarized in Table 6.30. The different forms of oxidants
provide a great deal of flexibility with respect to appropriate
chemistries, and each oxidant has benefits and weaknesses.
Some general differences are discussed in this section, and
then oxidant-specific benefits and weaknesses are discussed
in the following subsections.
The effectiveness of ISCO for dissolved-phase contami-
nation is predicated on achieving the greatest uniform and
homogeneous distribution of the chemical oxidizing reagents
possible. This general ISCO distinction presents comparative
benefits and weaknesses of the available oxidants. For exam-
ple, potassium permanganate (KMnO4) has a lower solubility
than the other available forms of oxidants. Therefore, a con-
siderably larger volume would need to be injected to achieve
a comparable oxidant load. Sodium permanganate (NaMnO4)
provides better solubility but influences the implementation as
it is only provided as a liquid reagent. Ozone (O3) is sparged
into aquifers and is therefore susceptible to similar mass
transfer limitations as biosparging applications and similar
physical limitations as with air sparging. The hydroxyl radi-
cal (OH•) associated with CHP has negligible lifetime in situ,
which may significantly limit its practical distribution within
286 Remediation Engineering

TABLE 6.30
Classes of Contaminants and Applicability to Various Forms of In Situ Chemical Oxidation
Oxidant
Permanganate Catalyzed Hydrogen SO4•− (Activated
(MnO4−) Peroxide (CHP [H2O2/Fe]) S2O82− (1) Persulfate)1 Ozone (O3)
Cited Literature for Applicability
Contaminant a b c d a b c d e/f a a b c a b c d
Petroleum hydrocarbons G 4 E4 G/E 4 E4 E4

TEX E4 E4 E E E4 E E E E4 E G4 E
Benzene P4 G4 P4 E4 E4 E G 4 G/E 4 E4 E4 G4
Phenols G E E E E E E E P/G G/E E E E E E
PAHs G E E E E G G E E G E G G/E E G E E
MTBE G G E E P/G E E G E
tert-Butyl alcohol E G E E
Chlorinated ethenes E E E E E E E E E G E E E E E E
Carbon tetrachloride P P P P/G G P P P P/G P/E P/G P
Chloroform P P P P P G/E P
Methylene chloride P G G P G/E G
Chlorinated ethanes5 P P G/E P P P G/E G P
Trichloroethane5 P P E P P P/E P
Dichloroethane5 P G G P G/E G
Chlorobenzene P E E E E E E
PCBs P P P P P G P P E P P P P/E P E P
Energetics (RDX, HMX) E E G E E
Explosives E E E G G G/E E E
Pesticides G G P P G/E6 G G/E P E
1,4-Dioxane7 E E E

Source: Huling, S.G. and Pivetz, B.E., Engineering issue paper: In-situ chemical oxidation. EPA 600-R-06-072. U.S. Environmental Protection
Agency (USEPA) Office of Research and Development, National Risk Management Research Laboratory, Cincinnati, OH, 60 p, 2006.
http://www.epa.gov/tio/tsp/issue.htm#EF.
Key: P = poor, G = good, E = excellent.
a: Sperry and Cookson (2002) [388]
b: ITRC (2005) [389]
c: Brown (2003) [390]
d: Siegrist (2001) [391]
e: Rating based on the second-order reaction rate constants between contaminants and OH reported in Buxton et al. (1988) and Haag and Yao
(1992): Excellent (>109 L/mol-s), Good (108–109 L/mol-s), Poor (<108 L/mol-s).
1 Persulfate/sulfate radical reactivity studies with 66 organic compounds and isomers under various conditions have been conducted elsewhere

(FMC, 2005).
2 The reaction between O and H O produces OH•. Therefore, the ratings from source (e) by catalyzed hydrogen peroxide (CHP) apply equally
3 2 2
to the O3/H2O2 (peroxone, HiPOx, Perozone) technology.
3 Source (c) rated Fe-catalyzed and heat-catalyzed persulfate (S O 2−) separately; the lower rating applies to Fe-activated and the higher rating
2 8
applies to heat-activated persulfate (S2O82−).
4 Benzene was rated separately from TEX or petroleum hydrocarbons; thus, the TEX or petroleum hydrocarbon rating excludes benzene.

5 Trichloroethane (CA) and dichloroethane (DCA) were rated separately by some sources, and the other sources rated chlorinated ethanes as a

class of contaminant.
6 A detailed summary of second-order reaction rate constants between pesticides and OH• is reported in Haag and Yao (1992).

7 Brown et al. (2004) present experimental results indicated that permanganate (MnO −), catalyzed hydrogen peroxide (CHP), persulfate (S O 2−),
4 2 8
and ozone (O3) are effective in oxidizing 1,4-dioxane.

a treatment ROI. Persulfate (S2O82−) has a favorable solubility
and the flexibility of activation chemistry supports better dis-
tribution of the oxidant, but manipulating propagating chain
reactions is contingent on achieving distribution of activat-
ing agents as well. The oxidant payload to the subsurface is
clearly reagent specific and must be a determining criterion
for reagent selection.
The relevance of ISCO to significant adsorbed mass/NAPL
was discussed in Section 6.3.2.1. If ISCO is still selected as the
preferred remedial alternative in the presence of significant
Injected Reagent–Based Remedies
adsorbed mass/NAPL, it is important to note that the chem-
istry is highly likely to be successful, but the cost efficiency
and degree of secondary water quality concerns are directly
linked to the selected reagent loading and longevity. A host
of literature has demonstrated oxidative destruction of differ-
ent NAPL,185–187,206–211 but the field-scale implementation of a
mature contaminant source zone will still be limited by the
hyperreactivity of the chemical oxidant with the separate-
phase adsorbed mass/NAPL. Permanganate (MnO4−) has
been observed to develop crusts at the NAPL mass–oxidant
interface, and it has been theorized that this crust may encap-
sulate the NAPL preventing further dissolution. Convincing
evidence in two-dimensional sand tank studies by MacKinnon
and Thomson212 clearly identifies manganese dioxide (MnO2)
crust at the interface of placed DNAPL that were described as
rocklike deposits. As the crust encapsulates the DNAPL dur-
ing injection of the permanganate (MnO4−), it would inhibit
destruction of the DNAPL in favor of a passivated DNAPL
surface. The longevity of such encapsulated DNAPL at the
field scale is not well understood and may be susceptible
to continuity and uniformity concerns associated with the
crust formation. CHP in contact with adsorbed mass/NAPL
is highly reactive and may exacerbate temperature and gas
generation issues associated with this oxidant. The aggressive
generation of gas in the presence of adsorbed mass/NAPL is
not necessarily specific to CHP, as ozone (O3) and persulfate
(S2O82−) activation may result in the formation of the highly
active hydroxyl radical (OH•) and field and laboratory studies
associated with permanganate (MnO4−) have demonstrated
considerable carbon dioxide (CO2) generation. A few consid-
erations associated with excessive gas formation are summa-
rized in the following:
1. Pore water displacement.  The displacement of pore
water by gas significantly reduces the hydraulic con-
ductivity of porous media. Reagent injection back-
pressures can increase to high levels as the aquifer
formation becomes “gas-locked.”
2. Oxygen gas buildup.  Most of the gas generated in
ozone (O3), persulfate (S2O82−), and CHP is oxygen,
which pushes its way into the vadose zone overly-
ing the treated volume. Oxygen partial pressures can
build to high levels in the vadose zone, creating sig-
nificant safety hazards. Vadose zone soils should be
vented as needed to maintain safe conditions.
3. Volatile organic carbon stripping. The elevated
temperatures associated with strong exothermic
oxidation reactions in the presence of NAPL and
rapid generation of gas combine to cause signifi-
cant mass transfer of volatiles from the aquifer into
the overlying vadose zone. These fugitive vapors
may constitute a significant contaminant removal
mechanism as well as a safety hazard. As with the
oxygen vapors, volatile organic carbon vapors that
accumulate in the vadose zone should be monitored
and vented/recovered, as needed, to maintain safe
conditions.
287
Lastly, in order to implement ISCO, the geochemistry
within the treatment ROI must be aggressively influenced
(Section 6.3.2.1), and a key geochemical parameter describ-
ing this influence is pH. The unique chemical reagents per-
form differently under acidic and alkaline pH. For example,
ozone (O3) radical chemistry is highly pH dependent, with
significant radical formation at alkaline pH and nearly all
direct oxidation (no radical chemistry) occurring under
acidic pH. CHP is most effective over the 3.0 to 5.0 pH
range. Depending on the selected activation method, per-
sulfate (S2O82−) injections characteristically result in acidic
pH with the dissociation of the persulfate into the bisulfate
anion (HSO 4 −). The wide range of extreme pH differences is
unique to ISCO and presents both challenges to and oppor-
tunities for remediation success.
6.3.2.3.1 Permanganate
The permanganate ion (MnO4−) is a selective oxidant that
can be effective for treatment of many aquifer contaminants,
particularly chlorinated alkenes over a wide range of pH.
Chlorinated ethenes, phenols, sulfides, organosulfur com-
pounds, and double-bonded, nonaromatic organics are suit-
able targets for permanganate oxidation, while fuels, aromatic
organic compounds (e.g., benzene), chloromethanes (e.g.,
carbon tetrachloride), and MTBE are not suitable targets for
permanganate oxidation.213 In particular, the permanganate
ion (MnO4−) is less reactive with single carbon–carbon bonds
(e.g., saturated hydrocarbons).214
As a selective oxidant, permanganate (MnO4−) is consid-
ered a fairly stable oxidant compared to the radical-based
alternatives. This “stability” enables better distribution
throughout an injection ROI but limits the contaminant list
that can be treated with permanganate (MnO4−).215–221 The
permanganate (MnO4−) oxidation chemistry follows second-
order rate kinetics but, in the absence of a considerable NOD,
may often be simplified as pseudo-first-order rate kinetics.
The permanganate (MnO4−) concentration is not considered
constant but is typically significantly greater than the con-
taminant concentration.
Permanganate is available as salts of potassium (K+) or
sodium (Na+), and the determination of which to use is based
on the required concentration, purity, and ease of handling.
The potassium permanganate (KMnO4; molecular weight =
158.03 g/mol) salt is sold as a fine crystalline solid that can be
dissolved in the field, creating injection concentrations of up
to 6.5% by weight at 20°C. It is important to incorporate the
aquifer temperature into the injected solution concentration
determination to avoid precipitation of permanganate (and the
associated aquifer clogging that might occur) at lower temper-
atures. Advances in mixing (i.e., dry powder, in-line eductors)
help to reduce material handling improving health and safety
when working with potassium permanganate (KMnO4).
The sodium permanganate (NaMnO4; molecular weight =
141.93 g/mol) salt is comparatively more soluble than potassium
permanganate (KMnO4) and can be used to generate higher
in situ concentrations. It is commercially available as a 40% by
weight liquid solution and should be handled with great caution.
288 Remediation Engineering

Sodium permanganate (NaMnO4) is normally diluted substan-
tially prior to injection into a chemical reactive zone.
It is possible for the commercially available permanganate
(MnO4−) salts to contain trace metals, including chromium,
which may cause secondary water quality impacts following
injection. For example, consider a 2.5% by weight (25 g/L)
potassium permanganate (KMnO4) injection of a reasonable
volume (18,900 L; approximately 485 kg KMnO4). The mate-
rial specification sheet indicates the potassium permanganate
contains a maximum of 7.5 milligrams per kilogram (mg/kg)
of chromium. This indicates that in the 18,900 L injection vol-
ume, it is possible to have a maximum concentration of chro-
mium of approximately 0.2 mg/L (200 µg/L). Considering the
oxidizing nature of permanganate (MnO4−), it is reasonable
to assume that most of this chromium will be in the form of
hexavalent chromium (Cr6+), and some states (e.g., California)
have primary MCLs for hexavalent chromium (Cr6+) as low
as 10 µg/L. The injection concentration will be diluted in situ
into the ambient groundwater, but even a 10% concentration
response at a dose-response monitoring well could have tem-
porary exceedances of some ancillary water quality criteria.
This simple calculation of the potential trace chromium con-
centration contribution to an aquifer should be completed prior
to injection, and a product-specific analysis may be requested
from the vendor to improve the accuracy of the estimate. It is
important to note that metals may be solubilized from aquifer
soils, independent of metal content of the injected oxidant for-
mulation, a topic discussed for each oxidant.
Permanganate (MnO4−) is typically injected over the
course of a few days to weeks using batch or in-line mixing
and injection equipment. Typically, potassium permanganate
(KMnO4) requires batch mixing and sodium permanganate
(NaMnO4) can be diluted in-line since it is delivered as a 40%
by weight liquid. However, as mentioned, dry powder in-line
mixing apparatus exist.
6.3.2.3.1.1  Reaction Mechanisms  The manganese (Mn)
atom in permanganate (MnO4−) has a “+7” valence and is
expressed as Mn7+. During the oxidation process over a prac-
tical pH range (3.5 to 12), the manganese (Mn7+) is reduced
to a “+4” valence and is expressed as Mn4+. The main reduc-
tion product is manganese dioxide (MnO2), which precipitates
from solution. Under strongly acidic conditions (pH <3.5), the
manganese may remain in solution as manganous manganese
(Mn2+), resulting in a greater electron transfer.214 Conversely,
under strongly alkaline conditions (pH >12), the green man-
ganate ion (MnO42−) may form with the transfer of only one
electron.214 As is evident by these pH ranges compared to
ambient aquifers, discussion in this section regarding perman-
ganate (MnO4−) oxidation will focus on manganese dioxide
(MnO2) generation with an electron transfer of three electrons
as the primary reaction mechanism.
Yan and Schwartz23 provided a reaction network for per-
manganate (MnO4−) oxidation of trichloroethene (TCE;
C2HCl3) that showed several alternative pathways, all of which
began with a two-center reaction that forms a hypomanga-
nate ester (Figure 6.78). From this point, several potential
unstable intermediates were postulated, leading to the forma-
tion of four intermediate products that were observed in their
experiments: formic acid (CHO2), glycolic acid (C2H2O3), gly-
oxylic acid (C2H2O3), and oxalic acid (C2H2O4). All of these
products were susceptible to reaction with permanganate
(MnO4−), forming the final product, carbon dioxide (CO2).
The general overall oxidation reaction of TCE (C2HCl3) to

O O O O
Mn Mn
O O– O O
+ Cl H
Cl H
C C
C C Acyclic
Cl Cl hypomanganate
Cl Cl Cyclic ester
hypomanganate
ester
Cyclic manganate Acyclic
ester hypomanganate ester Trichloroglycol

Additional unstable reaction intermediates

O O O O O O O

H C O H C C H C C OH C C
O OH OH
H
Formic acid Glycolic acid Glyoxylic acid Oxalic acid
MnO4– MnO4–
MnO4–
MnO4– O C O
Carbon dioxide

FIGURE 6.78  Reaction pathways for the permanganate (MnO4−) oxidation of trichloroethene (C2HCl3). (Redrawn from Yan, Y.E. and
Schwartz, F.W., Environ. Sci. Technol., 34(12), 2535, 2000.)
Injected Reagent–Based Remedies
carbon dioxide (CO2) coupled with the reduction of perman-
ganate (MnO4−) to manganese dioxide (MnO2) is presented as
Equation 6.118:
- - + permanganate is 5 mg/L213 and 50,000 mg/L is the maximum
2MnO 4 + C2HCl3 ® 2MnO2 + 2CO2 + 3Cl + H (6.118)
Of note from Equation 6.118 are the reaction products, which
include manganese dioxide (MnO2), carbon dioxide (CO2), and
acidity (H+). In the presence of NAPL or extremely high NOD,
the rate and extent of manganese dioxide (MnO2) solid forma-
tion may reduce the injection capacity (defined as injection flow
rate [Qinj] divided by the injection pressure [Pinj]) in the imme-
diate vicinity of the injection area by occupying the available
porosity.223–226 The formation of manganese dioxides (MnO2)
is likely to occur as a crust encapsulating the NAPL or within
the most permeable pore throats of the aquifer. Either way, the
distribution and resultant contaminant contact is inhibited.
The degree of carbon dioxide (CO2) generation may be effec-
tively controlled by the pH of a well-buffered aquifer. Based
on the discussion in Section 6.3.2.1.2, it is clear that under cir-
cumneutral pH with elevated carbonate (CO32−) and bicarbon-
ate (HCO3−) concentrations, carbon dioxide (CO2) generation
will be largely sequestered. Notice the acidity (H+) gener-
ated in Equation 6.118, and with high concentrations of TCE
(C2HCl3) (such as NAPL), the pH may shift below 6.3, which
would be expected to favor carbonic acid (H2CO3) formation
and resultant carbon dioxide (CO2) off-gassing. Gaseous car-
bon dioxide (CO2) will influence permeability and contami-
nant partitioning. Gaseous carbon dioxide (CO2) movement
is unpredictable in aquifers and could result in deposition of
contaminant mass in previously unimpacted unsaturated soils
or shallower groundwater. These observations, along with the
aforementioned limitations of ISCO treatment of NAPL, sup-
port considering other alternatives for NAPL impacts.
6.3.2.3.1.2  Kinetics  Reaction kinetics for permanganate
(MnO4−) oxidation are several orders of magnitude lower than
for reactions between similar target compounds and hydroxyl
radical (OH•). Compare, for example, the second-order
kinetic rate constants for oxidation of TCE by permanganate
(MnO4−) and the hydroxyl radical (OH•) summarized in Table
6.28. For permanganate (MnO4−), the average rate constant is
0.67/M ∙ s, while the rate constant for hydroxyl radical (OH•) is
4 × 109/M ∙ s. That 10 order of magnitude gap is largely closed
by the concentrations of oxidant that can be achieved: more
than 0.1 M for permanganate (MnO4−) compared to only 1 ×
10 −13 to 1 × 10 −11 M for hydroxyl radical (OH•). Still, hydroxyl
radical (OH•) reactions are, relatively, quite fast.
For oxidation reactions between permanganate (MnO4−)
and potential target compounds, it is helpful to calculate
expected concentrations as a function of time, at various per-
manganate (MnO4−) concentrations. This was conducted for
TCE (C2HCl3), PCE (C2Cl4), and MTBE (C5H12O). The results
of calculations are presented in Figure 6.79. For each plot, the
permanganate (MnO4−) concentration was held constant at the
level shown, and the target compound concentrations were
289
calculated by pseudo-first-order degradation (Equations 6.69
and 6.70). The starting concentration for each compound was
1 mg/L. Permanganate (MnO4−) concentrations ranged from
5 to 50,000 mg/L as MnO4−. The visual detection limit for
working strength of potassium permanganate (KMnO4) that
would conceivably be applied in a field application (higher
concentrations can be achieved with sodium permanganate
[NaMnO4], but significantly higher concentrations are not
recommended). These data can be interpreted to develop
expectations for permanganate (MnO4−) performance for
each compound in a field application.
6.3.2.3.1.3  By-Product Formation  Permanganate (MnO4−)
can influence the mobility of geogenic metals by changing the
ambient geochemistry (i.e., pH, oxidation–reduction potential,
and ionic strength). Additionally, manganese itself is a metal,
and the commercially available reagents may have other trace
metals (Section 6.3.2.2.1). The formation of manganese dioxide
(MnO2) may have the capacity to adsorb some liberated metals
(i.e., aluminum [Al], cadmium [Cd], cobalt [Co], copper [Cu],
lead [Pb], nickel [Ni], silver [Ag], titanium [Ti], uranium [U],
and Zn [Zn]), which would be expected to inhibit metal mobil-
ity. The interaction between manganese dioxide (MnO2) and
chromium (Cr) is well documented,227 suggesting that it is one
of only a few mechanisms available to oxidize trivalent chro-
mium (Cr3+) to hexavalent chromium (Cr6+) under most natural
conditions according to Equation 6.119:
CrOH 2 + + 3b-MnO2 + 3H 2O ® HCrO -4 + 3MnOOH (s) + 3H +

(6.119)
This process is somewhat limited because manganese diox-
ide (MnO2) and chromium hydroxide (Cr(OH)3) are typically
found as solids (decreasing the likelihood of contact), but col-
loidal interactions in groundwater may occur. Metal mobility
associated with permanganate (MnO4−) oxidation is consis-
tent with other oxidant metal mobility and is observed to be
transient and spatially limited from the injection point. One
nuance associated with permanganate (MnO4−) is the com-
paratively higher concentrations of total manganese follow-
ing an injection (23,100 mg/L as Mn for a 5% by weight as
MnO4− injection solution). Portions of this manganese will
be precipitated out as manganese dioxide (MnO2) and diluted
in the ambient groundwater, but temporary exceedances of
the secondary water quality standard of 50 µg/L should be
anticipated.
In addition to metal mobility, the reactivity of perman-
ganate (MnO4 –) with naturally occurring compounds and
co-contaminants may yield undesirable by-products. The
higher the permanganate (MnO4 –) solution strength, the more
likely it is to form by-products. The formation of nonmetal-
lic by-products, such as acetone (C3H6O), carbon disulfide
(CS2), chloroform (CHCl3), and some other THMs (trifluo-
romethane [CHF3], chlorodifluoromethane [CHClF2], tri-
chloromethane [CHCl3], bromodichloromethane [CHBrCl2],
290 Remediation Engineering

TCE PCE
1 1
5 mg/L MnO4–

0.1 0.1
Concentration (mg/L)

Concentration (mg/L)
0.01 0.01

5 mg/L MnO4– 50 mg/L MnO4–

0.001 0.001

50 mg/L MnO4– 500 mg/L MnO4–

0.0001 0.0001
0 2 4 6 8 10 0 2 4 6 8 10
(a) Time (days) (b) Time (days)

MTBE
1
500 mg/L MnO4–

0.1
5,000 mg/L MnO4–
Concentration (mg/L)

0.01

0.001

50,000 mg/L MnO4–

0.0001
0 2 4 6 8 10
(c) Time (days)

FIGURE 6.79  Pseudo-first-order reaction rates for permanganate (MnO4−) oxidation of trichloroethene (TCE; C2HCl3) [Curve a]; tet-
rachloroethene (PCE; C2Cl4) [Curve b]; and methyl tert-butyl ether (MTBE, C5H12O) [Curve c]. For each compound, reaction rates were
calculated for multiple permanganate (MnO4−) concentrations.

dibromochloromethane [CHBr2Cl], and tribromomethane 10

[CHBr3]), during bench testing is discussed below as an
example. cis‐DCE
TCE
A bench-scale treatability study was conducted to evalu- Chlorobenzene
Concentration (µmol/L)

ate the efficacy of sodium permanganate (NaMnO 4) to treat Chloroform

1
TCE (C2HCl3), cis-DCE (C2H 2Cl2), and chlorobenzene
(C6H5Cl). Four concentrations of sodium permanganate
(NaMnO4) were used (1%, 4%, 7%, and 10% by weight),
plus an untreated control. TCE (C2HCl3) and cis-DCE
0.1
(C2H 2Cl2) were both destroyed to below detectable lev-
els in the 1% by weight sodium permanganate (NaMnO 4)
solution, as shown in Figure 6.80. Treatment of chloroben-
zene (C6H5Cl) was less effective, with a 10-fold reduction
observed at the 7% by weight solution strength and reduc- 0.01
0 2 4 6 8 10
tion to below detectable levels observed only at the 10% by Permanganate treatment concentration (%)
weight sodium permanganate (NaMnO 4) solution strength.
Chloroform (CHCl3) was not observed in groundwater from FIGURE 6.80 By-product formation during permanganate
the site but appeared in treatments with sodium permanga- (MnO4−) oxidation bench trial. Chloroform (CHCl3) was observed
nate (NaMnO 4) concentrations of 4% by weight and greater as a by-product at concentrations that increased as a function of
(Figure 6.80). increasing permanganate (MnO4−) solution strength.
Injected Reagent–Based Remedies
6.3.2.3.1.4   Future Innovation and Current Research  The
chemistry associated with permanganate (MnO4−) is well
established and understood throughout the literature.
However, room exists for innovation and improvement. One
such area is the use of paraffin wax shells to emplace per-
manganate (MnO4−) into an in  situ chemical reactive zone.
The concept suggests that as the paraffin wax dissolves slowly
over time, incremental amounts of permanganate (MnO4−)
are released into the groundwater, hence creating a slow-
release source of a soluble chemical oxidant. The distribution
radius is limited to the cylindrical dimensions of the shell, and
emplacement into boreholes is likely to be inefficient from a
volume to distribution relationship perspective. Deployment
in a gravel trench of a funnel and gate permeable reactive bar-
rier (PRB) may be more appropriate if supported by sufficient
pilot-scale testing.
6.3.2.3.1.5  Monitoring  Performance monitoring associ-
ated with a permanganate (MnO4−) oxidation implementation
is required to demonstrate the effectiveness of the treatment
and also monitor the persistence and attenuation of by-prod-
ucts. The in situ residence time of permanganate (MnO4−) has
been observed to be months to years, indicating that a single
injection of permanganate (MnO4−) could require performance
monitoring for an extended duration. Visual observation of the
characteristic purple color may be tracked, and various com-
mercial field test kits for permanganate (MnO4−) analysis are
available. If contaminant analysis is required prior to exhaus-
tion of permanganate (MnO4−), quenching (Section 6.3.2.1.4)
is typically good practice and likely a regulatory requirement.
6.3.2.3.2  Catalyzed Hydrogen Peroxide
Chemical oxidation utilizing the highly reactive hydroxyl rad-
ical (OH•) is common practice for ex situ and in situ contami-
nant destruction and dates back to 1894 and H.J.H. Fenton’s
description of iron CHP228. The popularity of the hydroxyl
radical (OH•) for in  situ remediation influenced significant
research and development on the catalysis process, and what
was once formally referred to as “Fenton’s chemistry” is now
more broadly referred to as CHP. This section will describe
the basic associated reaction mechanisms, the remaining
prevalence of iron CHP, as well as the associated by-product
formation and the remaining implementation challenges.
When CHP is used in ex  situ treatment applications, the
reaction mixture contains the target compound to be oxi-
dized and the catalyst (typically ferrous iron [Fe2+]) that will
be required to quickly react with hydrogen peroxide (H2O2).
The reaction mixture is adjusted to a pH between 3.0 and 5.0.
Hydrogen peroxide (H2O2) is then added into the reaction
mixture at a rate that is controlled to minimize the loss of
hydrogen peroxide (H2O2) to disproportionation.*
* Disproportionation is simultaneous oxidation and reduction of a com-
pound. With respect to hydrogen peroxide (H2O2), the oxygen is in the
valence state of −1. When it dissolved into water, it can be reduced to water
(H2O) and a −2 valence state or dissolved as oxygen (O2) with a valence
state of 0.
291
In an in  situ chemical reactive zone application, it is not
possible to maintain the reaction conditions within the narrow
limits defined for ex situ treatment applications. The injected
hydrogen peroxide (H2O2) may be catalyzed by any number of
mineral species under a wide range of pH. There are several
critical challenges for the field application of CHP, some of
which are active field of research229:
1.
pH adjustment limitations.  Aquifer minerals at most
sites resist significant adjustments to pH. Injection of
acids to push pH into the preferred range (between
3.0 and 5.0) may generate large quantities of gas
(carbon dioxide [CO2]) and heat. Moreover, pH lev-
els typically rebound if acid loading is too small, and
sizable acid doses are expensive and dangerous.
2.
Large-scale gas production.  Even under ideal stoi-
chiometry, CHP generates large quantities of gas
that displace groundwater. At an injection rate of
only 1 gal/min of 10% peroxide, more than 11 moles
of hydrogen peroxide (H2O2) is being injected each
minute. If one-third of the injected hydrogen perox-
ide (H2O2) is converted to oxygen (ideal stoichiom-
etry), oxygen is being generated at a rate of 83 L/min
(nearly 3 cfm) at standard temperature and pressure.
Under ideal stoichiometries, even this small liquid
injection rate generates off-gas that is comparable to
an aquifer sparge well. In the event that dispropor-
tionation reactions are significant, off-gas rates can
climb even higher.
3.
Short-duration reactions.  The speed of reagent con-
sumption in CHP may cause reagents to be expended
before the nonaqueous contaminant mass is desorbed
or dissolved into groundwater. Contaminant rebound
will most likely occur as nonaqueous-phase target
mass enters the aqueous phase where hydroxyl radi-
cal (OH•) reactions occur.
CHP is implemented through the injection of hydrogen per-
oxide (H2O2) and the catalysis (typically ferrous iron [Fe2+]
in the form of ferrous sulfate heptahydrate [FeSO4 * 7H2O]).
The injections are typically implemented separately to avoid
the rapid activation of hydrogen peroxide (H2O2) ex situ. The
geochemistry of the aquifer to be treated could scavenge
hydrogen peroxide (H2O2) or ferrous iron (Fe2+) depending
on the oxidation–reduction potential, and there is no broad
preference on which to inject first. If the temperature can be
controlled, mixing in-line may be an option, but this is less
desirable because of the heat and gas generated relatively
quickly.
6.3.2.3.2.1  Reaction Mechanisms  The reaction mecha-
nisms associated with CHP are categorized as radical pro-
cesses and, kinetically speaking, are completely driven by
radical chain reactions (Section 6.3.2.1.2). A proposed reac-
tion mechanism for CHP, using ferrous iron (Fe2+) as the
catalyst, is summarized in Equations 6.120 through 6.127
and represents an intensive literature search by Petri et al.230
292
summarizing proposed reactions by both Haber and Weiss231
and De Laat and Gallard232:
2+ 3+ -
Fe + H 2O2 ® Fe + OH + OH   k = 6.3 ´ 10 M s
• 1
(6.120)
-1 -1
OH + H 2O2 ® H 2O + HO2  k = 3.3 ´ 10 M s (6.121)
• • 7
HO•2 + H 2O2 ® H 2O + O2 + OH • (6.122)
Fe 2 + + OH • ® Fe3+ + OH -  k = 3.2 ´ 108 M -1s-1 (6.123)
HO•2 « O•2- + H +  pK a = 4.8 (6.124)
3+ 2+ + -1 -1
Fe + HO2 ® Fe + O2 + H   k =< 2 ´ 10 M s (6.125)
• 3
Fe3+ + HO2- ® Fe 2 + + HO•2   k = 2.7 ´ 10 -3 s-1 (6.126)
Fe + H 2O2 « Fe ( HO2 ) + H   k = 3.1 ´ 10 unitless
2+
3+ + -3
(6.127)
Fe ( HO2 )
2+
® Fe 2 + + HO•2   k = 2.7 ´ 10 -3 s-1 (6.128)
Identification of each of the radical species in Equations
6.120 through 6.128 is summarized in Table 6.27, as well as
the standard reduction potential233 and speciation influenced
pH.191 A brief discussion of crucial radicals is provided in
Section 6.3.2.2.2.1.2.
The reaction mechanism presented in Equations 6.120
through 6.127 provides examples of the initiation, propagation,
and termination reactions discussed in Section 6.3.2.1.2. In
Equations 6.120 and 6.126, nonradical reactants ferrous iron
(Fe2+) and ferric iron (Fe3+) initiate the generation of a radi-
cal. In Equations 6.121 and 6.122, propagation reactions are
shown as the hydroxyl radical (OH•) and the perhydroxyl radi-
cal (OH2•) react with hydrogen peroxide (H2O2) to form radi-
cals. Lastly, termination reactions are observed in Equations
6.123 and 6.125 when the hydroxyl radical (OH•) and the per-
hydroxyl radical (OH2•) engage in reactions that do not gen-
erate new radicals. The value of initiation and propagation
reactions is intuitive, and the value of termination reactions
may be either the regeneration of the catalyst (Equation 6.125)
or the destruction of an organic contaminant. Undesirable
termination reactions are associated with nontarget species
(i.e., Section 6.3.2.1.2) and, because of the universal nature
of reactivity of radicals, represent a considerable source of
inefficiency of CHP. The regeneration of the catalysis (in this
example ferrous iron [Fe2+]) is an important consideration as
it is directly related to maximizing the residence time of radi-
cal chemistry in situ. Regeneration of the ferrous iron (Fe2+)
catalysis is demonstrated in Equations 6.125 and 6.126 and
coupled with 6.127 and 6.128. At the typical pH values of most
CHP implementation (3.0 to 5.0), Equations 6.127 and 6.128
are the primary regeneration reaction, as the acid dissociation
Remediation Engineering
constant (Ka) for the hydrogen peroxide (H2O2)–hydroperoxide
anion (HO2−) pair is 11.6. Also, note that there is a four and
eleven order of magnitude difference between the reaction rate
-1 -1 constants (k) for the oxidation of ferrous iron (Fe2+) to ferric
iron (Fe3+) and the reverse reduction. This implies that regen-
eration of ferrous iron (Fe2+) will be the rate-limiting step in
initiating continued hydroxyl radical (OH•) formation. It is also
possible for the superoxide radical (O2•−) to reduce ferric iron
(Fe3+) to ferrous iron (Fe2+) (Equation 6.124). The superoxide
anion (O2•−) provides moderate reductive capacity at compara-
tively more neutral pH (greater than 4.8).
CHP provides radical-based oxidation and reduction
facilitating contaminant destruction of a broad range of
contaminants (Table 6.30). The nonselective reactivity of
the hydroxyl radical (OH•), which is the most powerful oxi-
dant available (Table 6.27), offers strong oxidation and is
often the benchmark as to whether chemical oxidation is
feasible. The  three mechanisms of oxidation most likely
attributable to the hydroxyl radical (OH•) are hydrogen
abstraction, addition to multiple bonds, and direct electron
transfer.234
6.3.2.3.2.1.1  Direct Oxidation  Direct oxidation of
hydrogen peroxide (H2O2) of organic carbon contaminants
is a great example of kinetic control over governing reac-
tion mechanisms. Direct oxidation here is defined as electron
transfer reactions (Section 6.3.1.3.1). Take, for example, the
direct oxidation of benzene (C6H6) by hydrogen peroxide
(H2O2) in Equation 6.129:
15H 2O2 + C6H 6 ® 6CO2 + 18H 2O (6.129)
This reaction has a strongly negative change in Gibbs free
energy (ΔGrxn) of approximately −4900 kJ235 (Table 6.21),
which implies an exothermic reaction and spontaneity.
However, from a reaction kinetics perspective, in situ direct
oxidation by hydrogen peroxide (H2O2) is comparatively
much slower than radical oxidation reactions to be of any sig-
nificance.236 Therefore, aside from recognizing the thermody-
namic feasibility of this reaction, no further attention is given
to direct oxidation by hydrogen peroxide (H2O2).
6.3.2.3.2.1.2  Radical Oxidation  The list of generated
radicals in Equations 6.120 through 6.128 is summarized in
Table 6.26. In addition to those reactions shown in Section
6.3.2.2.2.1, it is noteworthy to mention that organic radicals
(R•) may form as propagating or terminating reactions. Two
potential examples of organic radical (R•) propagation reac-
tions are presented in Equations 6.130 and 6.131160,237:
OH • + RH ® + R • + OH - (6.130)
R • + H 2O2 ® ROH + OH • (6.131)
The radicals included in CHP are difficult to characterize
because their half-lives range from microseconds to seconds,
Injected Reagent–Based Remedies
and analysis requires indirect measurements that are consid-
erably complex.230
The hydroxyl radical (OH•) is extremely reactive over a
wide range of pH, and, based on the precise mechanism of
generation, its lifetime in an in situ system could be as short
as 10 −7 s.191 Therefore, often the applicability of the hydroxyl
radical (OH•) to the destruction of a particular contaminant
is determined by the comparative scavenging kinetics of
hydroxyl radical (OH•) interactions with other species. Such is
the difference between in situ and ex situ applications of CHP.
The perhydroxyl radical (HO2•) is the protonated (i.e., hydro-
gen [H+] attached) form of the superoxide anion (O2•−) and is
the dominant form at pH below 4.8. The perhydroxyl radical
(HO2•) is important in propagation reactions of the CHP pro-
cess but is only a mild oxidant.238 The superoxide anion (O2•−)
is the conjugate base to the perhydroxyl radical (HO2•) and
serves as a mild reductant and nucleophile. At higher con-
centrations of hydrogen peroxide (H2O2) and in the presence
of aquifer solids, the generation and reactivity of superoxide
anion (O2•−) can be improved, and its involvement in regener-
ating the catalyst (Equation 6.124) improves the effectiveness
of CHP.
6.3.2.3.2.2  Iron Catalysis Strategies  Although Fenton’s
chemistry is more broadly referred to as CHP, ferrous iron
(Fe2+) is still the most popular engineering catalysis process.
It is not possible to deploy “classic” Fenton’s chemistry to
in  situ chemical reactive zones because the porous medium
constrains mixing, and the aquifer matrix participates in
many of the oxidation or reduction reactions that accom-
pany the process. One of the most important deviations from
classic Fenton’s chemistry is the natural aquifer’s tendency
to buffer pH through carbonate (CO32−) and other alkalinity
mechanisms. This introduces competition for hydroxyl radi-
cal (OH•). A more neutral pH supports the predominance of
the superoxide radical (O2•−), which can facilitate the regen-
eration of iron at higher hydrogen peroxide (H2O2) concen-
trations, but the speciation of iron at circumneutral pH and
oxidizing conditions supports ferric iron (Fe3+).
Three hydroxyl radical (OH•) production approaches have
been suggested for use in aquifers, and all are attempting to
generate Fenton’s or Fenton-like reactions:
1.
Conventional. The conventional Fenton’s process
relies on soluble ferrous iron (Fe2+) as the radical
initiator. This is normally achieved by adding fer-
rous iron (Fe2+) in the reaction mixture and adjust-
ing the pH to near 3.0. In a reactive zone, aquifer
minerals may buffer pH into a range too high to
sustain iron recycling reactions, so the conventional
Fenton’s strategy may only be operable in short epi-
sodes of acidification (with iron) followed immedi-
ately by hydrogen peroxide (H2O2) injection. The
acidification–oxidation cycle is repeated as needed
to achieve remedial objectives. It is also possible to
simply accept the ferric iron (Fe3+) loss rate and sup-
ply ferrous iron (Fe2+) to match its consumption by
293
initiation reactions. This strategy increases injection
volume significantly and may reduce hydraulic con-
ductivity through iron precipitation.
2.
Iron chelation.  The main limitation on radical pro-
duction strategies is loss of ferrous iron (Fe2+) from
solution when pH exceeds 3.0. The ferrous iron
(Fe2+) that is injected to serve as the radical initia-
tor is sufficiently soluble, but the initiation reaction
converts the ferrous iron (Fe2+) to ferric iron (Fe3+),
which has a low solubility above pH 3.0 (Equation
6.120). Effective Fenton’s reactions require recycling
of ferrous iron (Fe2+; Equations 6.125 and 6.126 and
coupled with 6.127 and 6.128), and this cannot be
sustained above pH 3.0. Chelation of injected fer-
rous iron (Fe2+) has been recommended as a strat-
egy to avoid the loss of ferrous iron (Fe2+). Chelation
solves the iron retention problem and allows opera-
tion of the process at pH above 3.0. Competition for
hydroxyl radical (OH•) scavengers is another pH-
related limitation on Fenton’s efficiency, and it can-
not be addressed by chelation.
3.
Mineral iron strategies.  Many aquifers contain iron
(or other metal) minerals that can catalyze radical
formation from hydrogen peroxide (H2O2). In these
cases, it has been suggested that the Fenton’s reac-
tion can be developed with injection of hydrogen
peroxide (H2O2), alone, relying on aquifer miner-
als in lieu of ferrous iron (Fe2+) injections or pH
adjustment.198–200,239
6.3.2.3.2.2.1   Conventional Fenton’s Process  The con-
ventional approach to in situ application of Fenton’s chemistry
is to acidify groundwater to low pH (3.0 to 5.0) to maintain
solubility of ferric iron (Fe3+), supporting the iron regenera-
tion reactions. This approach requires significant acid addi-
tion and, in high-carbonate (CO32−) aquifers, neutralization
reactions may limit the duration of pH suppression and gen-
erate considerable carbon dioxide gas (CO2). Bench-scale
treatability testing can be performed to determine the neu-
tralization capacities of aquifer soils. Repeated acidification
suppresses the neutralization capacity of aquifer soils, likely
due to occlusion of the carbonate mineral surface by reaction
products. Acidification of the carbonate minerals may limit
competitive hydroxyl radical (OH•) scavenging.
6.3.2.3.2.2.2  Iron Chelation Strategies  Ferrous iron
(Fe2+), or a comparable reduced metal species, is critical to
initiation of the hydroxyl radical (OH•) chain reaction. The
initiation reaction oxidizes ferrous ion (Fe2+), and the result-
ing ferric ion (Fe3+) rapidly precipitates from solution when
the pH is greater than 3.0.240 It is possible to use chelating
agents that maintain dissolved-phase iron concentrations for
extended periods of highly oxidizing and acidic pH conditions.
Chelating agents (ligands) are soluble compounds that have the
ability to bind to metal cations or soil minerals. Once chelated,
the metal may interact with hydrogen peroxide (H2O2) differ-
ently than the metallic cationic form. The use of chelation may
294
be desirable in aquifers with high pH-buffering capacity or in
geochemical environments where strongly acidic pH may sig-
nificantly enhance the mobility of heavy metals in groundwa-
ter. Examples of organic-based chelating agents that have been
used are citric acid (C6H8O7), cyclodextrins (sugar molecules
bound in a ring), EDTA (C10H16N2O8), and amino-poly-acetic
acids.230,241–243 Studies in the literature identified nitrilotriac-
etic acid (C6H9NO6), as well as other organic acids (i.e., gallic
[C7H6O5] and picolinic [C6H5NO2] acids), and pyrophosphate
(P2O74−) as effective chelators for iron to support CHP oxida-
tion.240,244 The organic acids were observed to improve rate
kinetics and are believed to be destroyed by the hydroxyl radi-
cal (OH•), as opposed to inorganic chelators. The destruction
of the chelate is likely a terminating reaction but does elimi-
nate the chelation of metals following ISCO.
6.3.2.3.2.2.3   Aquifer Mineral Strategies  The catalysis
strategy relying on geogenic minerals to result in the forma-
tion of the hydroxyl radical (OH•) continues to be an area of
focus and ongoing research. Studies available in the literature
have evaluated several specific minerals in terms of hydrogen
peroxide persistence and catalysis of reactions, and in general
iron and manganese have been observed to be the most pro-
nounced.239,245–249 Natural mineral interaction with hydrogen
peroxide (H2O2) appears to be pH dependent. For example,
goethite (α-FeOOH) appears to generate the hydroxyl radi-
cal (OH•) faster under acidic conditions than hematite (Fe2O3),
which appears to be more active at neutral pH.230 Forgoing an
initiator of CHP in favor of mineral catalysis should be pilot
tested in the field prior to full scale.
The following example describes a field trial for hydrogen
peroxide (H2O2) treatment without an initiator at a site where
moderate dissolved-phase iron levels (0.36 mM or 20 mg/L)
indicated that Fenton’s reactions might be sustained by iron
minerals in the aquifer soils. The baseline aquifer pH was 6.1,
0.4
0.3
Dissolved iron (mM)
0.2
0.1
0 0
–40 10
Elapsed time (days)
FIGURE 6.81  Loss of soluble iron (ferrous iron [Fe2+]) from aqueous phase during a catalyzed hydrogen peroxide (CHP) reagent oxidation
test to determine reaction rates with mineral iron radical initiation.
Remediation Engineering
and the oxidation–reduction potential was generally reduc-
ing. A 1150 gal batch of 5% hydrogen peroxide (H2O2) was
injected steadily over a 30 h period, at a location 10 ft upgra-
dient from the observation point with the highest baseline
iron concentration. The observation well was located outside
the radius that could be reached by the liquid injection; how-
ever, gases generated by the reactions reached the observation
location within 5 h of the start of injections. Dissolved oxygen
concentrations immediately increased to three times atmo-
spheric saturation from a baseline concentration of <1 mg/L.
Losses of dissolved iron were observed beginning 24 h after
the start of injections, a period during which the oxidation–
reduction potential increased, but only traces of hydrogen
peroxide (H2O2) were observed. On the eighth day following
injection, hydrogen peroxide (H2O2) measurements climbed
to more than 30 mM (1000 mg/L), and dissolved iron levels
fell to less than 1 × 10 −3 mM, as groundwater directly influ-
enced by the injected reagent reached the observation well.
The complementary loss of soluble iron and arrival of hydro-
gen peroxide (H2O2) at the observational well are presented in
Figure 6.81. Unreacted hydrogen peroxide (H2O2) is an indi-
cation that the Fenton’s reaction sequence lacked the soluble
iron needed for complete radical initiation.
6.3.2.3.2.3  Kinetics  Conceptualizing the kinetics of
CHP ISCO is challenged by the rapid rate of hydroxyl radi-
cal (OH•) consumption. Of the kinetic reaction order and rate
equations discussed in Section 6.3.1.2.4.1, second-order rate
kinetics most aptly fits CHP reactions. Considering that the
hydroxyl radical (OH•) has near universal reactivity and there
are an unquantifiable amount of reduced species in any given
contaminated aquifer, attempting to model second-order
rate kinetics for CHP would require numerous differential
equations to be solved simultaneously. Indeed, second-order
rate constants have been developed for contaminants and
35
Dissolved Fe (mM)
H2O2 (mM) 30
Hydrogen peroxide (mM)
25
20
15
10
60 110 160
Injected Reagent–Based Remedies
scavengers throughout the literature (Table 6.28), but cau-
tion should be used in applying these rate constants for site-
specific predictions as the differences in geochemistry will
drastically influence the calculations.
Petri et  al.230 discuss three methods of CHP rate kinetic
evaluations, which are briefly summarized here, but the com-
mon recognition is that all of the kinetic evaluations are based
on the variable persistence of the hydroxyl radical (OH•) in an
aquifer:
1.
Fundamental chemistry models. This approach
involves determining individual rate constants for
significant reactions within a radical chain reaction
and developing a set of balanced chemical equa-
tions upon which to base the individual mass bal-
ances for each reactive species. This set of nonlinear
differential equations is then solved simultaneously
for an overall oxidant and contaminant degradation
rate, informed by site-specific data of mineral con-
tent, aqueous concentrations, existing reaction rates,
etc. To underscore the complexity of this approach,
a “simple” hydrogen peroxide (H2O2) and iron cata-
lyst aqueous-phase-only system was modeled over a
range of pH, and it was found to have 21 reactions
to obtain an acceptable model to fit the experimen-
tal data.232 This example is rudimentary compared
to in situ applications of CHP, which would be site
specific.
2.
Competition kinetic analysis. This approach is a
simplified model that is more of a comparison of the
various sources of radical consumption. This form of
kinetic analysis can be used to understand the gen-
eral order of contaminant degradation and the role
of potential scavengers and to evaluate the feasibility
of CHP in a given aquifer considering the scavenger
concentrations. This approach does not include reac-
tion intermediates, which can be responsible for con-
taminant transformation or propagation reactions.
The many limitations of this approach suggest that
it should be used as a general assessment of reaction
conditions.
Simplified pseudo-first order. This method is offered
3. ity of ferric iron (Fe3+) to initiate hydrogen peroxide
in two ways. First, a steady-state hydroxyl radical
concentration ([OH•]ss) may be approximated based
on laboratory treatability testing. The approxi-
mated hydroxyl radical concentration ([OH•]ss) is
then used in pseudo-first-order rate calculations of
the target contaminants under similar CHP geo-
chemistry. The main limitation of this approach is
that it violates two of the three basic pseudo-first-
order conditions that the injected reagent is pres-
ent at concentrations significantly higher than the
targeted contaminant and that the injected reagent
is not reactive with other chemical species in the
reactive zone (Section 6.3.1.2.4.5). The lifetime and
estimated concentration of a hydroxyl radical (OH•)
in situ are likely less than 10 −7 s and 10 −13 to 10 −11 M,
295
respectively.190, 191 The second approach, offered by
Miller and Valentine,250 is to simplify CHP reactions
into three pseudo-first-order reactions occurring in
two steps. The first is the hydrogen peroxide (H2O2)
reaction with aquifer minerals and the catalyst, and
the second is the resultant undefined radicals with
the contaminants or scavengers. Neither of these
approximations is anticipated to produce universally
accurate rate kinetic evaluations.
6.3.2.3.2.4  Competitive Inhibitors  CHP is imple-
mented in  situ to destroy targeted contaminants, and any
use of the hydroxyl radical (OH•) other than targeted con-
taminant destruction could be considered competitive inhi-
bition. Known competitive inhibitors of the hydroxyl radical
(OH•) chemistry include carbonate (CO32−) and bicarbon-
ate (HCO3−), chloride (Cl−), sulfate (SO42–), and biological
enzymes. The following is a brief description of the inhibit-
ing mechanism:
• Carbonate (CO32–) and bicarbonate (HCO3–). A
detailed example of carbonate (CO32–) and bicar-
bonate (HCO3–), taken together here as bicarbonate
(HCO3–) with respect to competitive inhibition, is
presented in Section 6.3.2.1.3.3 for hydroxyl radical
(OH•) oxidation of TCE (C2HCl3). The conclusion of
that demonstration is that when ISCO with CHP is
used to target MCLs, bicarbonate (HCO3–) exerts a
considerable competitive inhibition. Bicarbonate
(HCO3–), which predominates at pH less than 10.3
(Figure 6.76), is considered for inhibition of CHP
because there are literature studies that suggest
highly alkaline applications of hydrogen peroxide
(H2O2) may generate a unique radical reaction mech-
anism series related to carbonate (CO32–).245,251–252
Sodium percarbonate (Na2CO3 * 3H2O) is an oxidant
that uses alkaline pH and hydrogen peroxide (H2O2)
to purposefully form the carbonate radical (CO3•–).
• Chloride (Cl–). Chloride (Cl–) may interfere with
CHP in two ways. First, chloride (Cl–) can com-
plex with ferric iron (Fe3+), reducing the availabil-
(H2O2) reactions. Second, chloride (Cl–) may react
directly with hydroxyl radicals (OH•), forming the
dichloride radical (Cl2•−) under acidic pH in the pres-
ence of high chloride concentrations (greater than
1000 mg/L) and when the hydrogen peroxide (H2O2)
concentration is less than 1000 mg/L.253,254 The gen-
eration of the dichloride radical (Cl2•−) could form
chlorine gas (Cl2), which could halogenate other
organic compounds.
• Sulfate (SO42−). The interaction of the hydroxyl radi-
cal (OH•) and sulfate (SO42−) is beneficial, in that the
sulfate radical (SO4•) is formed. In some instances,
sulfate (SO42−) has been observed to strongly com-
plex ferric iron (Fe3+) reducing its availability to
react with hydrogen peroxide (H2O2).254
296 Remediation Engineering

• Biological enzymes. Although present in most The reactions that comprise CHP ISCO occur rapidly,
groundwater at low concentrations, biological generating significant quantities of gas and heat. The gas
enzymes (such as catalase and peroxidase) may mix that erupts from the aquifer surface during the injec-
quench CHP. These microbial generated enzymes tion can provide clues as to the reaction process. These
are antioxidants and protect microorganisms from gases can be monitored as the reaction proceeds, allowing
the damaging hydroxyl radical (OH•). adjustments to be made during the course of the oxidation
treatment.
6.3.2.3.2.5  By-Product Formation  CHP can influence Several processes contribute to the gas mixtures observed
the mobility of geogenic metals by changing the ambient geo- in the vadose zone soils overlying CHP reactions:
chemistry (i.e., pH, oxidation–reduction potential, and ionic
strength). Additionally, assuming complete mineralization to • Carbon dioxide propagation. The presence of ele-
carbon dioxide (CO2) of the targeted organic contaminants by vated carbon dioxide (CO2) in the off-gas is an indi-
CHP, the main by-products specifically associated with the cation that organic carbon oxidation is occurring. If
injection of hydrogen peroxide (H2O2) and an associated cata- carbon dioxide (CO2) is not present in the off-gas,
lyst are oxygen (O2), carbon dioxide (CO2), and the catalyst organic carbon oxidation is not occurring, which
(typically iron). The iron is most likely present as a precipi- may indicate lack of radical formation or may be
tated ferric iron (Fe3+) and poses minimal risk. The reactivity an indication that no organic carbon remains in the
of the hydroxyl radical (OH•) may result in the generation of formation.
incomplete oxidation by-products that may also be regulated • Oxygen propagation.  Disproportionation of hydro-
constituents. For example, the oxidation of MTBE (C5H12O) gen peroxide (H2O2) is an alternative reaction path-
can lead to the generation of TBA (C4H10O), which can be way, often consuming a large fraction of injected
more mobile in groundwater. Treatability testing prior to hydrogen peroxide (H2O2). Reaction of hydrogen
field-scale implementation is recommended and will provide peroxide (H2O2) with ferric iron (Fe3+) is a major
clues as to which contaminants may require either numerous source of oxygen (O2) in the off-gas. Because pro-
hydrogen peroxide (H2O2) injections or focused attenuation ductive (radical-forming) reactions of hydrogen per-
monitoring to evaluate the incomplete oxidation by-product oxide (H2O2) with ferrous iron (Fe2+) result in the
persistence. formation of ferric iron (Fe3+), the disproportionation
reaction and formation of significant quantities of
6.3.2.3.2.6   Future Innovation and Current Research  ​ oxygen (O2) are unavoidable.
Briefly, future work on CHP will likely focus on improved sta- • Vaporization of target compounds.  Oxygen (O2) and
bilization methodology to enhance hydrogen peroxide (H2O2) carbon dioxide (CO2) gases escaping the aquifer also
distribution in an aquifer and potentially extend the reactivity of carry gas-phase volatile and semivolatile organic
the reagent. Recent research by Watts et al. showed that sodium compounds into the vadose zone. Gas-phase con-
citrate (C6H7NaO7−), sodium malonate (C3H2O4Na2), and sodium taminant concentrations often surge in the vadose
phytate (C6H6Na12O24P6) can be potentially slow hydrogen per- zone at the start of a CHP injection and remain ele-
oxide (H2O2) decomposition rates by up to 50-fold.229 New min- vated until oxidation reactions are completed.
eral surfaces that are capable of behaving as catalysts may be
explored. As computational software improves, more accurate 6.3.2.3.3 Persulfate
kinetic models may be attempted, involving complicated numer- An exciting and comparatively newer approach to ISCO is
ical methods for solving a series of mathematical equations. persulfate (S2O82−) chemistry. Persulfate (S2O82−) chemistry
Finally, the influence of gas generation on porous media trans- has been established for more than 50 years, but only since the
port may also be further explored to understand the magnitude beginning of the 2000s was it applied in laboratory- and field-
and duration of its influence. scale applications for in  situ chemical reactive zones with
increased frequency.214 Owing to the potential for radical-
6.3.2.3.2.7  Monitoring  Performance monitoring associ- based oxidation, there are numerous similarities with CHP
ated with a CHP implementation is required to demonstrate the ISCO, and some of the initiation and propagation reactions
effectiveness of the treatment and also monitor the persistence result in the formation of hydrogen peroxide (H2O2) and the
and attenuation of by-products. The in situ residence time of hydroxyl radical (OH•).
hydrogen peroxide (H2O2) has been observed to be minutes Persulfate (S2O82−) may also be referred to as peroxydisul-
to days (depending on the level of catalysis), indicating that a fate because there is another form of “persulfate” called
single injection of hydrogen peroxide (H2O2) will not persist peroxymonosulfate (SO52−) that exists and is also a strong
for an extended duration. Field parameters (specifically tem- oxidant. For all practical applications, peroxydisulfate is the
perature, pH, and specific conductivity) may be good aque- available form of “persulfate,” and therefore in this chapter,
ous indicators of hydrogen peroxide (H2O2) and ferrous iron peroxydisulfate is referred to as persulfate (S2O82−). With
(Fe2+) breakthrough and the associated chemistry. Quenching respect to the commercial availability of persulfate (S2O82−),
(Section 6.3.2.1.4) is typically not required for CHP because ammonium ((NH4)2S2O8), potassium (K2S2O8), and sodium
of the short lifetimes of the hydroxyl radical (OH•). (Na2S2O8) salts are available (Table 6.31), and the most
Injected Reagent–Based Remedies 297

persulfate (S2O82−) ISCO, but considerably more attention is

TABLE 6.31 directed toward the engineered activation and radical oxida-
Physical and Chemical Properties of Available Forms tion mechanisms.
of Persulfate (S2O82−)
Common name Ammonium Potassium Sodium
6.3.2.3.3.1.1  Direct Oxidation  A potential chemical
persulfate persulfate persulfate equation expressing the direct oxidation of benzene (C6H6) by
Chemical name Ammonium Potassium Sodium persulfate (S2O82−) is presented in Equation 6.134:
peroxydisulfate peroxydisulfate peroxydisulfate
Physical form Crystalline Crystalline Crystalline C6H 6 + 12H 2O ® 6CO2 + 30e - + 30H + (6.132)
(monoclinic) (triclinic) (monoclinic)
Formula (NH4)2S2O8 K2S2O8 Na2S2O8
( )
15 ´ Na 2S2O8 + 2e - ® 2SO24 - + 2Na + (6.133)
Molecular weight 228.2 270.3 238.1
Crystal density 1.98 2.48 2.59 + -
(g/cm3) 15Na 2S2O8 + C6H 6 + 12H 2O ® 6CO2 + 30Na + 30HSO 4
Color Off-white White White
(6.134)
Odor None None None
This oxidation is built on the half reaction of persulfate
Loose bulk 1.05 1.30 1.12
density (g/cm3)
(S2O82−) to sulfate (SO42−), which involves the sulfur element
Solubility (g/100 85 6 73 reducing from the +7 valence state in persulfate (S2O82−) to the
g H2O) 25°C +6 valence state in sulfate (SO42−). Other relevant reactions at
Solubility (g/100 116 17 86 different pH are included as Equations 6.135 through 6.136,255
g H2O) 50°C and all demonstrate that pH is highly influential on the specia-
tion of the persulfate (S2O82−) anion:
Source: FMC, Persulfates technical information. Informative brochure, 2001.
1
S2O82 - + H 2O ® 2HSO 4- + O2 pH 3.0 to 7.0 (6.135)
2
commonly used for in  situ chemical reactive zones is the
sodium salt (Na2S2O8). Therefore, throughout this chapter, 2- -
S2O8 + 2H 2O ® 2HSO 4 + H 2O2 pH > 0.3; [H ] < 0.5 M
+
persulfate refers to sodium persulfate and will be abbreviated
as persulfate (S2O82−). (6.136)
Persulfate (S2O82−) is an oxidant that allows for engineered
H+
“activation.” Whereas in Section 6.3.2.1.2, reactants that began
S2O82 - + H 2O ® HSO -4 + HSO5- [H + ] > 0.5 M (6.137)
radical chain reactions were referred to as initiators or as part
of an initiation reaction, the ISCO vernacular has adopted the
term activation, and therefore, throughout this chapter, activa- 1
S2O82 - + OH - ® HSO 4 - + SO 4 2 - + O2 pH > 13.0 (6.138)
tion and initiation are used synonymously. The various forms 2
of engineered persulfate (S2O82−) activation include heat acti-
vation, activation with dissolved/chelated metals, activation The direct oxidation rate kinetics associated with the persul-
with hydrogen peroxide, and alkaline pH activation. Direct fate (S2O82−) anion are similar to the CHP direct oxidation
oxidation with electron transfer reactions from persulfate rate kinetics in that they are comparatively reasonable to other
(S2O82−) to more reduced organic molecules is also possible. electron transfer reactions, but in comparison to the radical
Certain aspects of the reaction mechanisms are understood oxidation kinetics they are less significant.
quite well and supported by a reasonable amount of literature
citations. However, some reaction mechanisms are not well 6.3.2.3.3.1.2  Radical Oxidation  Whereas the direct
understood and will be identified through this section. Gaps oxidation reactions with the persulfate (S2O82−) anion are
in the literature typically represent current focuses of research selective and comparatively slower from a kinetic standpoint,
agencies and academic institutions. radical oxidation reactions via the sulfate radical (SO4•−) are
Persulfate (S2O82−) is injected similarly to permanganate faster and less selective. The radical-based reactivity of the
(MnO4−) when there is no engineered activator and similar sulfate radical (SO4•−) is slightly slower than the hydroxide
to CHP when there is an activator. Several configurations radical (OH•), but the universal reactivity is somewhat compa-
are possible with alternating partial volumes of persulfate rable. Hydroxyl radicals (OH•) destroy targeted contaminants
(S2O82−) and activator, mixing both in-line, or injecting all of through numerous mechanisms at estimated second-order
the persulfate (S2O82−) or activator first and injecting the other. rates of 106 to 1011 M−1 s−1.191 Hydroxyl radical (OH•) oxida-
tion rates are said to be diffusion controlled and occur more
6.3.2.3.3.1  Reaction Mechanisms  Similar to CHP, the readily than the rate of diffusion. This limits the extent of
reaction mechanisms for persulfate (S2O82−) include both overall contact that can be achieved between the hydroxyl
direct and radical oxidation. The direct oxidation reaction radical (OH•) and the targeted contaminant in cases where
mechanism is discussed briefly to acknowledge its role in the contaminant is stored in less accessible soil matrices.230
298
The sulfate radical (SO4•−) is also a powerful oxidant, but
its reaction mechanism is primarily direct electron transfer
with estimated second-order rates of 105 to 109 M−1 s−1.195,256
These rates are likely near diffusion-controlled rates as
well but are comparatively slower than the hydroxyl radical
(OH•) and may explain the longer in  situ residence time of
the persulfate (S2O82−) anion (i.e., days to weeks) compared
to the hydroxyl radical (OH•; minutes to hours). Propagation
reactions with the sulfate radicals (SO4•−) are likely to exist
just as with the hydroxyl radicals (OH•); however, the differ-
ent activation strategies and widely diverse geochemistry of
available implementations have yet to discern consistent and
predictable propagation mechanisms. For example, consider-
able research is published on highly oxidized compounds (i.e.,
carbon tetrachloride [CCl4]) being destroyed by the hydroxyl
or sulfate radical (OH• and SO4•−, respectively). This would
imply that the superoxide radical (O2•−), which may act as a
reductant or nucleophile, is generated and could also regener-
ate oxidized minerals to initiate new radical chemistry.238,257
The most comprehensive way to discuss the available radi-
cal oxidation mechanisms for the persulfate (S2O82−) anion is
to step through each of the activation mechanisms and their
associated radical chemistry. The first activation method is
thermal activation or heat, as shown in Equation 6.139:
Heat
S2O820 ® 2SO•4- (6.139)
The rate of oxidation is intuitively increased through the
application of heat, not only by generating the sulfate radi-
cal (SO4•–) but also through the Arrhenius equation (Equation
6.83) discussed in Section 6.3.1.4.1. Another noteworthy
component of heat activation is reported increases in hydro-
lysis rates, consistent with discussion in Section 6.3.1.3.2.
Analytical data from studies by Huang et  al. and Jeffers
et al. reported a consistent and improved degradation rate in
2,2-dichloropropane with temperature increase, regardless of
persulfate (S2O82–) concentration in Huang’s study.257,258
The second activation strategy is using transition metals
(most commonly ferrous iron [Fe2+]) to react with the persul-
fate (S2O82–) anion to yield a series of reactions. The metals
may be dissolved in solution (i.e., ferrous sulfate heptahydrate
[FeSO4  *  7H2O]) or be chelated with an organic acid259 (i.e.−.,
citric acid [C6H8O7]). Using metals to activate the persulfate
(S2O82−) anion avoids the need to heat the aquifer, and using
a chelating agent enables activating metal solubility over a
wider range of pH. The relatively straightforward implemen-
tation with fewer health and safety risks has led to this form of
activation becoming one of the more readily implementable.
The use of ferrous iron (Fe2+) for persulfate (S2O82−) activation
is well understood260–264 and is likely a one-electron transfer
reaction with ferrous iron (Fe2+) as shown in Equation 6.140:
2- 2+ •- 2- 3+
S2O8 + Fe ® SO 4 + SO 4 + Fe k = 8.3 M -1s-1 (6.140)
It has been noted in the literature that ferric iron (Fe3+)
may also activate persulfate, and commercially available
Remediation Engineering
activators are available as chelated ferric iron (Fe3+) with
EDTA (C10H16N2O8). Conflicting reports from the literature
demonstrate that persulfate (S2O82−) activation with ferric
iron (Fe3+) is less understood; however, the proposed ferric
iron (Fe3+)–persulfate (S2O82−) interactions in Equations 6.141
through 6.144 provide a possible mechanism for ferric iron
(Fe3+) to regenerate ferrous iron (Fe2+):
S2O82 - + 2H 2O « 2HSO 4 - + H 2O2
k = 6.12 × 10 −6 min−1 (pH = 1.7, 25°C) (6.141)
Fe3+ + H 2O2 « Fe ( OH 2 ) + H + k = 3.1 ´ 10 -4 (equilibrium)
2+
 (6.142)
Fe ( OH 2 )
2+
® Fe 2 + + HO•2 k = 2.7 ´ 10 -3 s-1 (6.143)
3+ 2+ + -1 -1
Fe + HO2 ® Fe + O2 + H k = 2 ´ 10 M s (6.144)
• 3
The noticeably lower rate constants observed in Equations
6.141 through 6.144 suggest this process is slow, and the first
reaction (Equation 6.141) is believed to occur under strongly
acidic conditions.265 The injection of persulfate (S2O82−) can
create strongly acidic conditions, which would support this
reaction mechanism, but under neutral or alkaline conditions
the generation of hydrogen peroxide (H2O2) is not as prevalent.
The combination of persulfate (S2O82−) and hydrogen per-
oxide (H2O2) is a powerful activation technique that is poorly
understood.259,264 It seems logical that hydrogen peroxide (H2O2)
is first catalyzed by aquifer minerals (Section 6.3.2.2.2.2.3) and
then in the presence of persulfate (S2O82−) forms the sulfate
radical (SO4•−) similarly to that discussed in Section 6.3.2.2.2.4
and repeated here slightly differently as Equation 6.145:
1
S2O82 - + OH • ® SO24 - + SO•4- + O2 + H + (6.145)
2
The reason why this type of chemistry may be poorly under-
stood is due to the futility of attempting to separate sulfate
radical (SO4•−) chemistry from the hydroxyl radical (OH•)
chemistry. The nearly universal reactivity of both of these
radicals in geochemically diverse aquifers at estimated sec-
ond-order reaction rates ranging from 105 to 1011 M−1 s−1 make
it challenging to separate the relative contributions of both
radical chemistries in field settings.
Lastly, activation with alkaline pH provides a highly ver-
satile activation strategy for persulfate (S2O82−). Alkaline
activation is typically most successful at pH values >11.0 to
decompose the persulfate (S2O82−) anion to form the sulfate
radical (SO4•−). Once formed, the sulfate radical (SO4•−) inter-
acts with the hydroxide anion (OH−) to form the hydroxyl
radical (OH•) according to Equation 6.146230:
SO•4- + OH - ® SO24 - + OH • (6.146)
A benefit of the highly alkaline activation of persulfate (S2O82−)
is the formation of the moderate reductant and nucleophilic
Injected Reagent–Based Remedies
superoxide radical (O2•−). Recall from Section 6.3.2.2.2.1.2
that the superoxide radical (O2•−) is the conjugate base to the
perhydroxyl radical (HO2•), with an acid dissociation constant
(pKa) of 4.8. Under strongly alkaline pH and because of the
longer residence time of sulfate radicals (SO4•−), the genera-
tion of the superoxide radical (O2•−) can be appreciable and
could provide a justifiable mechanism for the destruction of
highly oxidized halomethanes and chloroethanes.185,239,259,266
Clearly, the complexities of activated persulfate (S2O82−)
ISCO bring new challenges and exciting opportunities. The
combination and seemingly inseparable reaction mechanisms
of the hydroxyl radical (OH•) and the sulfate radical (SO4•−)
present a powerful oxidant alternative with areas for innova-
tion and research yet to come.
6.3.2.3.3.2  Kinetics  The kinetic discussion associated
with persulfate (S2O82−) is somewhat similar to the hydroxyl
radical (OH•) discussion (Section 6.3.2.2.2.3) because of the
high reactivity and short lifetimes of the radical species. A
comparison of the summarized rate constants from the lit-
erature and field observations of hydrogen peroxide (H2O2)
and sodium persulfate (Na2S2O8) injections supports the cur-
rent understanding that persulfate (S2O82−) has a longer in situ
residence time than hydrogen peroxide (H2O2). This does not,
however, provide an indication of the residence time of the
hydroxyl (OH•) radical versus the sulfate radical (SO4•−). The
flexibility of engineered activation provides the opportunity
to impart some control over how quickly the sulfate radi-
cal (SO4•−) is created in  situ, which can help match oxidant
consumption to contaminant availability. This control over
sulfate radical (SO4•−) generation may support a pseudo-first-
order rate approximation more closely because even though
the reactant (i.e., the sulfate radical [SO4•−]) is short-lived, its
rate of introduction into the aqueous phase compared to the
contaminant destruction rate may fit for the pseudo-first-order
assumptions.189,257,263,267–269 As would be expected, this is not
a rule and diversions from the pseudo-first-order assumption
have been observed as reactions stalling suggesting other
unaccounted influences.261,262 Rate kinetics are best predicted
with treatability testing at the bench scale and detailed geo-
chemical characterization for scaling up to field scale.
6.3.2.3.3.3  Competitive Inhibitors  The prevalence and/
or potential generation of aqueous compounds in the natural
aquifer is an important consideration for persulfate (S2O82−)
ISCO design. The predicted radical chemistry is somewhat
simplistic compared to the potential geochemistry encoun-
tered in  situ, and Section 6.3.2.2.2.4 discussed some of the
leading competitive inhibitors for hydroxyl radicals (OH•).
There are many similarities with respect to sulfate radical
(SO4•−) scavenging, and therefore this discussion is focused to
observed persulfate (S2O82−)-specific competitive inhibitors.
• Chloride. Chloride is a known radical scavenger and
has the potential to complex transition metals used
as activators for persulfate (S2O82−). As part of the
radical scavenging, chloride is believed to facilitate
299
the temporary formation of THMs and chloroeth-
anes.270 The reaction mechanism summarized in the
following (Equations 6.147 through 6.152) is hypoth-
esized as the explanation, which has been adapted
after Liang et al. 2006268:
SO•4- + Cl - « SO24 - + Cl• k = 6.1 ´ 108 M -1s-1(6.147)
Cl• + Cl - « Cl•2- k = 7.8 ´ 109 M -1s-1 (6.148)
Cl•2- + Cl•2- « 2Cl - + Cl 2 k = 7.2 ´ 108 M -1s-1 (6.149)
Cl• + H 2O « OHCl• - + H + (6.150)
OHCl• - « OH • + Cl - (6.151)
Cl•2- + H 2O ® OHCl• - + H + + Cl - (6.152)
In this reaction mechanism, chloride (Cl−) reacts
with the sulfate radical (SO4•−) to form the chlo-
ride radical (Cl•), which then reacts with more
chloride (Cl−) to form the dichloride radical (Cl2•−).
The dichloride radical (Cl2•−) results in the genera-
tion of chlorine gas (Cl2), which in water tends to
speciate as hypochlorous acid (HOCl) under acidic
pH (pKa of 7.53). The hypochlorous acid (HOCl•−),
chloride (Cl•), and dichloride (Cl2•−) radicals along
with the chlorine gas (Cl2) have the potential to form
THMs, not unlike chlorine treatment in wastewater
treatment plants. This is not unlike the observations
from the case study described in Section 6.3.2.2.1.3,
except in this instance radical chemistry is involved.
In addition to the formation of THMs, the generation
of organic radicals (R•) and subsequent interaction
may lead to chloroethane contaminants. The exact
mechanism is not fully understood but is believed
to be associated with chloride (Cl•) and dichloride
(Cl2•−) radical interaction with contaminant mass,
DOC, or the NOD of the aquifer. These reactions
create intermediate organic radicals (R•), which react
with each other to form chloroethanes. An example
demonstration of these potential by-products is pre-
sented in Figure 6.82. The data from the subject site
represent data from an approximate 70,000 gal 4%
by weight sodium persulfate (Na2S2O8) injection
into alluvial deposits in the western United States.
Successful distribution of the injected oxidant was
achieved and correlated with a resultant order of
magnitude reduction in trichloroethene (TCE). After
the injection, chloroethanes and THMs are observed
to increase and subsequently attenuate. Clearly,
the potential for generating these constituents is an
important consideration and believed to be closely
tied to chlorine radical chemistry.
300 Remediation Engineering

1000

100

10

CVOCs (µM/L)
1

0.1
cis‐1,2‐DCE
trans‐1,2‐DCE
0.01
TCE
Injection
0.001
5/28/2005 6/17/2007 7/6/2009 7/26/2011 8/14/2013
(a)

1000

100

10
CVOCs (µM/L)

1
Acetone
Chloroethane
0.1
Chloromethane
1,2‐DCA
0.01 1,1,2,2‐TCA
Chloroform
Injection
0.001
5/28/05 6/17/07 7/6/09 7/26/11 8/14/13
(b)

FIGURE 6.82  (a) Chlorinated ethene response to a sodium persulfate (Na2S2O8) injection. Analytical data confirm a sustained order of
magnitude reduction following a single sodium persulfate (Na2S2O8) injection, despite a two order of magnitude rebound during postin-
jection monitoring. (b) Acetone, trihalomethanes (THMs), and chlorinated ethane intermediary response to sodium persulfate (Na 2S2O8)
­injection suggesting that temporary by-products other than mobilized metals may need to be considered during ISCO implementation.

• Aquifer minerals. One appropriate form of activa-
tion not discussed previously was ambient activation,
which relies on the naturally occurring metals in
the aquifer to activate the persulfate (S2O82−) anion.
There are a few reports in the literature that study
the interaction of persulfate (S2O82−) with natural
minerals,198–200 and “persulfate (S2O82−)-only” injec-
tions, implicitly relying on ambient activation, occur
frequently in the remediation industry. A common
result of this type of activation is strong acidity, as
Equation 6.141 shows the formation of the bisulfate
ion (HSO4−), which has a pKa of 1.9. This acidity may
be buffered by the aquifer, but in some instances
considerable acidic pH may last for a long period
of  time. Increased acidity can further activate per-
sulfate (S2O82−) through hydrolysis reactions or by
dissolving more transition metals.
6.3.2.3.3.4  By-Product Formation  Sodium persulfate
(Na2S2O8) can influence the mobility of geogenic metals
by changing the ambient geochemistry (i.e., pH, oxidation–
reduction potential, and ionic strength). Commercially avail-
able sodium persulfate (Na2S2O8) for use in in situ remediation
has lower reported metal impurities than permanganate prod-
ucts, though technical specifications of the purchased product
should still be requested. Certainly chelating metal activators
for persulfate (S2O82−) will result in increased metal concentra-
tions, and the acidity associated with the dissociation of per-
sulfate (S2O82−) in groundwater may enhance metal solubility
in a weakly buffered aquifer. Lastly, THMs and intermediary
contaminants may temporarily be detected within or immedi-
ately downgradient of the ROI of a persulfate (S2O82−) injection.
6.3.2.3.3.5  Future Innovation and Current Research 
Persulfate (S2O82−) is a comparatively new oxidant, and the
Injected Reagent–Based Remedies
flexibility of activated radical-based chemistry enables a wide
range of applicability to existing and emerging contami-
nants. Cyclic ether contaminants like 1,4-dioxane (C4H8O2)
are amenable to destruction by radical oxidation processes,
particularly persulfate (S2O82−) ISCO. In addition to a broad-
based applicability, new activation strategies may be possible,
prolonging the residence time of persulfate (S2O82−) in  situ,
increasing the oxidizing power, or prolonging the propagation
reactions in the radical mechanism.
6.3.2.3.3.6  Monitoring  Performance monitoring associ-
ated with a persulfate (S2O82−) oxidation implementation is
required to demonstrate the effectiveness of the treatment and
also monitor the persistence and attenuation of by-products.
The in  situ residence time of persulfate (S2O82−) has been
observed to be days to months (depending on the level of acti-
vation), indicating that a single injection of persulfate (S2O82−)
could require performance monitoring for an extended dura-
tion. Commercially available field test kits for persulfate
(S2O82−) analysis are readily available. If contaminant analysis
is required prior to exhaustion of persulfate (S2O82−), quench-
ing (Section 6.3.2.1.4) is typically good practice and likely a
regulatory requirement.
6.3.2.3.4 Ozone
Ozone (O3) for use in an in situ chemical reactive zone pres-
ents many benefits and limitations that are markedly different
from the other oxidants discussed. Ozone (O3) is a suitable
oxidant for many compounds and facilitates both direct and
radical-based oxidation. The most popular uses of ozone (O3)
are in aboveground treatment systems, in which ozone (O3)
is used for its direct oxidation capacity, or in combination
with another oxidant, such as hydrogen peroxide (H2O2), to
generate hydroxyl radicals (OH•). Ozone (O3) has also been
deployed in situ through injection of an ozone (O3)–air com-
bination in aquifer sparging. Both aboveground and in  situ
ozonation systems combine the effects of direct ozone (O3)
oxidation of target compounds with ozone (O3)-driven forma-
tion of hydroxyl radical (OH•).
Ozone (O3) is a gas that can be generated from air or oxy-
gen at the location where it is intended to be used. Ozone
(O3) is highly unstable with a decomposition half-life rang-
ing from several hours to several days. Ozone (O3) solubil-
ity and the concentration of ozone (O3) in the injected gas
stream are variables affecting the rate of treatment that
can be achieved. Commercial ozone (O3) generation equip-
ment produces ozone (O3) from air or oxygen. Typical air-
based systems can produce 10,000 ppmv (1% by vol) to
20,000 ppm (2% by vol), and oxygen-fed systems can pro-
duce up to 80,000 ppmv (8% by vol) to 100,000 ppmv (10%
by vol). Ozone (O3) generation is often referred to in pounds
of ozone (O3) generated per day, and larger ozone (O3) gen-
eration systems are typically limited to 50 pounds of ozone
(O3) per day. The aqueous-phase solubility of ozone (O3)
in balance with gas-phase ozone (O3) concentrations rang-
ing from 0 to 1,000 ppmv and from 0 to 60,000 ppmv at
temperatures ranging from 10°C to 35°C is presented in
301
Figure 6.83. The  calculations for Figure 6.83 were made
from Henry’s law data for ozone (O3) given in Sander.271 At
20°C, a 6% by vol ozone (O3) injection gas is expected to
generate approximately 7 × 10 −4 M ozone (O3) in solution,
if no reactions occur to scavenge the injected ozone (O3).
However, ozone (O3) is the target of numerous aqueous-
phase reactions, and the sustainable ozone (O3) concentra-
tion in an aquifer is likely to be much lower. Assuming the
7 × 10 −4 M ozone (O3) concentration is achievable, that is a
mass concentration of approximately 30 mg/L. The atmo-
spheric dissolved oxygen concentration at 20°C mg/L is
approximately 10 mg/L, and it is clear that ozone (O3) has
a higher solubility in groundwater than dissolved oxygen.
This has been reported to have a beneficial aerobic biologi-
cal benefit.272–275 However, as a highly scavenged oxidant
in an in  situ chemical reactive zone, sustained ozone (O3)
distribution may be a challenge. Additionally, as demon-
strated in Figure 6.83, the solubility of ozone (O3) decreases
with increases in temperature. As most radical-based ISCO
results in some modest temperature increase, physical solu-
bility may also limit the distribution of ozone (O3).
When ozone (O3) injection is deployed to create an in situ
chemical reactive zone, three modes of ozone (O3) demand are
observed. When ozone (O3) is first injected, a large transient
demand is observed as reduced inorganic species, aquifer
matrix material, and target contaminants combine to rapidly
consume injected ozone (O3). After the transient ozone (O3)
demand has been satisfied, the reactive zone is expected to
settle into a lesser, constant demand composed of two com-
partments: target contaminant demand and ozone (O3) scaven-
ger losses. If the scavenging demand is sufficient to generate
an ozone (O3) half-life in the range of 10 to 15 min, which may
be typical for groundwater, the effective treatment zone that
can be established around any injection point will be limited
by time of travel of the injected gas through the formation.
The aqueous-based half-life of ozone is contrasted with the
gaseous half-life of 3 days and is believed to be related to the
reactivity between the ozone (O3) molecule and the hydroxide
ion (OH−).276
In order to meet the requisite oxidant demand of the for-
mation and contamination, the implementation of an ozone
(O3) injection may be extended several months. This differs
from that of aqueous-based oxidants that can be injected
over an ROI over a few days to weeks. Typically, a tempo-
rary enclosure is required for an air compressor and ozone
(O3) generator to remain operating at a pulsed frequency
for the duration of the ozone (O3) injection. Ozone (O3)
injections can be constructed to include telemetry and pro-
grammable logic to reduce the on-site labor of operating
the system. A cost–benefit analysis between investing in a
system with sophisticated logic and the ozone (O3) injection
duration will generally determine the level of detail of the
system.
6.3.2.3.4.1  Reaction Mechanisms  The unstable
nature of ozone (O3) provides decomposition to radical
intermediates that can propagate radical chain reactions.
302 Remediation Engineering

2.0E–05

10°C
1.5E–05

Aqueous-phase ozone (mol/L)

15°C

20°C
25°C
1.0E–05 30°C
35°C

5.0E–06

0.0E+00
0 200 400 600 800 1000
(a) Gas‐phase ozone (ppmv)

0.0016

0.0014

0.0012
Aqueous-phase ozone (mol/L)

0.001 10°C
15°C
0.0008
20°C
25°C
0.0006 30°C
35°C
0.0004

0.0002

0
0 10,000 20,000 30,000 40,000 50,000 60,000
(b) Gas‐phase ozone (ppmv)

FIGURE 6.83  (a) Aqueous-phase ozone (O3) solubility for gas-phase concentrations of ozone (O3) up to 0.1% ozone (O3), by volume (0 to
1000 parts per million by volume), at 1 atm total pressure. (b) Aqueous-phase ozone (O3) solubility for gas-phase concentrations up to 6%
ozone (O3), by volume (0 to 60,000 parts per million by volume), at 1 atm total pressure.

Additionally, ozone is a powerful oxidant from an electron
transfer perspective. These two reaction mechanisms are
discussed in this section. It is noted that gaseous phase oxi-
dation has been reported in the literature via the sparging
of ozone (O3) into the unsaturated zone of an aquifer. The
discussion here is limited to aqueous-phase reactions in
groundwater.
Because ozone (O3) is a gas, it is sparged into an aquifer.
This means the dissolution of ozone (O3) into groundwater
is a mass transfer–limited process. Sparging is typically
implemented in a pulsed operation to prevent preferential
vertical conduits from forming and focusing the ozone
(O3) delivery to isolated seams. The high chemical oxidant
demand for ozone (O3) of most natural systems drives the
dissolution into groundwater but does so as the sparged
bubbles migrate vertically through the aquifer. A high
chemical oxidant demand and a mass transfer–limited dis-
solution process further complicate ozone (O3) distribution
in situ.
Lastly, direct oxidation is expected to be the more active
oxidation mechanism under acidic conditions in the absence
of catalysts. Ozone (O3) radical chemistry is closely tied to pH
and under alkaline conditions is expected to be the predomi-
nant reaction mechanism.
6.3.2.3.4.1.1  Direct Oxidation  The direct oxidation
mechanism is a selective process that general follows either
cycloaddition of an alkene bond (a carbon-to-carbon double
Injected Reagent–Based Remedies 303

O O and intermediates within the chain. Hoigne, Staehelin, and

+ + Bader278–280 propose the HSB model (shown in the following
O O O O
– – as mechanism A), and Tomiyasu et al.281 propose mechanism
(a) B. Both mechanisms are shown to highlight the similarities
O and differences:
+
O O Mechanism A—the HSB model
O
C C
O O O3 + OH - ® HO•2 + O•2- k = 70 + / - 7 M -1s-1 (6.153)
C C
(b) HO•2 « O•2- + H + pK a = 4.8 (6.154)

C O O3 + O•2- ® O3- + O2 (6.155)

O O3- + H + « HO•3 (6.156)

O O C

C O HO•3 ® OH • + O2 (6.157)

O C OH • + O3 ® HO•4 (6.158)
(c)
HO 4 ® HO2 + O2 (6.159)
FIGURE 6.84  (a) Ozone (O3) is a zwitterion, an electrically neu-
tral molecule that carries a resonating charge concentration that HO 4 + HO 4 ® H 2O2 + 2O3 (6.160)
imparts reactivity. (b) Sequence of ozone (O3) reaction with an eth-
ene (C2H4). (c) Breakup of the reaction intermediate to form water
and two aldehyde molecules. HO•3 + HO•4 ® H 2O2 + O3 + O2 (6.161)

Mechanism B—Tomiyasu, Fukutomi, and Gordon model

bond) or electrophilic attack on an aromatic hydrocar-
bon.276,277 Typically, alkene bonds, aromatic rings, and phe- O3 + OH - ® O3- + OH • (6.162)

nolic contaminants are most susceptible to ozone (O3) direct
oxidation.
O3 + OH - « HO2- + O2 (6.163)
The direct ozonation through cycloaddition with an ethene
(C2X4) is presented in Figure 6.84. The ozone (O3) molecule
is electrically neutral but carries opposing charge concentra- O3 + HO2- ® HO•2 + O3- (6.164)
tions. This structure is known as a zwitterion and contributes to
the reactivity of ozone (O3). Reaction with ozone (O3) requires HO•2 « O•2- + H + (6.165)
bonding at two sites simultaneously, forming the first reaction
intermediate known as a primary ozonide. Formation of the O3 + O•2- ® O3- + O2 (6.166)
initial linkage is a relatively improbable event for an ozone
(O3)–ethene (C2X4) reaction, and the probability decreases as O3- + H 2O ® OH • + OH - + O2 (6.167)

the level of chlorination increases. This low reaction probabil-
ity is reflected in the second-order kinetic rate constants for
O3- + OH • ® O•2- + HO•2 (6.168)
ozone (O3) reaction with ethenes (C2X4), and by far the low-
est rate with tetrachloroethene (PCE; C2Cl4), the most highly
chlorinated of the ethenes. O3- + OH • ® O3 + OH - (6.169)
Electrophilic attack on an aromatic ring is primarily the
electron attraction to the ozone (O3) molecule. This can cre- OH • + O3 ® HO•2 + O2 (6.170)
ate the superoxide radical (O2•−) and typically results in ozone
(O3) further attacking and breaking the aromatic ring. The similarity between these two proposed mechanisms
is that they both start with the ozone (O3) molecule react-
6.3.2.3.4.1.2  Radical Oxidation  Ozone (O3) radical ing with the hydroxyl anion (OH−), which means that the
chemistry is complex and disputed in the literature. There is most powerful ozone (O3) radical chemistry is at alka-
an agreement as to how the ozone (O3) radical chemistry is line pH. A  major difference between these two proposed
brought about, but there are two separate propagating chain mechanisms is the hydroperoxide anion (HO2−) versus the
mechanisms. These mechanisms differ over the exact radicals superoxide radical (O2•−), which is important when ozone is
304
combined with hydrogen peroxide because the hydroperox-
ide anion (HO2−) is a key catalyst.276
6.3.2.3.4.2  Kinetics  The challenges with attempting to
quantify ozone radical second-order rate kinetics are not
unlike those for the hydroxyl radical (OH•) and the sulfate
radical (SO4•−) and are not repeated here. Briefly, direct oxi-
dation with ozone (O3) is observed to obey second-order rate
kinetics as well, likely because of the decomposition reaction
of the ozone (O3) molecule.
6.3.2.3.4.3  By-Product Formation  Ozonation gener-
ates numerous classes of partial decomposition products and
reaction end products that may be of concern for drinking
water protection. Reaction intermediates include ketones,
aldehydes, and carboxylic acids. Many of these intermediates
are less reactive with ozone (O3) or hydroxyl radical (OH•)
than the original organic in the reaction and are susceptible
to accumulation when there is kinetic competition from more
reactive substrates. Formaldehyde (CH2O) is an example of
a potential product of ozonation reactions, and the second-
order kinetic rate constant for its decomposition with ozone
(O3)192 is 0.1 M−1 s−1, which is lower than for many potential
ozonation targets. In most cases, these highly soluble reaction
intermediates and by-products are biodegradable in the aero-
bic aquifer conditions that follow application of ozone (O3).
Ozone (O3) also has the capacity to react with bromide
anion (Br−) forming the bromate anion (BrO3−),192 which often
has a low regulatory threshold concentration (e.g., 10 µg/L or
lower). The rate of bromate (BrO3−) formation from bromide
ion (Br−) increases with increasing pH and with increasing
ozonation intensity. Von Gunten provided a detailed review
of ozone oxidation chemistry and by-product formation and
minimization and indicated that bromate (BrO3–) formation
can be limited somewhat by operation of ozonation systems
at reduced pH and through the addition of ammonia (NH3),
which suppresses formation of a key intermediate in the bro-
mate (BrO3–) formation reaction sequence.282,283
Ozone (O3) can influence the mobility of geogenic metals
by changing the ambient geochemistry (i.e., pH, oxidation–
reduction potential, and ionic strength). The decrease in pH is
generally associated with naturally occurring organic mate-
rial that is partially oxidized by the ozone (O3).162,284 The gen-
eral by-products from the injection of ozone into the aquifer
is an increase in dissolved oxygen. The secondary water qual-
ity constituents that may be liberated by radical-based ISCO
or competitively inhibit the radical formation (i.e., carbonate
[CO32−], bicarbonate [HCO3−], chloride [Cl−]) are similar and
therefore not repeated here (Sections 6.3.2.2.2.4, 6.3.2.2.2.5,
6.3.2.2.3.3, and 6.3.2.2.3.4).
6.3.2.3.4.4  Monitoring  Performance monitoring associ-
ated with an ozone (O3) oxidation implementation is required
to demonstrate the effectiveness of the treatment and also
monitor the persistence and attenuation of by-products. The
in  situ residence time of ozone (O3) has been observed to
be minutes, indicating that after a pulsed ozone (O3) cycle
Remediation Engineering
ends, the likelihood of sustained ozone (O3) in situ is highly
unlikely. The best metric for observing the distribution and
influence of ozone (O3) during sparging is to observe the dis-
solved oxygen concentration of the groundwater. Quenching
of residual oxidant is likely not an issue as the ozone (O3) has
a small half-life.
6.3.2.3.5 Combined Reagents (Advanced
Oxidation Processes)
Based on the discussion in this section, there are clear syn-
ergies between the four major classes of chemical oxidants.
Combining oxidant chemistries to harness the benefits and
offset weaknesses of radical-based chemistry is an ongoing
area of study and research. Activating persulfate (S2O82−) with
hydrogen peroxide (H2O2) is an example of combined chemi-
cal oxidants that produces both the hydroxyl radical (OH•) and
the sulfate radical (SO4•−). Another example is the combina-
tion of ozone (O3) and hydrogen peroxide (H2O2), which is the
subject of multiple patents throughout the remediation indus-
try. When applied in  situ, this form of combined advanced
oxidation process is known as peroxone or Perozone®. When
combined ex situ, it is known as HiPOx®. There are numerous
nuances to the implementation, such as slipstream ozone (O3)
diffusers that are coated in hydrogen peroxide (H2O2), shal-
low injection of hydrogen peroxide (H2O2) and deep sparging
of ozone (O3), and groundwater circulation with aboveground
HiPOx® through vendor-supplied mobile ex situ systems.
The peroxone chemistry relies on alkaline pH and the
formation of the hydroperoxide anion (HO2−) to create super­
oxide (O2–) radicals and hydroxyl radicals (OH•), according to
Equations 6.171 and 6.172:
H 2O2 « HO2 - + H + pKa = 11.6 (6.171)
O3 + HO2 - ® OH • + O2-• + O2 (6.172)
Although combining oxidants provides the benefits of both
respective oxidants, it may also compound or create circum-
stances that require special attention. For example, when
ozone (O3) and hydrogen peroxide (H2O2) are combined
in situ, ozone (O3) is sparged as a gas and hydrogen peroxide
(H2O2) may disproportionate or be oxidized to oxygen (O2).
This has the potential for considerable oxygen off-gassing.
Implications of combined oxidant systems have yet to be
fully realized. With each new novel application of an oxidant,
or combination of an oxidant system, more information is
gained about radical propagating chain reactions, hazards and
secondary water quality considerations, and interactions with
particular aquifer minerals. Effective and safe combination of
chemical oxidants is likely to be critical as regulatory limits
for recalcitrant contaminants are continually scrutinized and
emerging contaminants present new challenges.
6.3.3 Chemical Reduction
Reductive dechlorination and precipitation processes can also
be driven abiotically through reagent injections. Lacking the
Injected Reagent–Based Remedies
catalytic function of microbially driven reduction processes,
direct chemical reduction approaches require injection of
energetic reagents at high concentrations, in lieu of the car-
bohydrates or organic acids that are used to stimulate bacte-
rial reductions. Chemical reduction follows a similar design
construct as chemical oxidation, except it relies on chemical
reactions that reduce more oxidized contaminants. Chemical
reduction is inseparably linked to anaerobic biological strate-
gies because it is primarily driven by speciation cycling of
iron and sulfur, two elements that are routinely encountered
in natural aquifers. Tratnyek cites several studies that con-
firm the acknowledged abiotic reductants are of three types:
ferrous iron (Fe2+), sulfide (S2−), and components of natural
organic matter such as quinones.285–296 A summary of natu-
rally occurring minerals suspected to be critically involved
in abiotic chemical reduction is provided in Table 6.32.
Considerable research and focus have been spent on the syn-
ergy of ISCR and anaerobic biological strategies,297–302 mainly
because these mineral forms are generated as precipitates fol-
lowing organic carbon injections.
One separation made in this book is chemical reduction of
contaminants and metal precipitation. In  situ metal precipi-
tation is the subject of Chapter 7, but there are many reme-
diation technologies that are chemical in nature and involve
immobilizing metals from groundwater. Some discussion of
chemical reductant applicability to commonly encountered
metal contamination (i.e., hexavalent chromium [Cr6+] and
arsenic [As5+, As3+]) in this section is unavoidable, but for all
detailed discussion of metal removal from groundwater, the
reader is referred to Chapter 7.
The literature base for ISCR is broad and heavily domi-
nated by ZVI (Fe0) focused studies. Metal precipitation and
abiotic reductive dechlorination (for chlorinated ethenes
and ethanes) have received the primary attention, but other
contaminants include 1,2,3-trichloropropane (1,2,3-TCP;
C3H5Cl3),303 organic chlorinated pesticides (OCPs),304–307
nitrate (NO3−), chlorinated benzenes, chlorinated methanes,
perchlorate (ClO4−), and explosives.309 For more detailed and
specific reading on chemical reduction, the reader is referred
to the numerous short courses and guidance documents for
PRBs that focus intently on ZVI (Fe0)309–312 and the aforemen-
tioned citations here.
Lastly, chemical reduction is limited by the achievable
contact between the contaminant and the chemical reducing
TABLE 6.32
Naturally Occurring Chemical Reductants
Mineral Chemical Formula
Troilite Fe(1−x)S (x = 0 to 0.2); Fe2 to 2.5+
Mackinawite Fe(1+x)S (x = 0 to 0.11); Fe1.8 to 2+
Pyrite FeS2; Fe2+
Goethite α-FeO(OH)
Green rust sulfate Fe2+4Fe3+2(OH)12SO4 × yH2O
Green rust carbonate Fe2+4Fe3+2(OH)12CO3 × yH2O
Magnetite Fe3O4; Fe2.7+
305
reagent. Similar to ISCO, interactions of the reductants with
the natural geochemistry (viz., oxygen) result in rapid unpro-
ductive or scavenging reactions. Oxidation of sulfide (S2−) to
sulfate (SO42−) and ferrous iron (Fe2+) to ferric iron (Fe3+) is
thermodynamically and kinetically favorable in natural aqui-
fers. Many of the naturally occurring chemical reductants
summarized in Table 6.32 are generated in organic carbon
injection IRZs. As oxygen influxes from upgradient ground-
water into these zones, the available surface area for abiotic
reduction may be passivated with ferric iron (Fe3+) coatings,
which inhibits further abiotic chemical reduction. Therefore,
incorporating ISCR into remedial alternative strategies should
recognize that the treatment area influenced with either the
injected chemical reducing reagent or where TOC has trans-
ported and influenced the ambient geochemistry is limited.
Therefore, propagation of a chemically reducing signature in
support of an injection well transect in situ remediation strat-
egy is not appropriate.
6.3.3.1  Reagent Selection/Types
Commercially available chemical reductants are available for
ISCR, the most popular of which is ZVI (Fe0), but also include
polysulfides (Sx2−), ferrous iron (Fe2+), and sulfur oxyanions
(i.e., dithionite S2O42−). Additionally, more innovative products
combining sparingly soluble carbon sources and fine-grained
ZVI (Fe0) are available to actively pursue simultaneous abi-
otic and biotic reduction. A summary of available chemi-
cal reductants and recent pricing is provided in Table 7.8. A
consideration of the commercially available chemical reduc-
tants is the different technical specifications for use. In some
respects, chemical reduction as a stand-alone in  situ reme-
dial technology with a line of supportive chemical reagents
is in its infancy, with considerable research and development
throughout the 2000s. Creative and innovative applications
of commercial reductants used in water/waste­water treatment
may require a level of purity for in situ remediation that is not
readily available. Some chemical reductants in ex situ water/
wastewater treatment rely upon treatment train approaches,
and impurities in a particular reagent are either addressed at
a later time or diluted by massive quantities of treated water.
The vendor providing the chemical reducing reagent should
provide an SDS and technical specifications to ensure safe
handling and storage and allow for calculations of expected
loading to groundwater of metal impurities.
The selection of the appropriate chemical reducing reagent
is similar to the selection process for the appropriate chemi-
cal oxidant. It is a balance of the contaminant applicability,
the matrix reductant demand, and the contaminant reductant
demand. An important difference between chemical oxida-
tion and chemical reduction is contaminant applicability.
Chemical oxidation can destroy a wide range of contami-
nants, including even compounds that exist in a highly oxi-
dized state, whereas chemical reduction (to date) is primarily
geared toward oxidized compounds that are amenable to
reductive destruction or immobilization (i.e., heavy metals,
oxidation–reduction potential sensitive metals, chlorinated
ethenes and ethanes, OCPs, 1,2,3-TCP). Reduction reactions
306
are electron transfer reactions, and only minimal forms of
radical chemistry are reported.
Discussion in this section is focused on three popular chem-
ical reductants, dithionite (S2O42−), to represent the sulfur oxy-
anion classification, polysulfide (Sx2−), and ZVI (Fe0), which
will include some discussion on ferrous iron (Fe2+). Based on
Tables 6.32 and 7.8, it is clear that there are other forms of
chemical reductants available, some more so for ex situ water
treatment instead of in  situ remediation (i.e., trisodium salt
or TMT-15 [C3N3Na3S3], phosphites [PO33−] including sodium
and calcium [NaH2PO2 and CaH4P2O4, respectively], and
sodium borohydride [NaBH4]).
6.3.3.1.1  Sulfur Oxyanions
The dithionite anion (S2O42−) is a moderately strong reducing
agent that is used in paper-making processes to bleach pulp.313
Dithionite (S2O42−) is available as a sodium salt and has his-
torically been used to generate strong reducing conditions
in aquifers to support in situ metal precipitation and abiotic
reductive dechlorination.314 The dithionite anion (S2O42−) dis-
sociates to form two sulfoxyl radical anions (SO2•−), as shown
in Figure 6.85 and Equation 6.173:
S2O4 2 - « SO2 2 - + SO2 2 - (6.173)
The back reaction to reform dithionite (S2O42−) is quite fast
(k  = 1.7 × 109 M−1 s−1 at 25°C, pH 6.5 according to Ross
et al.),315 so the molarity of the sulfoxyl radical anion (SO2•−) is
likely to remain low. The sulfoxyl radical anion (SO2•−) that is
generated is highly reactive with dissolved oxygen, producing
the strong reductant superoxide radical anion (O2•-) and sul-
fur dioxide gas (SO2). The kinetic rate constant for the reac-
tion is 2.4 × 109 M−1 s−1, and the dithionite (S2O42–)-generated
sulfoxyl radical anion (SO2•–) is an effective oxygen scavenger
(Equation 6.174):
SO2 2 - + O2 ® SO2( g ) + O2 2 - (6.174)
This demonstrates the potential to engineer an aquifer using
dithionite (S2O42–) to support anoxic metal precipitation or
chemical reducing conditions for chlorinated volatile organic
compounds. As the sulfoxyl radical (SO2•–) reacts with dis-
solved oxygen (as well as other constituents), the sulfoxyl
radical (SO2•–) is consumed driving continued dithionite
(S2O42–) dissociation until the dithionite (S2O42–) is exhausted.
The dithionite (S2O42–) reactions that are valuable from an
in situ chemical reactive zone perspective are heterogeneous
–O O –O O Rickard and Luther), the exact number of polysulfide (Sx2−)
S S S• + •S
••
O O– O O–
FIGURE 6.85  Dissociation of dithionite anion, forming two sulf-
oxyl radical (SO2•−) anions.
Remediation Engineering
reactions that occur with soil minerals. The sulfoxyl radi-
cal (SO2•–), formed by dissociation of dithionite (S2O42–)
(Equation 6.173), can react with solid-phase ferric iron (Fe3+)
and water to form solid-phase ferrous iron (Fe2+) and the sul-
fite anion (SO32−), as shown in Equation 6.175316:
SO2 2 - + Fe(s)3+ + H 2O ® Fe(s)2 + + SO32 - + 2H + (6.175)
This solid form of ferrous iron (Fe2+) is likely to be present as
one of the forms in Table 6.32 and engage in abiotic reduc-
tive reactions once groundwater with amenable contaminants
interacts with its surface. The reduced form of sulfur (+3
compared to sulfate [SO42−] as +6) in dithionite (S2O42−) may
donate electrons directly to more oxidized contaminants or
form metal sulfide (MeS) precipitates as direct chemical treat-
ment. A case study example of conditioning an in situ chemi-
cal reducing zone for hexavalent chromium (Cr6+) treatment is
presented in Chapter 7. The primary by-products associated
with dithionite (S2O42−) treatments are reduced and subse-
quently oxidized species of iron and sulfur. In metal precipi-
tation strategies, contaminant metals are immobilized rather
than destroyed. To ensure permanence of the precipitated
immobilization, predesign consideration of the solubility of
targeted metals compared to natural geochemical conditions
is necessary to ensure that targeted treatment standards are
achieved.
6.3.3.1.2 Polysulfide
Polysulfides (Sx2−) have commercial and industrial appli-
cations of vulcanizing natural rubber and other polymers
(i.e., improving durability),317 in the production of dyes,318 and
in photoelectrochemical solar cells as electrolytes for elec-
trochemical storage.319,320 Additionally, they have been used
for agricultural processes to limit infection and prevent the
spread of certain fungal diseases for fruit trees.321 Polysulfide
(Sx2−) reagents are nonhazardous and typically available as
sodium polysulfide (Na2Sx; 33% by weight assay with 27%
by weight as sulfur) and calcium polysulfide (CaSx; 27% by
weight assay with 20.5% by weight as sulfur) (Table 7.8). The
pH of these assays ranges from 10.0 to 12.0, and the specific
gravity is approximately 1.25–1.39. They are solid as ruby-red
colored liquids dissolved in water and smell strongly of hydro-
gen sulfide (H2S; i.e., rotten eggs).
The complexities of polysulfide (Sx2−) speciation far exceed
the scope of this chapter, and for more in-depth reading on the
history and advances of understanding polysulfide (Sx2−) spe-
ciation, the reader is referred to Maronny,322 Schwarzenbach
and Fischer,323 Cloke,324 Teder,325 Giggenbach,326 Boulegue
and Michard,327 Kamyshny et  al.,328 and Rickard and
Luther.329 From all of the research reviewed and the general
consensus from more recent publications (Kamyshny and
species existing in aqueous media remains unknown, and it is
likely that S42−, S52−, and S62− are the dominant forms of poly-
sulfide at pH > 7.5.328,329 In Chapter 7, many forms of polysul-
fides (Sx2−) over the available oxidation states for sulfur are
presented in Figure 7.3, and consider Figure 6.86, which was
Injected Reagent–Based Remedies
0 reactive species have short residence times in  situ because
Total sulfur
S5=
S6=
2 S4=
S7=
S3=
S8=
pC
S2=
4 mine the reactivity of ZVI (Fe0), including surface area per
HS4– HS–
HS5 H2S
– HS2–
H2S2
HS6– HS3–
6 to 2 mm, a bulk density of 160 lb/ft3 (2.6 g/cm3), a specific
6 7 8 9 10 11 12
pH
FIGURE 6.86  Concentration of different sulfide (S2−) and poly-
sulfide (Sx2−) species in oversaturated solution of 50 mM polysulfide
precursor (K 2S5) as a function of pH (I = 0.3).328
generated by Kamyshny et al., and is a speciation diagram for
the polysulfide (Sx2−) system for an oversaturated solution of
5 × 10 −2 M potassium polysulfide (K 2S5). This graph supports
the current thought that S42−, S52−, and S62− are the dominant
forms of polysulfide (Sx2−) at pH > 7.5. It is noteworthy that
HS2− is the dominant polysulfide (Sx2−) species over the envi-
ronmentally significant pH range of 6.0 to 7.0329 because of
the presence of the disulfide ion (S22−) in key minerals such
as pyrite (FeS2). Even though pentasulfide (S52−) is expected
to be the predominant sulfide species in aqueous polysulfide
(Sx2−) solutions (Figure 6.86), the potential for other forms
complicates even the chemical formula used to refer to poly-
sulfide (Sx2−).
The predictive speciation work and geochemical graphs
supported by available thermodynamic constants are theo-
retical and highly sensitive to the equilibrium constants used
to generate them. Based on the pE–pH stability diagram for
the sulfur system presented in Figure 7.6, sulfide (S2−) is not
expected to predominate in aqueous systems, and under cir-
cumneutral mildly oxidizing geochemical conditions, sulfide
(S2−) is expected to oxidize to sulfate (SO42−) or elemental sul-
fur (Figure 7.6). Transferring the nebulous and complicated
oversaturated sulfide (S2−) aqueous chemistry to in situ chemi-
cal reactive zone design and implementation requires that the
practitioner recognize the geochemical challenge of injecting
a strongly alkaline sulfide (S2−)-rich chemical reagent into the
natural aquifer.
Similar treatment interaction and by-product formation
associated with dithionite (S2O42−) are observed for polysul-
fide (Sx2−) injections. Although not yet reported in the litera-
ture, polysulfide (Sx2−) may form the superoxide radical (O2•−)
or donate electrons directly to oxidizing contaminants. As
demonstrated in Figure 7.3, there are a wide variety of aque-
ous species associated with injection polysulfide (Sx2−) into an
aquifer (polysulfides [Sx2−], sulfane monosulfonic acids [poly-
thiosulfates; SxO32−], sulfane disulfonic acids [polythionates;
SxO62−], sulfite [SO3−], and sulfate [SO42−]).330 Most of these
307
they are rapidly oxidized to sulfate (SO42−), indicating that
there is an extensive degree of reductive capability of the
polysulfide (Sx2−) compound.
6.3.3.1.3  Zerovalent Iron
ZVI metal (Fe0) can be used as a solid-phase reducing agent
in chemical in situ reactive zones. A number of factors deter-
volume, processing and handling protocols, and alloys and
impurities. Some typical physical characteristics of commer-
cially available granular ZVI (Fe0) include a grain size of 0.25
surface area of 2600 m2/L, and a hydraulic conductivity of
5 × 10 −2 cm/d.310 Costs are market driven but typically fluctu-
ate around $0.50 per pound. The purity of ZVI (Fe0) is usu-
ally good, with few trace metals and a low carbon content
(typically less than 3%). Surface area is important because
many chemical reduction reactions (metal precipitation and
solvent destruction) occur on the surface of the ZVI (Fe0). A
larger surface per volume implies greater treatment potential
(Section 6.3.3.1.3.5). Processing and handling influences the
reactivity of ZVI (Fe0) because prolonged exposure to oxygen
can result in oxidation of the ZVI (Fe0; i.e., corrosion) from
Fe0 to ferrous (Fe2+) or ferric (Fe3+), effectively decreasing
the treatment payload. Lastly, a well-documented method for
increasing the chemical reactivity of ZVI (Fe0) is to create an
alloy with another metal (i.e., bimetallic ZVI; e.g., Pd, Pt, Ag,
Ni, Cu).331
ZVI (Fe0) reactive zones initiate a complex network of
homogeneous (same media; i.e., solid to solid) and hetero-
geneous (different media; i.e., solid to liquid) reactions that
may directly or indirectly destroy or precipitate contami-
nants. Some of the reactions may be catalyzed by mineral
surfaces or by metal-reducing microbial populations that
develop in situ. Many reactive zone processes consume the
ZVI (Fe0), and any ZVI (Fe0) application has a finite life
span that is directly related to the flux and chemical com-
position of groundwater passing through the reactive zone.
To achieve effective reduction, the iron surface area con-
centration (defined as the surface area of soil per volume of
liquid; m2/L) must be significant, and the contact time must
be comparatively longer than other in  situ chemical reac-
tive processes. To achieve these requirements, ZVI (Fe0)
is generally deployed in a trench oriented perpendicular to
groundwater flow. The trench is typically backfilled with a
mixture of ZVI (Fe0) and sand or other porous supporting
media to create a reactive barrier (based on hydrogeological
and geotechnical considerations; Chapter 10). The most com-
mon applications of ZVI (Fe0) reactive barriers have targeted
chlorinated solvents, polychlorinated biphenols, explosives,
etc.332–343 Other ZVI (Fe0) applications have been applied for
hexavalent chromium (Cr6+)344–354 and other dissolved metals
and radionuclides.355–365
Numerous competing reactions are expected in aquifer for-
mations, and the longevity of ZVI (Fe0) in situ is more likely
to be determined by consumption of nontarget compounds.
308 Remediation Engineering

Furakawa et al.366 provided two examples of competing reac- charge concentration supported the multiple-electron-transfer
tions (Equation 6.176 and 6.177): reactions of reductive dechlorination.
Homogeneous reactions occur in the same media; in the
-
2Fe(s0 ) + O2(g) + 2H 2O(l) ® 2Fe(aq)
2+
+ 4OH (aq) (6.176) case of ISCR with ZVI (Fe0), this is within the groundwater.
Because ZVI (Fe0) is a solid granular material, the homoge-
+
Fe (0s ) + 2H 2O( l ) ® Fe (2aq - neous reactions in groundwater associated with ZVI (Fe0) are
) + H 2 ( g ) + 2OH ( aq ) (6.177)
likely in the form of ferrous iron (Fe2+) as a result of Equations
6.176 and 6.177.
The oxic reaction shown in Equation 6.176 is likely to occur
in the upgradient interface between the ZVI (Fe0) mass and
influent groundwater. Further along the migration pathway, 6.3.3.1.3.1.2  β-Elimination Reaction  With respect to
the anoxic reaction shown in Equation 6.177 is likely to occur. abiotic reductive dechlorination of chlorinated ethenes and
Reactions with ZVI (Fe0) lead to pH increases through con- ethanes facilitated by ZVI (Fe0), the β-elimination reaction
sumption of protons as well as release of hydroxyl anions (e.g., is most simply defined as eliminating chloride (Cl−) ions from
Equation 6.176 and 6.177). the more chlorinated starting compound. This reaction chain
is sometimes referred to as the acetylene pathway because
the sequential elimination of chloride (Cl−) ions from each
6.3.3.1.3.1  Reaction Mechanisms  There are three gen-
molecule results in sequentially less chlorinated acetylenes
eral reaction mechanisms related to ZVI (Fe0), which will be
(dichloroacetylene [C2Cl2], chloroacetylene [C2HCl], and
discussed in this section: elimination reactions, hydrogena-
acetylene [C2H2]). The β-elimination reactions for chlorinated
tion, and hydrogenolysis. Additionally, because ZVI (Fe0) is a
ethenes are presented as Equations 6.178 through 6.181:
solid and is mostly used to treat dissolved contaminants, there
are reactions that occur over the two phases, referred to as
C2Cl 4 + Fe 0 ® C2Cl 2 + 2Cl - + Fe 2 + (6.178)
homogeneous and heterogeneous.

C2Cl 2 + Fe 0 + H + ® C2HCl + Cl - + Fe 2 + (6.179)

6.3.3.1.3.1.1  Heterogeneous versus Homogeneous
ZVI (Fe0) Reactions  Heterogeneous reactions involve two C2HCl + Fe 0 + H + ® C2H 2 + Cl - + Fe 2 + (6.180)

phases, the liquid and solid phases, in the case of reactive
zone chemistries (particularly ZVI (Fe0)). Solid surfaces can C2H 2 + Fe 0 + 2H + ® C2H 4 + Fe 2 + (6.181)

participate in reactive zone chemistry in several ways:
The half-lives of the chlorinated acetylenes (dichloroacety-
• Catalysis. Electrical charge concentrations on the lene [C2Cl2], chloroacetylene [C2HCl], and acetylene [C2H2])
mineral surfaces can attract ions or polar molecules are short, and they are rarely captured in most practical in situ
to the surface. There, reaction geometries can be field applications.
optimized for aqueous-phase molecules reacting
with atoms on the mineral surfaces or with other
6.3.3.1.3.1.3  Hydrogenolysis  With respect to abiotic
aqueous-phase molecules.
reductive dechlorination of chlorinated ethenes and ethanes
• Regenerable reactive centers. Mineral surfaces can
facilitated by ZVI (Fe0), the hydrogenolysis reaction is most
be activated, amended, or reactivated through injec-
simply defined as exchanging a chloride (Cl−)–carbon (C)
tion of reagents such as dithionite (S2O42−) or iron
bond with a hydrogen (H+)–carbon (C) bond. In this sequen-
sulfide (FeS). This is the basis for the creation of
tial process, two electrons are added to the carbon as part
in situ reactive zones from iron minerals in aquifer
of the “reductive” dechlorination. The hydrogenolysis reac-
soils.
tions for chlorinated ethenes are presented as Equations 6.182
• Adsorption sites. Aquifer minerals also can provide
through 6.185:
adsorption sites for contaminants such as the chlo-
rinated alkenes and for reactive metal ions such as
ferrous iron (Fe2+) and arsenic. C2Cl 4 + Fe 0 + H + ® C2HCl3 + Cl - + Fe 2 + (6.182)

The reduction reactions mediated by reduced iron compounds
are likely heterogeneous processes. Amonette et  al.,288 for
example, studied the abiotic reductive dechlorination of car-
bon tetrachloride (CCl4). They found that the mineral goethite
(α-FeOOH) adsorbed ferrous iron (Fe2+) from aqueous solution
and promoted dechlorination of carbon tetrachloride (CCl4),
while ferrous iron (Fe2+) in the aqueous phase was unreac-
tive. A similar observation has been made by others.297–302
They postulated that the ferrous iron (Fe2+) was adsorbed to
the hydroxyl groups of the goethite (α-FeOOH) and that the
C2HCl3 + Fe 0 + H + ® C2H 2Cl 2 + Cl - + Fe 2 + (6.183)
C2H 2Cl 2 + Fe 0 + H + ® C2H 2Cl 2 + Cl - + Fe 2 + (6.184)
C2H 3Cl + Fe 0 + H + ® C2H 4 + Cl - + Fe 2 + (6.185)
In each reaction, the half reaction of ZVI (Fe0) is oxidized
to ferrous iron (Fe2+) and gives up two electrons that are
transferred to the carbon. Of the ZVI (Fe0) reaction mecha-
nisms, hydrogenolysis is less desirable because it results in
Injected Reagent–Based Remedies 309

sequentially less chlorinated by-products, which have their

own regulatory standard and toxicity profile. Fortunately, TABLE 6.33
based on both laboratory and field studies in the litera- Degradation Rates Reported as Half-Lives Normalized
ture,312,367,368 >90% of the degradation of tetrachloroeth- to 1 m2 Surface Area per mL Solution
ene (PCE; C2Cl4) and trichloroethene (TCE; C2HCl3) is
Compound ZVI (Fe0)-Mediated Half-Life(t1/2), h
expected to follow the β-elimination reaction. However, a
recent evaluation of a 15-year PRB in Elizabeth City, North Chlorinated ethenes
Tetrachloroethene 2.1–10.8a; 3.2f
Carolina, suggested that some sequentially less chlorinated
Trichloroethene 1.1–4.6a; 2.4f; 2.8a
by-products from abiotic reductive dechlorination of influent
1,1-Dichloroethene 37.4f; 15.2a
TCE (C2HCl3) were observed at maximum concentrations
trans-1,2-Dichloroethene 4.9c, 6.9f, 7.6a
of 10% of the influent TCE (C2HCl3) downgradient of the
cis-1,2-Dichloroethene 10.8–33.9a; 47.6f
PRB.369 A possible explanation for this may be that passiv-
Vinyl chloride 10.8–12.3a; 4.7f
ation of available ZVI (Fe0) surface area over an extended
Chlorinated ethanes
operation may inhibit TCE (C2HCl3) contact with the ZVI
Hexachloroethane 0.013b
(Fe0), and abiotic dechlorination facilitated by dissolved-
1,1,2,2-Tetrachloroethane 0.053b
phase ferrous iron (Fe2+) or biological reductive dechlorina-
1,1,1,2-Tetrachloroethane 0.049b
tion facilitated by hydrogen (H2) from anoxic corrosion of
1,1,1-Trichloroethane 1.7–4.1a
the ZVI (Fe0) may be contributing to reductive dechlorina-
1,1-Dichloroethane Not reported
tion as the PRB matures. 1,1-Dichloroethane No treatment observeda
Methanes
6.3.3.1.3.1.4  Hydrogenation  For completeness, hydro-
Tetrachloromethane (carbon 0.31–0.85a
genation, or simply the addition of hydrogen to a compound, is
tetrachloride)
mentioned as a final reaction mechanism in the β-elimination Trichloromethane (chloroform) 4.8a
reaction. Note that Equation 6.181 in Section 6.3.3.1.3.1.2 Tribromomethane (bromoform) 0.041b
does not involve the removal of a chloride (Cl−) ion because Dichloromethane No treatment observedb,h,i
acetylene (C2H2) does not have a chloride (Cl−) remaining Chloromethane No treatment observeda
to remove. Nevertheless, acetylene (C2H2) may be further
Other compounds
reduced to ethene (C2H4) via hydrogenation.
1,1,2-Trichlorotrifluoroethane 1.02a
(Freon 113)
6.3.3.1.3.2  Kinetics  Because ZVI (Fe0) is typically 1,2,3-Trichloropropane 24d
emplaced in a trench such as a PRB, at the beginning of treat- 1,2-Dichloropropane 4.5d
ment, the ZVI (Fe0) and reactive surface sites are plentiful 1,3-Dichloropropane 2.2a
in comparison to the influent contamination and therefore 1,2-Dibromo-3-chloropropane 0.72a
first-order rate kinetics are an appropriate assumption for 1,2-Dibromoethane 1.5–6.5a
ZVI (Fe0) treatment kinetics. The rate constant (which is typi- n-Nitrosodimethylamine (NDMA) 1.83a
cally ZVI [Fe0] product specific) is influenced by the available Nitrobenzene 0.008e
surface area of the ZVI (Fe0), the type of iron, the inorganic 1,4-Dichlorobenzene No treatment observeda
composition of the groundwater, the temperature, and the
Source: Gillham, R.W., In-situ treatment of groundwater: Metal-enhanced
concentration/competition effects (i.e., scavenging losses).312
degradation of chlorinated organic contaminants, in Advanced in
A summary of available contaminant half-lives and first-
Groundwater Pollution Control and Remediation, 1996, pp. 249–274,
order rate constants for several common chlorinated volatile Kluwer Academic Publishers, Amsterdam, the Netherlands.
organic compounds of concern is summarized in Table 6.33. Note: Italicized results were performed with pure iron.
Of all of the factors influencing the rate constant, the surface a Gillham (1996)375

area is likely the most influential. b Gillham and O’Hannesin (1994)374

c Unpublished Waterloo data (no date or author provided by Gillham 1996)

6.3.3.1.4  Implementation Methods d Focht (1994)392

For all intents and purposes, it is an appropriate assumption e Agrawal and Tratnyek (1994)370

f Sivavec and Horney(1995)371

that granular ZVI (Fe0) is insoluble. The direct injection of
h Matheson and Tratnyek (1994)372
granular ZVI (Fe0) into semipermanent injection wells is not
i Schreier and Reinhard (1994)393
recommended and will almost certainly result in considerable
permeability reduction of the injection well and poor distribu-
tion of the iron. By far, the most common method of injection
ZVI (Fe0) into the subsurface is via the use of pressure- In addition to injection-based delivery, ZVI (Fe0) can be
based fracture tooling. As described in Section 6.1.2.2, these installed in a trench as a PRB or used as a slurry with benton-
included slurried injection with direct push tooling, hydraulic ite grout in an in situ soil stabilization/solidification (ISSS)
fracturing with a liquid carrier, or pneumatic fracturing with implementation. The use of ZVI (Fe 0) in PRBs and ISSS
a combination of gas and sand. implementations is well established and well understood,
310
and numerous successes are reported throughout the litera-
ture and technical conferences. Uniform and homogeneous
distribution of the ZVI (Fe0) is achieved through manual
placement in the trench or through the mixed monolith
without the burden of soil structure straining an insoluble
slurry solution.
6.3.3.1.4.1  Iron Type  Different types of ZVI (Fe0) are
available, and the differences generally originate from how
the ZVI (Fe0) is prepared. The different types of ZVI (Fe0)
include acid-washed, high-purity iron; oxide-coated commer-
cial materials; slag products from spent foundry sand; and
other waste products from iron and steel industries.312 Some
of the iron materials may have the potential for oil or grease
coatings if they originate from the automotive or manufactur-
ing industry, and it is generally good practice to avoid the use
of ZVI (Fe0) with oil or grease coatings.
A critical observation from a literature review by Gillham
et al. is that the metallic iron component is the treatment effi-
ciency differentiator among the different iron types. Among
the different types of ZVI (Fe0), there was not a large range in
reactivity, implying that if a comparable percentage of metal-
lic iron is present in different iron types, selecting the least
expensive will have minimal impact on the reactivity.312
Other forms of zerovalent metals are available, such as
zerovalent zinc (Zn0) and zerovalent tin (Sn0).303,332,377–379
However, a concern with these heavy zerovalent metals is that
they themselves are typical contaminants of concern. The
designed process of zerovalent metal is to facilitate oxidation
of the metal, and zerovalent zinc and zerovalent tin both oxi-
dize to the stable +2 valence as dissolved zinc (Zn2+) and tin
(Sn2+); however, these are stable valence states that promote
transport in groundwater.
6.3.3.1.4.2  Nanoscale ZVI  An alternative material to
“macro” ZVI (Fe0) (i.e., millimeters in size) that can achieve
high surface area concentrations by unit volume is nanoscale
ZVI (Fe0) (nZVI; 10 to 200 µm in size). The characteristics
that make nanoparticles qualitatively different from larger
particles are greater surface area to volume ratios and higher
natural reactivity of the reactive surface sites.380,381
Although the greater surface area concentration makes
nZVI seem like the best choice, there are many issues with
nanoparticles that are actively being addressed and researched
in the industry. Over the past 15 years, several advancements
in nZVI have improved its workability and mobility in situ;
however, industry-wide acceptance of nZVI for in situ reme-
diation via injection is not universal. Some of the complica-
tions and proposed solutions are discussed here, but for a more
thorough review of the advancements in nZVI, the reader is
referred to Keane,308 Crane and Scott,331 and Liu et al.382 for
“snapshot” critical reviews of nZVI throughout the develop-
mental timeline. There are three main forms of nZVI avail-
able for remediation efforts: bare nZVI, bimetallic nanoscale
particles (BNPs) (or alloys with other metals), and emulsified
zerovalent iron (EZVI).
Remediation Engineering
Bare nZVI particles tend to agglomerate (or aggregate),
meaning that the separate particles form larger particles by
adhering to themselves or soil particles. This decreases the
surface area of the nZVI, which decreases the mobility and
reactivity and limits the achieved ROI.383 The agglomeration
on soil grains clogs the porosity and limits the distribution of
nZVI in situ. Several conditions can cause the nZVI particles
to agglomerate, including the nZVI particle concentration, the
magnetism of the particles, and the zeta potential (ζ) (or sur-
face charge).384,385 Agglomeration caused by magnetism and
high concentrations are intuitive, and we will briefly discuss
the influence of the zeta potential (ζ). The zeta potential (ζ) is
the electric potential of a particle and dictates the attraction
to other particles. Generally, a zeta potential (ζ) greater than
+30 mV or less than −30 mV is considered stable (there is sig-
nificant surface charge to facilitate particle-to-particle repul-
sion). The highest attraction of a particle to other particles
occurs when the zeta potential (ζ) equals 0.386 Many param-
eters (e.g., surfactants, solution pH, and ionic strength) influ-
ence the zeta potential (ζ); thus, the industry has attempted
to manipulate these parameters to make a nZVI product that
is stable and distributable in situ. The influence of pH on the
zeta potential (ζ) is shown in Figure 6.87.386
BNPs increase the kinetics of the oxidation–reduction reac-
tion and generally result in more reactive ZVI.381 BNPs are
essentially coatings of metal catalysts (Pt, Au, Ag, Cu, Ni, Pd,
etc.) over the surface of the nZVI to reduce agglomeration and
improve kinetics.383 The concept of BNPs is effective because
the ZVI (Fe0) is sacrificially oxidized to protect the catalyst,
with chemical reduction occurring at the bimetallic surface
either via direct electron transfer with the catalyst or by the
hydrogen (H2) generated through ZVI (Fe0) corrosion.331
Complications with BNPs arise from the cost of the catalysts
being market driven and regulated metals themselves. In addi-
tion to using BNPs, studies have been completed evaluating
coatings to support stabilization. Some coatings can be inhibi-
tory in  situ by interfering with contact of contaminants and
15
10
5
Zeta potential (mV)
0
7.6 7.7 7.8 7.9 8.0 8.1 8.2 8.3 8.4 8.5 8.6
–5
–10
–15
–20
–25
–30
pH
FIGURE 6.87  The influence of pH on the zeta potential. (From
Zhang, X.-W. and Elliott, D.W., Remediat. J., 16(2), 7, 2006.)
Injected Reagent–Based Remedies
reactive surface sites on nZVI.385 Ideal coatings are biodegrad-
able (i.e., eventually stop interfering with contact of contami-
nants) and facilitate strongly reducing conditions to minimize
oxic corrosion of the nZVI (such as polysaccharides like starch
and carboxymethyl cellulose).382 An example of one such coat-
ing is the third and final available form of nZVI, EVO coated
nZVI (EZVI). This formulation is an agglomerate of nZVI
particles packed into a droplet comprising surfactant and oil
that forms an oil–liquid membrane. The protective membrane
facilitates greater mobility of the iron throughout an aquifer
during injection by decreasing corrosion or nZVI sorption
onto soil grains. Note that similar EVO injection constraints
exist as described earlier in this chapter, and appropriate cali-
brations are necessary for soil straining of the reagent.
According to Liu et  al.,382 lab-scale studies have demon-
strated that stabilized nZVI can improve in situ remediation
of soil and groundwater, but field-scale data are minimal.
Stabilization has improved the achievable ROI of a nZVI
injection; however, the practical distribution distance still
remains a limitation to broad-scale implementation of nZVI
for in situ remediation, especially as permeability decreases.
6.3.3.1.4.3  Residence Time  The longevity of ZVI (Fe0)
reactive zones is determined by the rate of decrease of the
ZVI (Fe0) surface area concentration. There are two main
modes of surface area concentration loss:
Consumption. The reactions between ZVI (Fe0) and target
compounds, as well as reactions with nontarget oxidants, con-
sume the ZVI (Fe0) reagent. Nontarget reactions (e.g., with
oxygen [O2], nitrate [NO3−], and sulfate [SO42−]) are expected
to dominate ZVI (Fe0) consumption in most aquifers.
Passivation.  The ZVI (Fe0) surfaces may become coated with
minerals that block the heterogeneous reactivity or passivate
the ZVI (Fe0). Formation of magnetite (Fe3O4), for example,
passivates ZVI (Fe0) surface area and has been observed in
field application sites.366 Laboratory batch and column tests
show that reacted ZVI (Fe0) developed a surface coating of
goethite (α-FeOOH) with trivalent chromium (Cr3+) concen-
trated at the outermost grain boundaries.387 Other groundwa-
ter constituents that may passivate the ZVI (Fe0) surface area
include calcium (Ca2+), carbonate (CO32−), sulfate (SO42−), and
silicate (SiO44−).309
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 7 In Situ Treatment of Metals
Remediation of groundwater impacted with dissolved metals,
metalloids, and radionuclides is perhaps one of the big-
gest challenges in in  situ environmental remediation today.
According to the U.S. Environmental Protection Agency
(USEPA), metals are present at more than 70% of the fed-
erally owned or federally regulated cleanup sites across the
United States (more than 11,000)—before considering sites
in state programs or the more than 30,000 abandoned mine
sites requiring environmental remediation.1 A recent query
(December 2015) of the USEPA National Priority List data-
base found that more than 86% of the approximate 1,830
superfund sites had metals in soil and/or groundwater.2 More
evidence of the magnitude of the issue lies with the increase
in stakeholder awareness, fueled by advancements in toxicol-
ogy coupled with press coverage of metal-related impairment
of drinking water resources.
This creates an opportunity for in situ remediation practi-
tioners. However, unlike organic contaminants, metals can-
not be destroyed or their recovery easily enhanced. Instead,
active and passive in situ remedial strategies for the treatment
of metals in groundwater generally involve direct precipita-
tion or sorption/coprecipitation, with the goal of permanently
sequestering and immobilizing the metals in the aquifer soil
matrix. Therefore, the end result is a reduction in the ground-
water concentrations, but the actual metals remain in situ. The
success of precipitation-based in situ treatment approaches is
dependent upon the following:
Kinetics: The ability to support meaningful rates of
precipitation is a minimum threshold that must be
met. If the reaction is thermodynamically spontane-
ous (i.e., requires no energy to occur) but the rate is
too slow, the approach will have limited usefulness.
The relationship of kinetics and thermodynamics is
discussed in Chapter 6.
Equilibrium solubility: The ability to achieve the
required cleanup standards for groundwater is criti-
cal. This is determined by the solubility of the pre-
cipitated solid phases as they form and mature in the
treatment zone.
Durability/permanence: The long-term stability of
the precipitated solids is a critical consideration.
Changes in the geochemical environment (pH, ionic
strength, or stimulation of oxidation/reduction reac-
tions) can affect this stability.
Thus, the concept of in situ metal precipitation extends beyond
numeric cleanup goals and invokes a required standard of
care that considers not only short-term solubility achieved
during active remediation but also the range of factors that
might erode or compromise the stability of the precipitated
solids over the long term.
7.1 TERMINOLOGY
A list of terms that are often associated with in situ metal
precipitation and aquifer geochemistry is defined here to
serve as a reference throughout the discussion presented in
this chapter. The terms selected are those commonly used in
environmental geochemistry vernacular, and some may be
an entire subject of study by themselves. Basic definitions
are provided here with clarifications as to how they are used
with respect to in  situ metal precipitation, and consistent
terms are maintained throughout this chapter to minimize
confusion.
Acid dissociation constants: The acid dissociation con-
stant (Ka) is a quantitative measure of the strength
of an acid in solution. It is the equilibrium constant
for a chemical reaction known as dissociation (i.e.,
deprotonation) in the context of acid–base reac-
tions. Numerous speciation diagrams are presented
throughout this chapter where they are relevant,
and they present the expected dissolved species at
a given concentration over a range of pH values.
For dissolved protonated compounds (protonated
meaning having one or more hydrogens [H+]), the
acid dissociation constant (Ka) defines the equilib-
rium between sequentially protonated compounds.
For example, carbonic acid (H2CO3) and bicarbon-
ate (HCO3−) are sequential protonated compounds of
the carbonate system. The acid dissociation constant
(Ka) to describe the equilibrium between carbonic
acid (H2CO3) and bicarbonate (HCO3−) is 4.7 × 10 −7.
When the ratio of products and reactants describ-
ing the balanced chemical equation of carbonic acid
(H2CO3) dissociation to bicarbonate (HCO3−) equals
this number, the dissociation is said to be in equi-
librium. Note, further dissociation (i.e., bicarbon-
ate [HCO3−] to carbonate [CO32−]) is described by a
unique acid dissociated constant (4.7 × 10 −11). The
speciation diagram for the carbonate system is pro-
vided in Chapter 6.
Alkali metals: The metals in Group 1A of the periodic
table (page ii): lithium (Li), sodium (Na), potassium
(K), rubidium (Rb), cesium (Cs), and francium (Fr).
Alkaline earth metals: The metals in Group 2A
of the periodic table (page ii): beryllium (Be),
323
324
magnesium (Mg), calcium (Ca), strontium (Sr), bar-
ium (Ba), and radium (Ra).
Anion: An ion that is negatively charged (e.g., sulfide
[S2−], carbonate [CO32−], hydroxide [OH−]).
Buffering capacity: Practically speaking, it is the aqui-
fer’s resistance to change. It could be related to
pH when acid or alkali is added or the oxidation–
reduction potential when an oxidant or reductant is
added. Classically, buffering capacity is tied to acid–
base chemistry and determined empirically in a lab-
oratory with titration testing. In this chapter, it may
also be used to describe changes in the oxidation–
reduction potential.
Cation: An ion that is positively charged (e.g., calcium
[Ca2+], uranyl [UO22+], ammonium [NH4+]).
Colloidal particle: A particle ranging in size between 1
and 1,000 nanometers in diameter.
Common ion effect: The reduction in the solubility of
an ionic precipitate when a soluble compound (con-
sisting of the ions of the precipitate) is added to the
solution in equilibrium with the precipitate.
Co-precipitation: The concept of an ion or compound
that is soluble, yet precipitates due to incorporation
into the crystal structure of another precipitating
mineral (either through substitution, adsorption, or
occlusion).
Heavy metal: A metal of relatively high density or high
relative atomic weight.
Heterogeneous reactions: A chemical reaction that
occurs between substances of different phases (e.g.,
solid and liquid). Another potential for heteroge-
neous reactions are on the surface of a catalyst of
a different phase. With respect to in situ metal pre-
cipitation, zerovalent iron (ZVI; Fe0) presents an
example of heterogeneous reactions.
Homogeneous reactions: A chemical reaction that
occurs between substances of the same phase.
Ionic strength: The measure of the concentration of dis-
sociated ions in a solution. The total concentration
of ions in solution influences the activity of the dis-
solved components (their availability for reaction)
and can drive the dissociation and increase the solu-
bility of some solids.
Lewis acid: A compound or ionic species that can
accept an electron pair from a donor compound.
Examples of Lewis acids include hydrogen (H+),
most metallic cations (MeX+), carbon dioxide (CO2),
and sulfur dioxide (SO2). Knowing whether a com-
pound or ionic species behaves as a Lewis acid (and
to what comparative degree) allows for prediction as
to how it will speciate at a given pH. Strong Lewis
acids will readily form bonds and complexes with
available Lewis bases.
Lewis base: A compound or ionic species that can
donate an electron pair to an acceptor com-
pound. Examples of Lewis bases anions (e.g.,
hydroxide [OH−], sulfide [S2−], carbonate [CO32−],
Remediation Engineering
phosphate [PO 43−], bicarbonate [HCO3 −]) as well
as all organic amines that by definition include
­a mmonia (NH 3).
Ligand: An anion or molecule that forms coordination
compounds or complexes with metals. Inorganic
ligands of primary importance in natural waters
are fluoride (F−), chloride (Cl−), sulfate (SO42−),
hydroxide (OH−), bicarbonate (HCO3−), carbonate
(CO32−), phosphate (PO43−), ammonium (NH4+), and,
in anoxic groundwater, bisulfide (HS−) and sulfide
(S2−). Nitrate (NO3−) does not form strong complexes
with metals.
Oxidation–reduction potential: A relative measure of
the potential for chemical species present to acquire
electrons (become oxidized) versus lose electrons
(become reduced), measured in volts (V) or millivolts
(mV) using a platinum electrode. In this chapter, the
oxidation–reduction potential may be referred to as the
aquifer’s “redox,” and may be abbreviated as EH or pE.
pH: The negative logarithm of the molar hydrogen con-
centration [H+]. pH is the direct measure of acidity
of the groundwater, and is related to water by the
water dissociation constant (Kw), which is 1 × 10 −14.
The “p” is the symbol for the negative logarithm.
The units for pH in the SI system are standard units,
abbreviated as s.u. For brevity, the units for pH will
not be carried through this chapter.
Point of zero charge: Specific to adsorption and
describes the condition when the electrical charge of
a surface is zero. pH is typically the parameter that
governs the surface charge and the pH at the point of
zero charge is referred to as the pHpzc.3
Precipitation: The formation of a solid mineral, which
typically happens when the concentrations of the
component ions of that mineral (more specifically
the product of the reactive dissolved molar concen-
trations, referred to as the ion activity product), are
greater than (or “saturated” compared to) the solubil-
ity product (Ksp).
Solubility product: The solubility product (Ksp) is an
equilibrium constant that captures the specific ratio
at which a mineral will dissolve in water to yield its
component ions. This concept was also discussed
earlier in Chapter 3.
Sorption: In this chapter, sorption will be used to refer
to adsorption, which involves a dissolved substance
becoming attached to the surface of a solid. This can
happen due to coulombic forces (electrostatic attrac-
tion) or electron sharing, through Lewis acid–base
interactions. It should not be confused with absorp-
tion, which is the incorporation of a substance in one
state into another of a different state.
Stability constants: (formation constant or binding con-
stant) An equilibrium constant for the formation of
a complex in solution. It is a measure of the strength
of the interaction between the reagents that come
together to form the complex.
In Situ Treatment of Metals 325

Transitional elements: Any of the set of metallic ele-
ments occupying a central block (groups IIIB–
VIIIB, IB, and IIB, or 3–12) in the periodic table
(page ii; e.g., iron, manganese, chromium, and cop-
per). Chemically, they show variable valence and a
strong tendency to form coordination compounds,
and many of their compounds are brightly colored.
7.2  METALS: AN OVERVIEW
The term “metals” is often used interchangeably for metals
and metalloids. Metals tend to lose electrons during chemi-
cal reactions, becoming positively charged ions (cations) in
groundwater, in addition to having specific physical proper-
ties.4 Examples of metallic elements include barium (Ba), cad-
mium (Cd), copper (Cu), lead (Pb), mercury (Hg), and zinc
(Zn). By comparison, metalloids exhibit physical properties
of both metals and nonmetals and tend to form negatively
charged ions (anions) in groundwater. Examples include arse-
nic (As), boron (B), and selenium (Se). Some metals, such as
chromium (Cr) and vanadium (Vd), will combine with oxy-
gen to form oxyanions depending on their oxidation state.
Thus, the oxidation–reduction (redox) potential sensitivity
and the geochemical behavior of different oxidation states
of the element targeted for remediation must be considered.
These differences can be critical when choosing a remedia-
tion approach as some metals may be more amenable to direct
precipitation in one oxidation state than another. A common
range of concentrations for environmentally relevant metals,
a list of their primary valence states, and the form of precipi-
tates that can be utilized to remove them from groundwater
are presented in Table 7.1.4,5
7.2.1 Metal Bonding Characteristics
The presence of metals in aquifers can be in many forms.
Metals can be present in elemental form, as metal alloys, in
ionic form, and/or in organometallic (i.e., a metal bound to at
least one carbon) form. Distribution of the commonly encoun-
tered metals in the subsurface can be categorized as summa-
rized in Table 7.2.
Metal cations can be classified as “hard,” “borderline,”
and “soft” cations. Note that most of the metals of interest
with respect to environmental remediation fall under the

TABLE 7.1
Common Concentration Range of Metals in Soils (mg/kg), Typical Oxidation States, and
Potential Metal Precipitates
Primary Oxidation States
Element Range Average in the Natural Environment Potential In Situ Precipitatesa
Aluminum (Al) 700–10,000 72,000 +3 Hydroxide, oxides
Antimony (Sb) 2–10 — +3, +5 Sulfide
Arsenic (As) 1–50 5 +3, +5 Typically requires coprecipitation
Barium (Ba) 100–3,000 430 +2 Sulfate
Beryllium (Be) 0.1–40 6
Cadmium (Cd) 0.01–0.7 0.06 +2 Carbonate, phosphate, sulfide
Chromium (Cr) 1–1,000 100 +3, +6 Hydroxide
Cobalt (Co) 1–40 8
Copper (Cu) 2–100 3 +1, +2 Hydroxide, phosphate, sulfide
Iron (Fe) 10,000–100,000 70,000 +2, +3 Hydroxide, carbonate, sulfide
Lead (Pb) 2,200 10 +2 Carbonate, phosphate, sulfide
Manganese (Mn) 1,000 1,000 +2, +3, +4 Oxide, carbonate
Mercury (Hg) 0.02–0.3 0.03 0, +1 +2 Sulfide
Nickel (Ni) 5–500 40 +2 Hydroxide, sulfide
Selenium (Se) 0.1–2 0.3 −2, 0, +4, +6 Elemental, mixed Fe–Se
Silver (Ag) 0.01–5 0.05
Tin (Sn) 2–200 1
Vanadium (V) 20–500 100 +3, +4, +5 Typically requires sorption
Zinc (Zn) 10–300 50 +2 Hydroxide, carbonate, sulfide

Sources: Sen Gupta, A.K., Environmental Separation of Heavy Metals: Engineering Processes, Lewis Publishers,
New York, 2002; Sposito, G., The Chemistry of Soils, Oxford University Press, New York, 1984 by permission
of Oxford University Press. Schacklette, H.T. and Boerngen, J.G., Element concentrations in soils and other
surficial materials of the conterminous United States, USGS Professional Paper 1270, USGS, Reston, VA, 1984;
Bowen, H.J.M., Environmental Chemistry of the Elements, Academic Press, London, U.K., 1979; Kotz, J.C.
et al., Chemistry and Chemical Reactivity, 5th edn., Thomson-Brooks/Cole, 2003.
a Reflects easily formed precipitates relevant to in situ remediation, not all possible solid phases. Sorption and coprecipi-

tation may also promote varying degrees of metal sequestration.

326
TABLE 7.2
Common Forms of Metals Encountered in Natural
Systems
Metallic Form Examples
Elemental Mercury, lead, gold, silver, and the other noble metals
Metal alloys Brass (copper and zinc), bronze (copper, tin, and zinc),
nickel–cadmium
Ionic Arsenic: As(III) arsenite, As(V) arsenate
Chromium: trivalent Cr(III), hexavalent Cr(VI)
Iron: ferrous Fe(II), ferric Fe(III)
Copper (Cu+, Cu2+), lead (Pb2+), zinc (Zn2+), cadmium
(Cd2+), mercury (Hg+, Hg2+)
Organometallic Dimethyl mercury, Hg(CH3)2; dimethyl arsenic,
As2(CH3)4; tetraethyl lead, Pb(C2H5)4; metal cyanide
complexes, Hg(CN)2, Zn(CN)42−, Cu(CN)2−, Fe(CN)64−
classification of “borderline” and “soft” (Cd2+, CH3Hg+, Cu2+,
Hg2+, Ni2+, Pb2+, Zn2+, etc.). In general, the toxicity of met-
als increases as it moves from hard to soft cations because
borderline and soft cations can deplete essential ligands from
biological systems and promote the potential for dysfunc-
tional reactions.9 Relative affinities of these metal ions to
form complexes with O-, N-, and S-containing ligands vary
widely. While hard cations prefer oxygen-donating ligands,
soft cations exhibit higher affinities toward nitrogenous and
sulfurous species. Borderline cations demonstrate relatively
equal affinity for O-, N-, and S-containing ligands.9
Classification of selected metal cations and the specific
characteristics of each type are described as follows10,11:
• Hard cations (Class A metals; A character behavior):
These include Al3+, Ba2+, Be2+, Ca2+, K+, Li+, Mg2+,
Na+, and Sr2+. These cations are spherically symmet-
ric and their electronic configurations conform to
inert gases; they form complexes only with ligands
containing oxygen donor atoms and have weak affin-
ity toward ligands with nitrogen and sulfur donor
atoms; of these, beryllium (Be2+) is the only one con-
sidered to be toxic at low concentrations.
• Borderline cations: These include Cd2+, Co2+, Cu2+,
Fe3+/Fe2+, Mn2+, Ni2+, Pb2+, and Zn2+. These cations
are spherically asymmetric, and their electronic con-
figurations do not conform to inert gases; they form
inner sphere complexes with O- and N-atom con-
taining ligands and have moderate affinity toward
S-atom containing ligands; all are toxic except iron
(Fe) and manganese (Mn).
• Soft cations (Class B metals; B character behavior):
These include Ag+, Au+, Bi3+, CH3Hg+, Cu+, Hg+/
Hg2+, and Tl3+/Tl+. These cations are spherically
asymmetric, and their electronic configurations do
not conform to inert gases; they have high affinity
toward S-atom containing ligands, and most of the
heavy metals are toxic.
Remediation Engineering
TABLE 7.3
Heavy Metals, Metalloids, and Light Metals of
Significant Environmental Concern
Classification Elemental Symbol and Specific Gravity
Regulated heavy metals Cr (7.19), Co (8.90), Ni (8.90), Cu (8.96),
Zn (7.13), Ag (10.5), Cd (8.65), Hg
(13.6), Ti (11.9), Pb (11.4)
Regulated metalloids As (5.78), Se (4.79), Sb (6.69)
Commonly occurring light Na (0.47), Mg (1.74), K (0.86), Ca (1.55),
metals Al (2.70)
Source: Sen Gupta, A.K., Environmental Separation of Heavy Metals:
Engineering Processes, Lewis Publishers, New York, 2002.
7.2.2 Heavy Metals
The term “heavy metal” is often used for both metals and met-
alloids. Despite its widespread use, this term does not have
a rigorous scientific basis or a chemical definition. Although
many of the elements listed as heavy metals have higher
atomic weights (e.g., heavy metals nickel [Ni; 58.69] and zinc
[Zn; 65.38] compared to “light metals” potassium [K; 30.10]
and calcium [Ca; 40.08]), major exceptions to this rule remain.
Heavy metals that are of significant environmental concern
along with commonly occurring light alkali and alkaline
earth metals are presented in Table 7.3 for comparison.4
In a typical aquifer, heavy metals may be classified into at
least two different categories:
• In true solution as free or complexed ions (e.g., Cu2+,
Fe2+, Zn(OH)42−, CrO42−)
• In particulates from adsorption onto other par-
ticles (e.g., mineral sediments or cations sorbed to
sediments), or incorporation into biomass of liv-
ing organisms and inorganic precipitates such as
hydroxides (OH−), carbonates (CO32−), sulfides (S2−),
and sulfates (SO42−)
These heavy metal elements also often exist in aquifers in dif-
ferent oxidation states. Aqueous reactivity, ionic charge, and
solubility of these metals vary widely. For their short- and
long-term impacts to receptors, the maximum permissible
concentrations of these heavy metals in drinking water and
groundwater are closely regulated through legislation (Section
7.2.5). Nevertheless, barring the exceptions of cadmium (Cd),
mercury (Hg), and lead (Pb), heavy metals are also required
micronutrients. Toxicity and inhibitory effects of these ele-
ments are, thus, largely a function of concentration. However,
nonessential heavy metal elements are considered to be inhib-
itory at all concentrations.4
7.2.3 Transition Elements
Some of the elements from the central portion of the peri-
odic table (page ii) can assume multiple oxidation states that
In Situ Treatment of Metals
are relevant to typical pressures and temperatures encoun-
tered in a natural system. Compounds including these
elements, especially the transition metals, may exhibit
variable solubilities according to the pH and oxidation–
reduction potential of the groundwater. For example, “plat-
ing metals” used in plating processes (e.g., cadmium [Cd],
iron [Fe], nickel [Ni], and zinc [Zn]) are typically associ-
ated with strong acidity and yield species that are highly
soluble. The plating metals are most often handled (and
released to aquifers) as soluble salts or acids, and their
mobility is somewhat constrained by interactions with the
aquifer soil matrix. Typical metals releases to the aquifer
from plating processes are characterized by high metal
concentrations and acidic pH. However, alternative valence
states and/or circumneutral pH render these metals effec-
tively insoluble under a wide range of natural aquifer chem-
istries. Other metals that are oxidation–reduction potential
sensitive (i.e., chromium [Cr], molybdenum [Mo], selenium
[Se], vanadium [Vd]) exist naturally at concentrations near
regulatory standards and may be liberated by anthropo-
genic influences. Reversion of these influences results in
precipitation. These observations provide an opportunity
to engineer the aquifer chemistry to mitigate the mobiliza-
tion of metals that can be harmful to receptors.
Most natural soil minerals are also compounds of transi-
tion elements. It is usually not the presence of these metals
that drives environmental concerns, but rather their mobility
in groundwater. Thus, modifications to the aquifer chemistry
in engineered reactive zone applications that influence their
solubility must be carefully designed. Transition elements
that form oxyanions (e.g., arsenic [a metalloid]) may have
high mobility in aquifers, especially under reducing condi-
tions. Clearly, implementing in  situ remedial technologies
to address metals contamination is complex, and it requires
careful consideration of the ambient aquifer chemistry
(Chapter 3).
7.2.4 Metals Characteristics Influencing
Transport and Toxicity
The ultimate fate and transport of all contaminants in  situ
is heavily influenced by the hydrostratigraphy of an aqui-
fer (Chapter 4). However, to understand the fate of metals
in an aquifer, it is equally important to understand the gen-
eral characteristics of the soil and the speciation of metals
in groundwater. The speciation and fate of metals in natu-
ral and engineered environments are ultimately governed
by the metal-specific chemical characteristics. Such charac-
teristics also dictate the biochemical reactions of metals as
nutrients or toxicants. In order to develop an insight, consider
the electron configurations of an alkaline earth metal cation
(calcium; Ca2+) and a heavy metal (transition metal) cation
(copper; Cu2+). The ground state electron configurations (the
assignment of electrons that result in the lowest energy for
the atom) for each element is provided in the periodic table
of elements (page ii).12 Conventionally, electron configura-
tions may be presented by listing the number of electron
327
shells (1,  2, 3,  4, etc.), followed by the relevant subshells
(s, p, d, and f) with orbital electrons present in comparison to
with the number of possible electrons in the subshells (s2, p6,
d10, and f14). The electron configuration for Ca2+ and Cu2+ is
shown in the following text:
Ca2+: 1s22s22p63s23p6
Cu2+: 1s22s22p63s23p63d9
The atomic number for Ca2+ is 20 and for Cu2+ is 29, indicat-
ing Ca2+ has 20 protons and Cu2+ has 29 protons. Therefore,
summing the electrons from the electron configurations ear-
lier for Ca2+ and Cu2+ to 18 and 27, respectively, confirms the
+2 charge on these ions.
Note that the outermost electron subshell of Ca 2+ (p) is
completely filled with six electrons, and the octet forma-
tion is satisfied. Thus, Ca2+ is not a good electron accep-
tor and, hence, a poor Lewis acid. Ions like Ca 2+ are hard
cations, and they form only outer sphere complexes with
aqueous-phase negatively charged ligands containing pri-
marily oxygen-donor atoms.4 They are typically referred to
as “Class A” metals, exhibiting “A character” behavior. In
contrast, Cu2+ has an incomplete subshell (d; 9 out of 10 pos-
sible electrons) and contains an electron cloud more readily
influenced by electric fields of other species. In general, Cu2+
is a fairly strong Lewis acid and tends to form inner sphere
complexes with aqueous-phase negatively charged ligands.
Electrostatically, Ca2+ and Cu2+ are identical, that is, both
Ca2+ and Cu2+ have +2 charges. However, Cu2+ is a stronger
Lewis acid and a relatively soft cation compared to Ca2+,
which is a poor Lewis acid and hard cation. This observation
provides specific insight into the fate and transport of Ca 2+
and Cu2+ in an aquifer, but more generally guides in situ met-
als treatment based on anticipated speciation and toxicity.
If the primary anions in the natural aquifer are correspond-
ingly borderline or soft anions/Lewis bases, then it would be
expected that the Cu2+ would preferentially form complexes
facilitating its mobility in groundwater. Conversely, if the
primary anions naturally occurring were hard Lewis bases,
Ca2+ formation would be expected (along with likely precipi-
tation), but Cu2+ would remain as a free ion. Therefore, by
simply knowing the characteristic Lewis acid/base behavior,
it is possible to frame the geochemical strategy for in  situ
metals treatment.
7.2.5 Regulatory Considerations
Relevant USEPA federally promulgated primary and second-
ary maximum contaminant levels (MCLs) for typical metals
of concern are summarized in Table 7.4. Where possible, up
to three standards per metal are provided in Table 7.4. These
represent the primary MCL, the secondary MCL, and the
MCL goal (MCLG). The MCLG is representative of the health
goal, and although not enforceable is the basis for the primary
MCL. For noncarcinogens, the MCLG is generally equivalent
to the primary MCL. For carcinogens, the MCLG is set to
328 Remediation Engineering

An important concept that extends beyond simply meet-

TABLE 7.4 ing regulatory standards in the short term is the permanence
Summary of Some Federal Maximum Contaminant of the in situ metals treatment. Careful consideration of the
Levels for Metals of Concern naturally occurring aquifer chemistry is necessary before
pursuing in situ metals treatment because as the engineered
USEPA Federal Standards in
Groundwater
influence dissipates, the precipitated or adsorbed metals may
be susceptible to dissolution. Effective management of stake-
Primary Secondary
holder expectations before remedy implementation through
MCL MCL MCLG
a holistic conceptual site model (CSM) approach will help
Metals Symbol (µg/L) (µg/L) (µg/L)
identify any potential limitations of compliance with federal
Antimony Sb 6 — 6
and state thresholds. This concept is more fully explained in
Arsenic As 10 — 0
Section 7.5.
Barium Ba 2000 — 2000
Beryllium Be 4 — 4
Cadmium Cd 5 — 5 7.2.6  pE– pH Diagrams
Chromium Cr, total 100 — 100
Cr, hexavalent — — — The status of an aquifer chemical environment can be sum-
Cr, trivalent — — — marized by two master variables*: pH, which measures
Cobalt Co — — — the tendency of the solution to accept protons, and pE (the
Copper Cu 1300 1000 1300 negative of the log of electron activity), which measures the
Iron Fe — 300 — tendency of the solution to accept electrons. The concept
Lead Pb 15 — 0 of pH and pE as master variables is described in Stumm
Manganese Mn — 50 — and Morgan,15 which is recommended for further reading.
Mercury Hg 2 — 2 Stability diagrams can be used to identify the compounds
Nickel Ni — — — of each element that are most stable for any pE–pH condi-
Selenium Se 50 — 50 tion, and an example comparison for zinc–water and zinc–
Silver Ag — 100 —
water–sulfur is presented in Figure 7.1. There are three
Tin Sn — — —
important limitations on the use of stability diagrams in
Vanadium V — — —
reactive zone design:
Zinc Zn — 5000 —

Source: California Environmental Protection Agency State Water Resources 1.

Control Board, www.swrcb.ca.gov/water_issues/programs/water_
quality_goals/search.shtml, accessed December 2015.
zero (e.g., lead [Pb] and arsenic [As]). The primary MCL is
enforceable and is as close the MCLG as possible given avail-
able treatment technologies and cost. The secondary MCL is
not enforceable and is generally applicable to metals that do
not pose a health risk. The secondary MCL provides a thresh-
old based on aesthetics such as color and odor (e.g., iron and
manganese).
The MCLs provided in Table 7.4 are federal and specific
to the USEPA. This means they are likely to be applicable
on environmental remediation projects governed by the
Comprehensive Environmental Response, Compensation,
and Liability Act where the USEPA is the lead regulatory
agency. State environmental regulatory agencies also have
state specific thresholds for metals, some of which are more
stringent than USEPA. For example, barium (1,000  µg/L),
total chromium (50 µg/L), and hexavalent chromium
(10  µg/L) are metals that have lower California primary
MCLs than USEPA. It is the responsibility of the remedia-
tion practitioner to identify the appropriate threshold driv-
ing the environmental concern prior to initiating engineered
remedies.
Availability of chemical equilibrium data: Stability
diagrams are built from chemical equilibrium data,
and published data may not adequately describe the
reactions that will occur in a treatment zone.
2.
Equilibria are thermodynamic properties: Chemical
equilibria, and the determination of the “most stable”
compound, are based on thermodynamic properties
of the compounds under study. The rate at which
reactions occur is also critical—it is possible to
identify “the most stable” compounds from stability
diagrams that are formed only over long time scales
at aquifer temperatures. The compounds that form
in reactive zones are determined by kinetic as well
as thermodynamic properties of potential reactions.
Kinetic rate constants often control the outcome of
reactive zone endeavors (Chapter 6).
3.
Reactive zones violate chemical activity assump-
tions: The chemical activity of charged elements
and compounds in solution (ions) is controlled by the
solution’s ionic strength, a measure of the effect of
charged species on solution chemistry (Section 3.2.6).
* For in situ chemical reactive zones, the conventional assumption of a dilute
aqueous-phase solution is often violated. Consequently, ionic strength may
also be considered as a critical variable in characterization of aqueous-
phase chemical environment. Ionic strength influences both homogeneous
and heterogeneous reactions.
In Situ Treatment of Metals 329

20 through 7.7). These experimentally determined constants can

vary by several orders of magnitude (Figure 7.2). Some of the
15 reasons for discrepancies associated with these solubility pre-
dictions were as provided by Stumm and Morgan15:
10
Zn2+ 1. The formation of a metal precipitate and its equilib-
5
rium with groundwater is a complicated process and
pE

Zincite (ZnO) is different than the equilibrium of dissolved ions

Zn(OH)42–
0
and complexes.
–5 2. The reactivity of a metal precipitate varies for dif-
ferent modifications of the same compound or for
–10
different forms of the same compound (i.e., chro-
–15 mium hydroxide as Cr(OH)3 versus chromium iron
0 2 4 6 8 10 12 14 hydroxide as Cr0.75Fe0.25(OH)3 versus chromium–
(a) pH iron hydroxide as Cr0.25Fe0.75(OH)3).
3. Variable species in a natural aquifer influencing the
20 solubility equilibrium of a metal precipitate have
been overlooked in defining solubility products (Ksp).
15
When selecting equilibrium constants as part of geochemical
10
Zn2+ modeling, it is important to establish a reliable and defensible
5 rationale for the selection. Matching the ambient geochemi-
pE

Zincite cal conditions to the specifications of a literature study is a

Zn(OH)42–

0 good way to do this. Building safety factors into the model

Sphalerite to account for one to two orders of magnitude difference in
–5 equilibrium constants of more generically tabulated values is
–10
another.

–15
0 2 4 6 8 10 12 14
(b) pH
FIGURE 7.1  (a) pE–pH diagram for zinc–water system. (b) pE–pH
diagram for zinc–water–sulfur system. This figure shows the influ-
ence of a reactive sulfide (S2−) over a broad range of pH level. Note
in (a) that zinc (Zn2+) and zincite (ZnO) are the primary forms of
zinc, with zinc (Zn2+) being soluble over a broad range of pH level
and mildly oxidizing conditions. In (b), sphalerite (ZnS) is the stable
species under mildly oxidizing conditions over nearly the entire pH
range, suggesting that insoluble sphalerite (ZnS) will form in the
presence of zinc (Zn2+), zincite (ZnO), and sufficient reactive sulfide
(S2−). This pE–pH stability diagram was calculated assuming a tem-
perature of 25°C and a zinc concentration of 7.7 × 10 −4 M. This fig-
ure was made using PH Redox Equilibrium EQuation in C language
with the wateq database.
7.3 GEOCHEMICAL STRATEGIES FOR
IN SITU TREATMENT OF METALS
The objective of in situ metals treatment is to create insoluble
compounds directly from the reaction of injected reagents with
target metals or indirectly through modification of the aquifer
geochemistry, reducing the solubility of the target metal in the
aquifer. The geochemical strategies that can be used to reduce
the concentrations of metals dissolved in groundwater are
transformation and immobilization. These mechanisms can
be induced by both abiotic and biotic pathways. Abiotic path-
ways include oxidation, reduction, precipitation, hydration,
and sorption. Biotic pathways include oxidation, reduction,
precipitation, biosorption, bioaccumulation, organometal for-
mation, and phytoremediation. This section presents various
strategies for achieving in situ metals treatment.

Many chemical reactive zones are operated at high

ionic strength, and chemical properties of poten-
tial reactants should be corrected for ionic strength
effects, when necessary.
7.2.7 A Need for Consistency in
Equilibrium Constants
The solubility products that are used in hand calculations
or modeled predictions of metal speciation (such as pE–pH
stability diagrams) are available in the literature (Tables 7.5
7.3.1 Direct Precipitation
Direct precipitation of a metal can involve reducing the metal
to its elemental form (e.g., selenium [Se0]), but most often
involves inducing its combination with a complimentary ion
to form a precipitate (e.g., ferric iron [Fe3+]). As an example,
the equations describing the reaction of a trivalent chromium
(Cr3+) ion with a hydroxide (OH−) ion and the corresponding
equilibrium expression are as follows:
Cr(aq )3+ + 3OH (-aq ) « Cr(OH)3(s) (7.1)
330 Remediation Engineering

TABLE 7.5
Solubility Product Data for Common Soil Minerals
Chemical Compound Name Mineral Name Chemical Formula Solubility Product, Ksp Temp. (°C) Data Source
Aluminum hydroxide Al(OH)3 3 × 10 −34 25 UNC14
Barium carbonate Witherite BaCO3 7 × 10−9 16
Barium sulfate Barite BaSO4 8.7 × 10−11 18
Cadmium hydroxide Cd(OH)2 7.2 × 10−15 25 UNC14
Cadmium sulfide Greenockite CdS 3.6 × 10−29 18
Calcium carbonate Calcite CaCO3 9.9 × 10−9 15
Calcium hydroxide Ca(OH)2 5.02 × 10−6 25 UNC14
Calcium sulfate Anhydrite CaSO4 1.95 × 10−4 10
Chromium fluoride Cr(F)3 6.6 × 10−11 25 Internet
Chromium hydroxide Cr(OH)3 6.3 × 10−31 25 Internet
Cobalt hydroxide Co(OH)2 5.92 × 10−15 25 UNC14
α-Cobalt sulfide CoS 5 × 10−22 25 UNC14
β-Cobalt sulfide CoS 3 × 10−26 25 UNC14
Copper hydroxide Cu(OH)2 4.8 × 10−20 25 UNC14
Copper(II) sulfide Covellite CuS 8.5 × 10−45 18
Copper(I) sulfide Chalcotite Cu2S 2 × 10−47 16–18
Ferric oxyhydroxide Goethite FeOOH 3.16 × 10−42 Internet
Iron(III) hydroxide Fe(OH)3 1.1 × 10−36 18
Iron(II) hydroxide Fe(OH)2 1.64 × 10−14 18
Iron(II) sulfide Troilite FeS 1 × 10−19 18
Iron(II) disulfide Pyrite FeS2
Lead(II) carbonate Cerussite PbCO3 3.3 × 10−14 18
Lead hydroxide Pb(OH)2 1.43 × 10−20 25 UNC14
Lead(II) sulfate Anglesite PbSO4 1.06 × 10−8 18
Lead(II) sulfide Galena PbS 3.4 × 10−28 18
Magnesium carbonate Magnesite MgCO3 2.6 × 10−5 12
Magnesium hydroxide Brucite Mg(OH)2 1.2 × 10−11 18
Manganese hydroxide Pyrochroite Mn(OH)2 4 × 10−14 18
Manganese sulfide Alabandite MnS 1.4 × 10−15 18
Mercury hydroxide HgO 3.6 × 10−26 25 UNC14
Mercury sulfide (black) HgS 2 × 10−53 25 UNC14
Mercury sulfide (red) HgS 2 × 10−54 25 UNC14
Nickel carbonate NiCO3 6.6 × 10−9 25 Kotz et al.12
Nickel hydroxide Ni(OH)2 2.8 × 10−16 25 Kotz et al.12
α-Nickel sulfide α-NiS 3 × 10−21 25 Kotz et al.12
β-Nickel sulfide β-NiS 1 × 10−26 25 Kotz et al.12
γ-Nickel sulfide γ-NiS 2 × 10−28 25 Kotz et al.12
Nickel sulfide Millerite NiS 1.4 × 10−24 18
Zinc hydroxide Zn(OH)2 1.8 × 10−14 18–20
Zinc sulfide Sphalerite ZnS 1.2 × 10−23 18

Sources: Weast, R.C. et al., Handbook of Chemistry and Physics, 65th edn., F-146, CRC Press, Boca Raton, FL, 1984; Kotz, J.C. et al., Chemistry
and Chemical Reactivity, 5th edn., Thomson-Brooks/Cole, 2003; North Carolina State University website: http://www4.ncsu.
edu/~franzen/public_html/CH201/data/Solubility_Product_Constants.pdf. Solubility Product Constants, accessed December 2015.
Note: Data source is Weast et al.5 unless otherwise noted.

K sp = [Cr 3+ ][OH - ]3 (7.2)
The equilibrium expression describes the degree to which the
constituent ions comprising the precipitate will dissolve in
water. This concept was introduced in Chapter 3 and is dis-
cussed in more detail in Section 7.4.1.1. Providing an excess of
the complimentary ion will drive down concentrations of the
targeted metal by precipitating it in the solid phase to maintain
this equilibrium. The resulting precipitates can form on the
surfaces of existing soil particles or in the pore water, where
they are subsequently immobilized through sorption, sedi-
mentation (gravity settling), or straining (filtering) through
soil pores. Hydroxides (–OH), carbonates (–CO3), phosphates
(–PO4), and sulfides (–S) represent the typical solids targeted
In Situ Treatment of Metals 331

conventional industrial wastewater systems. Alkaline solu-

TABLE 7.6 tions of lime (Ca(OH)2) or potash (KOH) are used as reagents
Solubility Products of Some Metal Sulfides16,17 and the for hydroxide (OH−) precipitation. Sodium sulfide (Na2S) and
Difference between the Metal Sulfide and Metal calcium or sodium polysulfide (CaSx, Na2Sx) are normally
Hydroxide used as the reagent to form extremely insoluble metallic sul-
fide precipitates. Injection of these chemical reagents into an
Metal Ksp of MeS Difference Factor
aquifer contaminated with dissolved metals (and potentially
Cadmium 3.6 × 10−29 3 × 108 acidity) creates a reactive zone that results in the precipita-
Chromium None — tion of targeted metals. Metal sulfides (MeS) are insoluble
Iron 1.1 × 10−19 5 × 103 over a broader range of natural geochemical conditions and
Copper 8.5 × 10−45 1 × 1011 are typically favored over metal hydroxides (MeOH; Section
Lead 3.4 × 10−28 3 × 108 7.4.1.3). Metallic cations (Mex+) precipitated out as metal
Mercury 2.0 × 10−49 6 × 1017
hydroxides (MeOH) could be resolubilized slightly as a result
Nickel 1.4 × 10−24 1 × 107
of any significant shift in groundwater pH. Obtaining the
Zinc 1.2 × 10−23 3 × 108
requisite permits to inject sulfide-rich, pH-altering chemical
Silver 1.0 × 10−51 5 × 1012
reagents in an aquifer requires regulatory approval, typically
Me(OH)2 solubility (mg/L) associated with a clear performance monitoring plan with
Note: Difference factor = .
MeS solubility (mg/L) sufficient sentinel wells to demonstrate the local extent of the
reactive zone.
Chemical precipitation strategies simply engineer an
aquifer chemical environment to facilitate the conversion of
soluble compounds to insoluble compounds. Development of
TABLE 7.7
a chemical precipitation strategy entails two main elements:
Comparison of Metal Oxides and Metal Sulfides (1) characterization of the chemical environment that will per-
Metal Oxide Solubility (mg/L) Metal Sulfide Solubility (mg/L) sist after the physical and chemical influence of the injected
Cr2O3 1 × 10 −4 CrS Dissolves reagent has dissipated, and (2) selection of a precipitation reac-
MnO2 3 × 101 MnS 6 × 100 tion that will maintain acceptable aqueous-phase contaminant
FeOOH 2 × 10−7 FeS 6 × 10−2 concentrations in the persistent chemical environment. It is
Co3O4 3 × 100 CoS 5 × 10−3 important to note that the chemical environment that devel-
NiO 5 × 103 NiS 2 × 10−5 ops during reagent injection (e.g., pH, ionic strength, EH) is
CuO 1 × 10−1 CuS 3 × 10−14 different from ambient conditions. In situ chemical strategies
ZnO 1 × 10−3 ZnS 8 × 10−9 for metals discussed here include adjustment of the pH and
CdO Dissolves CdS 4 × 10−13 oxidation–reduction potential and iron- and sulfide- mediated
PbO Dissolves PbS 1 × 10−13 precipitation.
SnO2 3 × 10−3 SnS2 3 × 10−5
Sb2O5 1 × 10−17 Sb2S3 5 × 10−3 7.3.1.1.1  pH Adjustment
Ag 1 × 100 Ag2S 2 × 10−14 Of the governing parameters dictating the speciation and
Au 1 × 10−15 Au 2 × 10−27 solubility of metals, pH is the most important. In  situ met-
Hg 4 × 10−5 HgS 6 × 10−36 als contamination is typically associated with some degree of
Source: Rickard, D. and Luther, G.W., Rev. Mineral. Geochem., 61, 421, pH extreme (either acidic or alkaline). Because many of the
2006. regulated metals are naturally occurring in the geochemical
Note: Solubility provided on a dissolved metal basis (e.g., Cr2O3 has a composition of soil (Table 7.1), a release of acid or alkaline
resultant chromium solubility of 1 × 10−4 mg/L). Bold values are the reagent devoid of metals will still likely result in exceedances
most soluble solid. The solubilities are calculated for pure water at of pH sensitive metals through dissolution of the site soils.
25°C, 1.013 bars total pressure, pH = 7, EH = 0.5 V (oxide), Eh = The buffering capacity of the soils can neutralize pH varia-
−0.2 V, total S2− = 32 mg/L. Where at least 1 g of solid dissolves in tions to some degree, but more than likely acidic or alkaline
1,000 g of water, solubility is defined as dissolves. release to the aquifer will be most rapidly addressed with a
chemical adjustment of the pH.
pH adjustment presents an effective in  situ metals treat-
in direct precipitation strategies (Table 7.1). Sulfates can also ment strategy for acidic/alkaline releases that are relatively
be important, as in the case of barium. Barium (Ba2+) can small and well understood. The cost of the reagents and the
combine with sulfate (SO42−) to form the insoluble precipitate health and safety procedures required to handle pH adjust-
barite (BaSO4). ment reagents (strong acids and bases) can become exces-
sive for larger source areas. Careful attention must be paid
7.3.1.1  Chemical Methods to the ambient pH and the targeted metals to be precipitated.
Chemical precipitation of metals using hydroxide (OH−) A pH adjustment strategy that requires sustaining a pH that is
and sulfide (S2−) precipitation has been used successfully in greater than ambient conditions is not practical.
332
1.0
0.9
0.8 NiS
0.7
Ni2+ solubility (mg/L)
0.6
0.5 1 2
0.4
0.3
0.2
0.1
0.0
5.0
FIGURE 7.2  Predicted dissolved-phase nickel concentrations in equilibrium with each of two compounds: nickel sulfide (NiS) and nickel
carbonate (NiCO3). Solubility of nickel carbonate was calculated at three alkalinities: 50 mg/L (A), 100 mg/L (B), and 300 mg/L (C), rep-
resenting low, midrange, and higher aquifer alkalinity values, respectively. Solubility of nickel sulfide (NiS) was calculated using Ksp values
from Kotz and Treichel12 for 25°C (1) and from Weast5 for 18°C (2).
pH adjustment can also be a component of other forms
of in situ chemical treatment for metals. For example, a dis-
cussion of sulfide acidity scavenging is presented in Section
7.3.1.1.3.1.
7.3.1.1.2 Reduction
Chemical-reducing reagents, such as polysulfide (Sx2−), dithi-
onite (S2O42−), and zero-valent iron (ZVI; Fe0), can be intro-
duced into the source zone to precipitate redox-sensitive
metals such as hexavalent chromium (Cr6+), molybdenum
(Mo), selenium (Se), and vanadium (Vd). A summary of some
available chemical-reducing reagents with their chemical for-
mula and relatively recent pricing is presented in Table 7.8.
Chemical reduction can be accomplished by directly transfer-
ring electrons to oxidized compounds of the targeted metal
(hence reducing the oxidation state of the targeted metal) or
by indirectly reducing the natural geochemistry, which then
interacts with the targeted metal. An example of direct reduc-
tion is the reduction of selenate (SeO42−) by ferrous iron (Fe2+)
summarized in the following equation:
SeO 4 2 - + 6Fe 2 + + 8H + ® Se 0 + 6Fe3+ + 4H 2O (7.3)
The selenium (Se) in the selenate (SeO42−) oxyanion is reduced
to elemental selenium (Se0), which has a considerably lower
solubility in groundwater than selenium in selenate (SeO42−)
in the plus six oxidation state. The ferrous iron (Fe2+) donates
the electrons and is subsequently oxidized to ferric iron (Fe3+).
This mechanism has been documented in the literature using
green rust carbonate (Fe42+Fe23+(OH)12CO3 * yH2O), ­magnetite
(Fe3O4), and mackinawite (Fe(1+x)S [x = 0–0.11]; Fe1.8 to 2+) as
sources of ferrous iron (Fe2+).20–24
Remediation Engineering
NiS NiCO3
C B
A
Generally accepted
regulatory standard
for nickel (Ni2+) in
groundwater
5.5 6.0 6.5 7.0 7.5 8.0 8.5 9.0
pH
7.3.1.1.3  Sulfide Precipitation
It should seem reasonable that an injection of an organic
substrate into an aquifer with naturally occurring sulfate
(SO42−) dissolved in groundwater will ultimately create sul-
fides (S2−) that are reactive with dissolved metals. This is one
way of achieving reactive sulfide in situ. Other ways to uti-
lize sulfur for metal precipitation is by using a sulfur-based
chemical reductant to condition an aquifer (i.e., dithionite;
S2O42−) or injecting a chemical reagent that is rich in sul-
fide (polysulfide; Sx2−). Some of the concepts behind these
reactive forms of sulfur are discussed in this section. It is
important to remember that while our attention for in  situ
metal precipitation may focus on sulfate (SO42−) and sulfide
(S2−), there are numerous metastable species of aqueous sul-
fur compounds that can form when a chemical reagent rich
in sulfur is used for remediation purposes.25 In this applica-
tion, the term metastable is defined as not stable, but chang-
ing so slowly over a long enough time frame that it can be
considered stable. A collection of the known sulfur species
with significant lifetimes in aqueous solutions is presented
in Figure 7.3 and demonstrates the major groups of aque-
ous sulfur compounds available: polysulfides (Sx2−), sulfane
monosulfonic acids (polythiosulfates; SxO32−), sulfane disul-
fonic acids (polythionates; SxO62−), sulfite (SO3−), and sulfate
(SO42−).25
Whether sulfide (S2−) availability is the result of abi-
otic or biotic processes, the metal sulfides (MeS) that form
occur through interaction of the metal (Me2+) and sulfide
(S2−) ions:
Me 2 + + S2 - ® MeS ¯ (7.4)
In Situ Treatment of Metals 333

concentrations of hydrogen sulfide (H2S), bisulfide (HS−), and

TABLE 7.8 hydroxides (OH−) with a more alkaline pH. A slight modera-
Available Chemical Reagents for In Situ Metal tion of an acidic aquifer pH will result in the precipitation
Precipitation of pH sensitive metals—such as aluminum (Al3+) and iron
(Fe3+)—and those precipitates will offer sorptive surfaces for
Cost
Reductant Chemical Formula Costa Unit
dissolved metals. Additionally, aluminum and iron hydroxide
precipitates will form a broader matrix of precipitates that can
ZVI Fe0 $1.011 $/ton
encapsulate and protect targeted metal precipitates, making
EHC (ZVI and carbon) Fe0-soybean oilb $1.60 $/lb
them less environmentally available and susceptible to dis-
Ferrous iron Fe2+ $0.65–$0.95c $/lb
solution. This approach is commonly used in ex situ treatment
Calcium polysulfide CaSxd $0.24–$0.87 $/lb
of industrial wastewater.4,27
Sodium polysulfide Na2Sxd $0.92 $/lb
Sodium dithionite Na2S2O4
A series of stability diagrams that depict general solubility
Trisodium salt (TMT-15) C3N3Na3S3 $2.15 $/lb
profiles for various metal sulfides, assuming crystalline min-
Sodium metabisulfite Na2S2O5 $0.49–$0.89 $/lb eral form, and that the mineral is the only source of reactive
Sodium sulfite Na2SO3 $0.49–$0.89 $/lb sulfide are presented in Figure 7.4. Metal sulfide stability can
Phosphites PO33− be enhanced in sulfide-rich environments, but depending on
Sodium hypophosphite NaH2PO2 the magnitude of free sulfide and pH, there is a point at which
Calcium hypophosphite CaH4P2O4 it can also be compromised through the formation of thio-
Formic acid CH2O2 sulfate complexes (S2O32−). At excess sulfide concentrations,
Oxalic acid C2H2O4 solubility of some metals can be increased by the formation
Ascorbic acid C6H8O6 $1.85–$2.35 $/lb of thiosulfate complexes (S2O32−) (Figure 7.3). However, the
Citric acid C6H8O7 $0.85–$1.20 $/lb stability of these complexes is still questionable. These thio-
Phosphorous acid H3PO3 sulfate anions may potentially preferentially form soluble
Sodium borohydride NaBH4 metal–thiosulfate complexes, which increase the solubility of
Indirectly formed H2 — — a targeted metal in groundwater. In addition, fresh precipi-
hydrogen tates are amorphous (finely divided) with high specific surface
a Costs based on estimates obtained in 2015. Many products are driven by
area that makes them more reactive and more soluble. Given
industrial markets and are subjective change. enough time, however, in an environment conducive to sulfide
b Soybean oil typically combinations of large chained fatty acids (i.e., pal- mineral precipitation, these amorphous forms mature into
mitic acid [C16H32O2], stearic acid [C18H36O2], oleic acid [C18H34O2], lin- more stable, crystalline forms. Note the 3 × 105 and 1.5 × 107
oleic acid [C18H32O2], and linolenic acid [C18H30O2]).19 times decrease in solubility products (Ksp) for β-, and γ-nickel
c Cost based on an iron basis and based on ferrous sulfate. sulfides (β-NiS and γ-NiS), respectively, compared to α-nickel
d Typical forms of polysulfide in sodium and calcium polysulfide likely to sulfide (α-NiS) presented in Table 7.5. Given this complexity,
be pentasulfide (S52−). equilibrium-based geochemical modeling software such as
PHREEQC (PH Redox Equilibrium EQuation in C language),
MINEQLT, MINTEQ, and Geochemists Workbench can be
It is the source of the sulfide (S2−) that determines whether a critical tools in evaluating and predicting the formation of
biological agent is implicated in metal sulfide (MeS) forma- precipitates and precipitate solubility for in situ remedies. It
tion. If the sulfide (S2−) results from bacteria reducing sulfate can be seen from Figure 7.4 that it is theoretically not fea-
(SO42−), it is of biotic origin. If sulfide (S2−) is provided via sible to reach the cleanup standards for Ni (100 μg/L) around
an injection of a chemical rich in sulfide (S2−), it is of abiotic neutral pH values due to the solubility of the dominant solid
origin. Metal sulfides (MeS) form readily at natural tempera- phases. However, achieving the Ni standards is possible once
tures and pressures and are comparatively less soluble than the precipitates have matured into stable crystalline forms and
other metal precipitates, such as metal oxides (MeO), metal under moderate groundwater velocity conditions resulting in
hydroxides (MeOH), and metal carbonates (MeCO3). A list nonequilibrium conditions.
of solubility products (Ksp) and some comparisons of common The sulfide ions (S2−) necessary to mediate metal sulfide
metal sulfides (MeS),16,26 metal oxides (MeO), metal carbon- precipitation can be directly injected into a reactive zone in
ates (MeCO3), and metal hydroxides (MeOH) are provided the form of dithionite (S2O42−), polysulfides (Sn2−), or bisul-
in Tables 7.5 through 7.7. Note in Table 7.718 that for all but fite (HSO3−). However, the sulfide ion (S2−) is one of the most
chromium (Cr), the solubilities of metal sulfides (MeS) are reduced ions, and its stability within the aquifer is short lived.
lower than metal oxides for metals that are typically contami- It will be oxidized to elemental sulfur (S(s)) and potentially
nants of concern (i.e., Cd, Co, Cu, Hg, Ni, Pb, and Zn). The sulfate (SO42−) quickly in the presence of oxidizing conditions
metal sulfide (MeS) solubilities presented in Table 7.7 are within the contaminated plume.
simple pure water systems and do not consider complexities The distribution of sulfide (S2−) between various phases
with competing ligands or pH neutralization. Under acidic is similar to that of the carbon dioxide (CO2)/bicarbonate
pH conditions, reactive sulfides (S2−) will scavenge hydro- (HCO3−)/carbonate (CO32−) interactions. At neutral pH, the dis-
gen (H+) during hydration, resulting in greater dissolved tribution between hydrogen sulfide (H2S) and bisulfide (HS−)
334 Remediation Engineering

Charge on Charge on
oxygen Charge on compound sulfur
Number of sulfur atoms S2– — — –2
1 2 3 4 5 6 7 SO32– –6 –2 4
–2 S2– SO42– –8 –2 6
–1 S22– S22– — — –1
–0.67 S32– S2O32– –6 –2 2
–0.5 S42– S2O42– –8 –2 3
–0.4 S52– S2O52– –10 –2 4
–0.33 S62– S2O62– –12 –2 5
–0.29 S72– S2O7 2– –14 –2 6
0 S2O8 2– –16 –2 7
Average formal charge on sulfur

0.57 S7O32– S32– — — –0.67

0.67 S6O32– S3O32– –6 –2 1.33
S5O3 2–
0.8 S3O62– –12 –2 3.33
1 S4O32– S42– — — –0.5
1.33 S3O32– S4O32– –6 –2 1
1.43 S7O62– S4O62– –12 –2 2.5
1.67 S6O62– S52– — — –0.4
S2O3 2– 2–
2 S5O6 S5O3 2– –6 –2 0.8
2.5 S4O62– S5O6 2– –12 –2 2
3 S2O42– S62– — — –0.33
3.33 S3O62– S6O32– –6 –2 0.67
2– S2O5 2–
4 SO3 S6O62– –12 –2 1.67
5 S2O62– S72– — — –0.29
6 SO42– S2O72– S7O32– –6 –2 0.57
7 S2O82– S7O62– –12 –2 1.43

FIGURE 7.3  Sulfur speciation diagram. (From Williamson, M.A. and Rimstidt, J.D., Geochim. Cosmochim., 56, 3867, 1992.)

5.0

4.5

4.0

3.5 CdS PbS ZnS NiS

Concentration (mg/L)

3.0

2.5

2.0

1.5

1.0

0.5
100 μg/L standard
0.0
2 3 4 5 6 7 8 9 10
pH

FIGURE 7.4  Metal solubility in equilibrium with associated crystalline sulfide phases.
In Situ Treatment of Metals 335

will be equivalent. Hydrogen sulfide (H2S) is a gas of inter- 0

mediate solubility (approximately 0.4% at 20°C), and may be –1 pKA1 = 7.04 System
  point [HS–]
stripped from solution. Higher H2S production per unit vol- [H2S]
–2
ume of the anaerobic IRZ system and a lower pH favor strip-
–3
ping of H2S from the groundwater system. Hydrogen sulfide
(H2S) is more water soluble at higher pH where it is predomi- –4

log[C]
nantly dissociated as hydrogen (H+) and sulfide (S2−) ions. As –5
[H+] [OH–]
the pH is decreased below 7.0, undissociated hydrogen sulfide –6
(H2S) gas begins to predominate and is released. Since vapor
–7
density of hydrogen sulfide (H2S) is greater than 1, hydrogen
sulfide (H2S) gas tends to settle in low places and can poten- –8
[S2–]
tially create a toxicity hazard.28 –9
–10
7.3.1.1.3.1  Acidity Consumption of Sulfide  Both dithi- 2 4 6 8 10 12
pH
onite (S2O42−) and polysulfide (Sx2−) demonstrate strong
protonation under low pH and therefore have some acidity
neutralization capacity (ANC). This is beneficial as many FIGURE 7.5  Logarithmic conversion of concentrations versus pH
groundwater contaminant plumes of dissolved metals are for the sulfur system. The graph is created for the total concentration
of 10 −2 M as sulfur.
associated with acidic pH. From a design perspective, bench-
scale treatability testing is recommended. Bench-scale treat-
ability testing can determine an appropriate chemical reagent 20
dose that accounts for the ANC of sulfide (S2−), provides
enough sulfide (S2−) to accommodate aqueous speciation 15
of sulfur species, and satisfies the dissolved metals sulfide HSO4–
10
demand, but not overdose the aquifer and cause health and
safety concerns (such as fugitive emissions of hydrogen sul- SO42–
5 S(s)
fide [H2S(g)]). Bench-scale treatability testing (an example of
pE

which will be discussed specific to polysulfides [Sx2−]) can be 0

H2S
a relatively low-cost endeavor that may facilitate regulatory
acceptance and gain valuable design insight. –5
HS–
A simple conceptualization of the sulfide (S2−) system can
–10
be described by the following two chemical equations:
–15
HS- + H + « H 2S (7.5) 0 2 4 6 8 10 12 14
pH

S2- + H + « HS- (7.6)

One mole of sulfide (S2−) will scavenge two moles of acidity
(H+). The first and second acid dissociation constants (Ka) for
this simple conceptualization of the sulfide system are pKA1 =
7.04 and pKA2 ~ 18, respectively,3,15,18,29,30 indicating that under
most aquifer pH conditions that are acidic to circumneutral,
sulfide (S2−) is anticipated to scavenge protons (i.e., acidity;
H+). This relationship highlights the sensitivity of metal sul-
fides (MeS) to the presence of acidity and to environments
low in reactive sulfide (S2−).
The equilibrium speciation of the sulfur–hydrogen–
oxygen system is presented in Figures 7.5 and 7.6. The graph
of the logarithm of the concentration versus pH (log C–pH)
(Figure 7.5) represents a mass balance for a given pH, where
pH in this example is provided from 2.0 to 12.0. In Figure 7.5,
the total concentration (CT) of sulfide is 1 × 10 −2 molar (M),
represented by a solid black line at log (1 × 10 −2) = −2. Note,
because the oxidation–reduction potential is held constant
for this graph, sulfur (S) may be referred to freely as sulfide
(S2−) at any pH. The speciation of hydrogen [H+] and hydrox-
ide [OH−] is also provided as two straight lines intersecting at
FIGURE 7.6  pE–pH stability diagram for the sulfur system for a
total concentration of 10 −2 M as sulfur.
pH = 7.0, governed by the water equilibrium constant K W =
1 × 10 −14 (log K W = −14). The only acid dissociation constant
(Ka) of meaning under ambient geochemical conditions for the
sulfur–hydrogen–oxygen system (pKA1 = 7.04) is presented
in Figure 7.5, and represents the system point at which the
concentration of hydrogen sulfide (H2S) is equivalent to the
concentration of bisulfide (HS−). Note that the only observa-
tion of sulfide (S2−) is at low concentration and highly alkaline
pH (pH > 10, log C < −8). The speciation shown in Figure 7.5
demonstrates the acidity scavenging potential of sulfide (S2−).
If a high concentration of sulfide (S2−) was injected into an
acidic aquifer, the predominant form of sulfide (S2−) would
be hydrogen sulfide (H2S), and the pH would be increased.
The injected sulfide (S2−) would deprotonate the water, remov-
ing hydrogen [H+] from the water by forming hydrogen sul-
fide (H2S). This would move the equilibrium condition in
Figure 7.5 from the left to the right, resulting in a decrease
of the hydrogen [H+] concentration (e.g., increasing the pH),
336
an increase of the hydroxide [OH−] concentration, and a neg-
ligible decrease and increase of the hydrogen sulfide (H2S)
and bisulfide (HS−) concentrations, respectively. Remember,
for the mass balance of Figure 7.5 to be maintained (e.g., CT =
[H2S] + [HS−] + [S2−]) at log CT = −2, the increase observed
in bisulfide (HS−) as the acidic pH is neutralized must result
in a decrease of hydrogen sulfide (H2S) even though a flat
line is presented in Figure 7.5 (e.g., the decrease is negligible
on a logarithmic scale). If we consider both the oxidation–
reduction potential and pH (Figure 7.6), we see a similar spe-
ciation under acidic and reducing conditions. The significance
of Figure 7.6 is that under ambient geochemical conditions
(mildly oxidizing and circumneutral), oxygen and acidity
scavenging can influence the effectiveness of chemically
induced sulfide (S2−) precipitation.
7.3.1.1.3.2  Dithionite Metal Precipitation  The use of
dithionite (S2O42−) as a chemical reductant was introduced in
Chapter 6. Here, a well-researched field demonstration for the
purposes of in situ metal precipitation is discussed.
In situ dithionite-driven chromium reduction/precipitation
strategies have been described by Chilakapati et  al.,31 Istok
et  al.,32 Fruchter et  al.,33 and Khan and Puls.34 Dithionite is
injected into aquifers to reduce solid-phase ferric iron (Fe3+)
in soil to solid-phase ferrous iron (Fe2+) or to generate other
reduced metallic compounds that can serve in dechlorina-
tion reactions. The reduction of soil minerals generates an
in  situ chemical-reducing zone that supports heterogeneous
reduction of redox-sensitive metals, such as chromium (Cr),
uranium (U), and technetium (Te) and reducible hydropho-
bic organics such as chlorinated ethenes and ethanes. With
respect to in  situ dithionite-driven chromium reduction/pre-
cipitation, the reduced iron species (Fe2+) was engineered to
react with soluble hexavalent chromium (Cr6+) in groundwater
to create trivalent chromium (Cr3+), which readily precipitates
out of solution as chromium hydroxide (with or without iron
substitution) potentially following one of the following pro-
posed reactions34,35:
2- 2+ -
CrO 4 + 3Fe + 4(OH ) + 4H 2O ® Cr(OH)3 + 3Fe(OH)3
(7.7)
CrO 4 2 - + 3Fe 2 + + 4(OH - ) + H 2O ® 4(Cr0.25Fe 0.75 )(OH)3 (7.8)
3CrO 4 2 - + FeS(s) + 9H 2O
® 4[Cr0.75Fe 0.25 ](OH)3 + Fe 2 + + S2O3 + 6OH - (7.9)
3Fe 2 + + HCrO 4 - + 8H 2O ® 4[Cr0.25Fe 0.75 ](OH)3 + 5H + (7.10)
In field trials reported by Fruchter et al.,33 77,000 L (20,500
gal) of a buffered dithionite solution (average 0.066 M) was
injected into a permeable formation that consisted of sandy
gravel overlying sandy silt/clay. The injection fluid was
pumped into the 8 in. diameter injection well at 20 gpm
for 17.1  h. The fluid remained in place for the next 18.5  h.
Remediation Engineering
The  spent dithionite solution was then recovered from the
aquifer by extracting 375,000 L (99,600 gal) of groundwater
and dithionite solution (4.9 times the initial injection volume).
Estimates of the recovery mass balance were not provided in
the cited publication.
The dithionite-induced reduction of solid-phase ferric
iron (Fe3+) was estimated by comparing the oxygen reduc-
tion capacity of post-dithionite-injection soil samples to
the baseline oxygen reduction capacity (measured from
pre-dithionite-injection soil samples). An average of 53%
of solid-phase ferric iron (Fe3+) within a 10 ft radius of
the injection well was converted to solid-phase ferrous iron
(Fe2+) (calculated from data in Fruchter et  al.33). A small
iron reduction effect (8% reduction) was detectable at
27 ft from the injection well. The pattern of iron reduction
achieved was shown by Fruchter et al.33 in cross-sectional
figures, indicating heterogeneity of dithionite distribution
(as would be expected). The significance of this observation
is that the highly reactive dithionite was preferentially dis-
tributed according to the natural heterogeneity and anisot-
ropy of the aquifer, which is typical. Repeat applications
are usually necessary when injecting a chemical reagent
like dithionite because stored metals and acidity contami-
nation in the less mobile fraction of the aquifer are likely
to be uninfluenced with a single injection. Subsequent slow
advection and (to a lesser extent) concentration gradient-
driven diffusion leads to increases in concentrations after
the effects of the injected reagent have dissipated (i.e.,
rebound) (Chapter 4).36
Chilakapati et al.31 described a process for creation of an
in situ reduced iron barrier, using periodic sodium dithionite
injections. The main reaction of the dithionite ion with solid-
phase ferric iron (Fe3+) is as follows:
S2O 4 2 - + 2Fe3(s+) + 2H 2O ® 2SO32 - + 2Fe(22+) + 4H + (7.11)
Chilakapati et al.31 noted that hydrolysis losses of dithionite
and iron reduction rate are maximized at high pH. To take
advantage of those reaction characteristics, they delivered
dithionite in a potassium carbonate/bicarbonate buffer, at four
times the dithionite concentration (pH 11). The tested aqui-
fer was poorly buffered by the soil matrix, and the high pH
condition was likely maintained while the dithionite reagent
remained active.
At elevated pH, the hexavalent chromium (Cr6+) precipita-
tion reactions are expected to be limited to the solid-phase
reaction (Equation 7.9). As ambient pH groundwater fluxes
through the reduced iron barrier, greater solid-phase ferrous
iron (Fe2+) dissolution is likely and aqueous-phase reactions
with hexavalent chromium (Cr6+) are likely to occur.
As the hexavalent chromium (Cr6+) is reduced to triva-
lent chromium (Cr3+), the solid-phase ferrous iron (Fe2+)
loses available surface area to continue to facilitate the
reaction. Reducing capacity of the iron barrier is also lost
to other electron acceptors such as dissolved oxygen and
nitrate (NO3−). Some of the lost reducing capacity can be
recovered (i.e., reversible reactions), but require periodic
In Situ Treatment of Metals
reapplication of the dithionite reductant to reestablish solid-
phase ferrous iron (Fe2+) in the reactive zone. The frequency
at which reapplication is required is determined by the total
electron acceptor flux (which determines the rate of con-
sumption of the solid-phase ferrous iron [Fe2+]). There are
reactions that are not reversible and permanently remove
reactive iron from the reactive zone (i.e., the inclusion of
iron into trivalent chromium [Cr3+] hydroxide precipitates).
Any irreversible mineral formation permanently removes
reducing capacity from the reactive zone. A critical design
objective is to ensure the dimensions of and iron loading to
the reactive zone are sufficient to accommodate irreversible
mineralization until remedial objectives are complete or the
hexavalent chromium (Cr6+) is sufficiently mitigated to pre-
vent harm to receptors.
7.3.1.1.3.3   Polysulfide Metal Precipitation  Implementing
polysulfide (Sx2−) injections for in  situ metal precipitation
can be highly successful, but also requires careful consider-
ation of numerous factors to be effective over long-term time
frames. In acidic metal-rich-contaminated aquifers, acidity
neutralization reactions (e.g., sulfide scavenging) can hap-
pen instantaneously and polysulfide (Sx2−) disproportionation
reactions (e.g., sulfide oxidation and speciation) can happen
on the order of seconds.37 As is predicted by Figure 7.6, dilut-
ing the polysulfide assays to concentrations relevant from an
in  situ metal precipitation perspective (i.e., 0.5%–10% by
weight) results in the precipitation of elemental sulfur due to
the oxidation of sulfide (S2−). For strongly acidic aquifers, it
may be beneficial to co-injection a source of alkalinity (e.g.,
sodium carbonate [Na2CO3], sodium bicarbonate [NaHCO3],
sodium hydroxide [NaOH]) to reduce sulfide (S2−) scaveng-
ing for acidity neutralization and optimize metal sulfide
(MeS) formation.
Practicality must be incorporated into key design
assumptions regarding achievable in  situ sulfide (S2−) dis-
tribution, sustainable injection flow rates, and acidity neu-
tralization. For example, the effectiveness of polysulfide
(Sx2−) for in  situ metal precipitation should be considered
only in the saturated interval influenced during the injec-
tion. This is different from an injection of a soluble carbon
substrate (i.e., molasses or lactate), which follows pseudo-
first-order reaction kinetics and has an approximate half-life
of 40 days (k = 0.02 day−1). Injected carbon is anticipated to
propagate degradable carbon downgradient of the injected
radius of influence (ROI) 10s–100s of feet before being con-
sumed to an insignificant level. Second-order reaction rate
constants available in the literature for metal sulfide (MeS)
formation are too rapid to determine experimentally, but are
estimated to be greater than 8 × 1012 M/day.18 This clearly
demonstrates that chemically induced in situ reactive zones
(IRZs) for metal precipitation using polysulfides (Sx2−) must
achieve contact with impacted groundwater during injection
with little to no reliance on propagation of reactive sulfide
(S2−) downgradient postinjection. The formation of targeted
metal sulfides (MeS) and coprecipitation of ancillary metal
oxides (MeO) and metal hydroxides (MeOH) as a result of
337
acidity neutralization may decrease the permeability of the
aquifer (Chapter 3). This “geochemical fouling” of the aqui-
fer permeability is intentional and beneficial from an in situ
metal precipitation perspective but may ultimately limit the
distribution and reduce the resultant contact efficiency with
impacted groundwater. More densely spaced injection loca-
tions may be necessary.
To demonstrate some of the concepts discussed in this
section, a treatability test case study with both bench-
scale and field-scale components is presented. Historical
releases associated with a former galvanizing operation in
the Southeastern United States lead to an acidic groundwa-
ter plume with dissolved concentrations of metals exceed-
ing applicable regulatory criteria for groundwater (Al, As,
Cd, Cr, Fe, Pb, Ni, and Zn). The site-specific geology is
conceptualized as fine to medium grained sands overly-
ing a low-permeability semiconfining layer. Discontinuous
depressions of variable thickness into the surface of the low-
permeability semiconfining layer are present throughout the
site as a result of natural erosion. The depressions are filled
with fine-grained silts and clays and are of lower perme-
ability than the overlying sand. Over time, acidity and high
concentrations of dissolved metals have collected in these
depressions through density-driven advection. Estimates
of the groundwater velocity using Darcy’s law suggest an
approximate 700 ft per year in the Sand Zone (SZ) and 10 ft
per year in the Transition Zone (TZ). Therefore, the CSM is
characterized as mildly acidic, moderate concentrations of
dissolved metals in groundwater within the overlying SZ,
and strongly acidic, high concentrations of dissolved metals
within the discontinuous depressions (referred to as the TZ).
The depth to groundwater is approximately 5–7 ft below
ground surface (bgs), the depth of the SZ is approximately
15 ft bgs, and the TZ has been observed to range from 0 to
50 ft in thickness.
A bench-scale treatability test using site-specific soil and
groundwater was conducted in March 2006. The objectives of
the bench-scale test were as follows:
• Assess whether the reagents (calcium polysulfide
[CaSx] and sodium hydroxide [NaOH] buffered
with sodium bicarbonate [NaOH/NaHCO3]) could
remove dissolved metals (primarily zinc and nickel)
from groundwater.
• Identify the more effective of the two reagents.
• Estimate the optimal dosage of the selected reagent.
Groundwater samples were collected from monitoring wells
representing background, low, and high metals concentra-
tions, and soil samples were obtained from both the SZ and
TZ. The bench-scale treatability test was conducted in three
separate phases, each using low and high groundwater in both
the SZ and TZ soil. Phase I used titration of groundwater
only to set pH endpoints (6.0, 7.0, 8.0, and 9.0) to estimate
appropriate reagent dosing for Phase II. Phase II tested the
determined reagent concentration on soil and groundwater
mixtures. Finally, Phase III tested the permanence of the
 338 Remediation Engineering

metal precipitation through exposure to background ground-
water under aggressive agitation.
1. Analytical results from Phase I demonstrated
CaSx was effective over a broader pH range than
NaOH/NaHCO3 in removing zinc and nickel from
site groundwater only (data not shown). This was
expected based on a comparison between the solubil-
ity constants of metal sulfides and metal hydroxides
(Table 7.6 and Figure 7.7). Dissolved zinc concen-
trations in the high groundwater trial were reduced
from approximately 140 mg/L to below 0.1 mg/L
as a result of CaSx treatment over all pH endpoints.
Sodium hydroxide/sodium bicarbonate was effective
at reducing zinc, but only at pH greater than 8.0.
2. In spite of the increased metal loading and acid-
ity associated with the addition of soil in Phase II,
CaSx removed 99% of zinc and 88%–97% of nickel
(Figure 7.8). Sodium hydroxide/sodium bicarbon-
ate did not achieve the treatment goals in all cases,
seemingly because the buffering capacity of the
NaOH/NaHCO3 was insufficient to account for the
increased acidity of the soil. The Phase II testing was
duplicated with more aggressive mixing to realize
the full acidity and metal loading of the soil, but CaSx
was consistently effective (data not shown). Because
CaSx out performed NaOH/NaHCO3, NaOH/
NaHCO3 was not carried through to Phase III.
3. Phase III of the bench-scale treatability test was to
test the permanence of the precipitated metal sul-
fides (MeS). Following the more aggressive mixing
trials of Phase II, treated soil was suspended in back-
ground groundwater and shaken for approximately
24 h. Measurements and analyses performed on the
supernatant indicated minor dissolution of zinc and
nickel (Figure 7.8), both below the treatment goals.
This is in good agreement with the literature solubil-
ity constants presented in Tables 7.5 through 7.7.
The results of the bench-scale treatability test confirmed
that sulfide precipitation was likely to be more effective at
this site. The optimal pH for sulfide precipitation with CaSx
was determined via titration to be approximately 7.0; how-
ever, according to the predictive speciation of nickel sulfide
(NiS; Figure 7.4) and the 100 μg/L treatment goal at this site, a
more alkaline pH was targeted for the in situ field-scale treat-
ability test. The in situ dosing strength was determined to be
0.4% by weight for the SZ and 0.8% by weight for the TZ.
Lastly, the permanence of metal sulfide precipitates appeared
to be recalcitrant to dissolution when subjected to background
groundwater.
The in  situ field treatability test was implemented in
November 2006 with monitoring conducted through June
2007. The field-scale treatability test was implemented using
direct-push technology (DPT) injection within a grid pat-
tern. This type of injection is amenable to polysulfide (Sx2−)

10,000

NiCO3 solubility
1,000

100 20
Concentration (mg/L)

15
Ni(OH)2 solubility
10 10 Ni2+

5 NiCO30
pE

1 Ni(OH)2
0

NiS solubility –5 Millerite

0.1
MCL = 100 mg/L
–10

0.01 –15
6 7 8 9 10 11 12 13 14 0 2 4 6 8 10 12 14
(a) pH (b) pH

FIGURE 7.7  (a) Comparisons of nickel solubility in equilibrium with common solubility controlling solid phases. Solubility calcula-
tions were performed using MINEQL+. (From Schecher, W.D. and McAvoy, D.C., MINEQL+, 4.5 ed., Environmental Research Software,
Hallowell, ME, 1998.) (b) pE–pH stability diagram for the nickel–sulfur–carbonate–water system. As expected, millerite (NiS) would form
under reducing conditions, likely precipitating nickel out of groundwater. Sequentially nickel (Ni2+), nickel carbonate (NiCO30), and nickel
hydroxide (Ni(OH)2) speciate according to pH. This pE–pH stability diagram was calculated assuming a temperature of 25°C and the fol-
lowing nickel, sulfur (as sulfate [SO42−]), and carbon (as bicarbonate [HCO3−]) concentrations, respectively: 1.7 × 10 −4 M, 1.0 × 10 −2 M, and
4.9 × 10 −3 M. This figure was made using PH Redox Equilibrium Equation in C language with the wateq database.
In Situ Treatment of Metals 339

Untreated NaOH CaSx Zn goal Untreated NaOH CaSx Ni goal

1000 1000

100

Nickel (μg/L)
100
Zinc (mg/L)

10

10
1

0.1 1
SZ/low SZ/high TZ/low TZ/high SZ/low SZ/high TZ/low TZ/high
(a) Soil type/groundwater type (b) Soil type/groundwater type

Untreated CaSx Back Zn goal Untreated CaSx Back Ni goal

1000 1000

100

Nickel (μg/L)
100
Zinc (mg/L)

10

1
10
0.1

0.01 1
SZ/low SZ/high TZ/low TZ/high SZ/low SZ/high TZ/low TZ/high
(d) Soil type/groundwater type
(c) Soil type/groundwater type

FIGURE 7.8  Calcium polysulfide (CaSx) treatability test data. (a) and (b) represent zinc and nickel treatment in sand zone and transition
zone under high and low contaminant loading with treatment by sodium hydroxide/sodium bicarbonate (NaOH/NaHCO3, abbreviated as
NaOH) and calcium polysulfide (abbreviated as CaSx). (c) and (d) represent posttreatment stability in ambient groundwater, abbreviated
as Back.

treatment because the spacing of the grid can be adjusted in
the field based on sulfide distribution and injection capacity
observations. There can be issues with the DPT rig compact-
ing the annulus of the borehole, and it is important to consider
the hydrostratigraphy before selecting the injection technol-
ogy. The dosing concentrations of CaSx in the SZ and TZ were
4% and 8%, respectively. The dosing concentrations were
increased an order of magnitude from those determined dur-
ing the bench-scale treatability testing to account for aquifer
dilution and an anticipated greater sulfide (S2−) scavenging at
the field scale. Approximately 9,600 and 3,150 gal of CaSx
were planned for injection into 12 injection locations. Each
location had two points, one screened over the SZ and one
screened over the TZ. Due to challenging injection hydraulics
and geochemical fouling, only 2,343 gal was injected into the
SZ (approximately 25% of the targeted volume), and 1,955 gal
was injected into the TZ (approximately 62% of the targeted
volume). Analytical data for zinc, nickel, and pH from a moni-
toring well located within the injection grid are presented in
Figure 7.9. In addition to the analytical data, the time of the
injection event and the zinc and nickel treatment goals are
presented in Figure 7.9 to facilitate this discussion.
Critical observations of in  situ metal precipitation treat-
ment effectiveness, metal sulfide permanence and stability,
and acidity neutralization can be made from the response
in zinc, nickel, and pH depicted in Figure 7.9. Perhaps the
most notable observation of the data is the simultaneous dip
in zinc and nickel accompanied by a peak in pH approxi-
mately 500 days after the injection event. Based on the rate
kinetics of metal sulfide precipitation discussed earlier, it is
unlikely that this reduction in zinc and nickel (and increase
in pH) was the result of this monitoring well being influ-
enced by the injection. If these results had been directly influ-
enced by the injection, a decrease in zinc and nickel and an
increase in pH would have been expected coincident with
the injection. The challenging injection hydraulics limited
the distribution of reactive sulfide (S2−), and it is likely that
treated groundwater from the injection influenced area moved
through this monitoring well, demonstrating a dilution sig-
nature. About 1,000 days after the injection, zinc and nickel
concentrations and pH measurements stabilize. The zinc and
nickel concentrations stabilized at concentrations less than
preinjection, most notably nickel stabilized below the treat-
ment goal. This demonstrates that upgradient treatment was
sufficient for nickel. The stabilization of zinc is an order of
magnitude below preinjection concentrations, but remains
above the treatment goal. Additionally, insufficient acidity
neutralization occurred to reestablish the background pH of
approximately 6.2. Therefore, it is likely that additional buf-
fer will be required for full-scale in situ metal precipitation.
340
100,000
Nickel and zinc concentrations (μg/L)
10,000
1,000
100
10
1 3.0
–1000 –500
Zinc
FIGURE 7.9  Groundwater concentration response of zinc (Zn2+), nickel (Ni2+), and pH to a calcium polysulfide (CaSx) injection. The delayed
decrease in groundwater concentrations indicates that the representative monitoring well was not influenced during injection, but that upgra-
dient treatment influenced migrated downgradient over the course of the post injection performance monitoring period.
The analytical data in Figure 7.9 are presented on a logarith-
mic y-axis, and therefore, it is not visually apparent that the
zinc concentration is slowly increasing over time. This is not
surprising considering that this field-scale implementation
was a small-scale in situ demonstration to support the broader
full-scale design. However, it is difficult to assign a specific
mechanism to the slow increase of zinc. Some explanations
are impacted groundwater further upgradient moving into the
field-scale treatability test area, slow-advective equilibrium
from the less mobile fraction of the aquifer, or acidic pH jeop-
ardizing the stability of the zinc-sulfide precipitates. Based on
the predictive speciation diagram in Figure 7.4, the pH range
of 3.5–4.5 should theoretically result in the dissolution of zinc
and nickel sulfide precipitates, but the nickel sulfides appear
to be comparatively stable. This may be the result of stable
crystalline nickel sulfides forming during the first 1,000 days
following the injection and the natural groundwater velocity
creating nonequilibrium conditions.38 Regardless of the precise
mechanism for slight increases greater than 2,000 days post-
injection for this field-scale treatability test, the results show
that in situ metal precipitation using polysulfides (Sx2−) can be
highly effective and permanent, but implementation is complex
and proper dosing and acidity neutralization is essential.
Another case study helps us evaluate the importance of
reagent distribution and secondary water quality concerns
for a calcium polysulfide (CaSx) injection. A small field-scale
comparison of delivery mechanisms for CaSx was conducted
in 2010 in the Western United States to primarily address
nickel and zinc in a shallow aquifer. The lithology at the sub-
ject site is characterized as fine to medium silts and sands
from 5 to 15 ft bgs (shallow aquifer), underlain by less perme-
able and highly heterogeneous sands, silts, and clays to the
Remediation Engineering
Aqueous zinc and nickel concentration versus time
6.0
5.5
5.0
pH
4.5
4.0
3.5
0 500 1000 1500 2000 2500 3000
Days elapsed since injection
Zn goal Nickel Ni goal pH Field-scale injection
maximum depth explored of 30 ft bgs (deeper aquifer). The
measured depth of water is shallow (approximately 5 ft bgs)
and may be tidally influenced. The baseline concentrations
in the two pilot study areas ranged from 19 to 1,800 μg/L
for nickel and 190 to 20,000 μg/L for zinc. The baseline pH
ranged from 4.1 to 6.5 and was classified as mildly acidic.
In general, higher dissolved metal concentrations and more
acidic pH were observed in the deeper aquifer. The CaSx was
injected into the shallow aquifer (5–15 ft bgs) through tempo-
rarily installed injection points over two discrete 5 ft screens
(5–10 and 10–15 ft bgs). Approximately 1,200 gal of CaSx solu-
tion was injected into the 5–10 and 10–15 ft bgs intervals in
the shallow aquifer at reasonable injection pressures and flow
rates. The CaSx was injected into the deep aquifer (25–30 ft
bgs) through DPT points due to the expected lower perme-
ability over 1 ft discrete intervals. Approximately 620 gal of
CaSx was able to be injected into the deep aquifer under chal-
lenging injection pressure and low flow rates. The distribution
of sulfide and an inert tracer (bromide) demonstrated more
meaningful response of the injected reagent in the shallow
aquifer. The analytical results for baseline and approximately
30 and 40 days after the injection are presented in Figure 7.10.
Two monitoring wells are shown for each aquifer with ana-
lytical results presented for arsenic (As), iron (Fe), selenium
(Se), cobalt (Co), nickel (Ni), zinc (Zn), and manganese (Mn).
Other metal analysis was completed, but the results of those
metals were negligible in comparison to those presented (cad-
mium, chromium, copper, lead, mercury, and molybdenum).
The graphs presented in Figure 7.10 are shown as normalized
concentrations (normalized to the baseline concentration; C/
C0) to account for the large variability in magnitude of the
different metals (e.g., iron was detected at concentrations as
In Situ Treatment of Metals 341

10.00 MW-A shallow aquifer (5–15 ft bgs) 10.00 MW-B shallow aquifer (5–15 ft bgs)

Normalized concentration
Normalized concentration

response (C/C0)
response (C/C0)

1.00 1.00
As As
Fe Fe
Se Se
0.10 Co 0.10 Co
Ni Ni
Zn Zn
Mn Mn
0.01 0.01
Baseline 30 days 40 days Baseline 30 days 40 days

10.00 MW-C deep aquifer (25–30 ft bgs) 10.00 MW-D deep aquifer (25–30 ft bgs)

Normalized concentration
Normalized concentration

response (C/C0)
response (C/C0)

1.00 1.00
As As
Fe Fe
Se Se
0.10 Co 0.10 Co
Ni Ni
Zn Zn
Mn Mn
0.01 0.01
Baseline 30 days 40 days Baseline 30 days 40 days

FIGURE 7.10  Normalized groundwater concentration responses for numerous metals prior to and 30 and 40 days following a calcium
polysulfide (CaSx) injection.

high as 350,000 μg/L compared to selenium that was detected
at concentrations as high as 150 μg/L). Presenting the data
as a normalized concentration enables quick identification of
increases and decreases in metal concentrations. Comparing
those changes on a logarithmic scale allows for a compari-
son of treatment effectiveness and secondary water quality
concerns. There are numerous observations that can be made
about this data set, and this summarizes some of the most
relevant observations:
1. The overall treatment effectiveness in the shallow
aquifer is higher than the deep aquifer. This is likely
attributed to better reagent distribution and polysul-
fide (Sx2−) contact with the targeted dissolved phase
metal and acidity. Neutralizing the pH may have
contributed to iron precipitation (and subsequent
arsenic precipitation; Section 7.4.4.2), particularly
in MW-B. The targeted metals concentrations of
nickel and zinc demonstrated 75% and 99% and 82%
and 99% reductions in MW-A and MW-B, respec-
tively. This contrasted with nickel and zinc decreases
of 12% and 53% and 28% and 30% in MW-C and
MW-D, respectively. As the shallow aquifer wells
showed a stronger dose response to the injection and
more volume was injected into the shallow aquifer,
this result underscores the importance of the vol-
ume to distribution relationship and reagent contact
for chemically induced sulfide precipitation. From
a design perspective, the deep aquifer will likely
need more temporary injection points with a tighter
spacing and potentially more than one application to
address stored acidity and high-concentration metals
in the immobile fraction of the aquifer.
2. Another indication that strongly reducing conditions
were more homogeneous in the shallow aquifer than
the deep aquifer is the response in selenium (Se). Large
increases in selenium (Se) are observed at MW-A and
MW-B, compared to a smaller response at MW-C and
a decrease in MW-D. The sorption of selenium (Se) to
iron surfaces is redox sensitive. Under reducing con-
ditions where iron is soluble as ferrous iron (Fe2+), an
increase in selenium (Se) is an indication that the tar-
geted engineered conditions were likely achieved in
the shallow aquifer and to a lesser extent in the deep
aquifer. However, selenium (Se) has a primary MCL
of 50 μg/L (Table 7.4) and can present a secondary
water quality concern. This side effect is expected to
be temporary as the naturally occurring geochemis-
try of the aquifer is reestablished upon flushing the
treated area. The solubilized ferrous iron (Fe2+) will
reprecipitate as iron oxyhydroxides, and selenium (Se)
is expected to sorb and coprecipitate.
3. Arsenic precipitation is highly associated with
iron precipitation (Section 7.4.4.2). Locations such
as MW-A, MW-C, and MW-D where stable or
increased arsenic concentrations are observed,
so are stable or increased iron concentrations.
However, at MW-B, a large decrease in iron and
an associated decrease in arsenic are observed.
The difference in magnitude between the iron and
342
arsenic at MW-B slightly mutes the effect, but the
decrease in iron and arsenic at MW-B is the greatest
of all four compared monitoring wells (iron decreased
from 200,000 to 7,100 μg/L and arsenic decreased
from 130 to 65 μg/L). Notice that baseline arsenic
concentration at all locations at the site exceeds the
primary MCL of 10 μg/L and was attributed to natu-
ral geogenic arsenic. The observed iron decreases
and associated arsenic decreases imply that the
injected CaSx resulted in the consumption of acidity
and the resultant precipitation of iron oxyhydroxides.
This is an important observation because had the per-
meability in the shallow aquifer been as challenging
as the deep aquifer, the iron and arsenic precipitation
may have clogged the porosity and inhibited further
distribution. The field-scale testing was essential to
demonstrate the porosity clogging was not a limiting
factor in the shallow aquifer. The arsenic (As), iron
(Fe), nickel (Ni), and zinc (Zn) results at MW-A seem
to imply that insufficient ANC was provided to result
in precipitation of iron and arsenic; however, enough
reactive sulfide (S2−) was distributed to result in some
reductions of nickel and zinc. Slight increases in
arsenic at MW-A may be associated with enhanced
solubility of arsenic under reducing conditions with a
higher concentration of anions (Chapter 3).
As a closing note on polysulfides (Sx2−), an observation in
Tables 7.6 and 7.7 is highlighted for discussion. These tables
show the comparison of metal sulfides (MeS) to metal hydrox-
ides (MeOH) and metal oxides (MeO), and for the majority of
metals that typically cause concern in aquifers, metal sulfides
(MeS) are superior from precipitation and stability perspec-
tives. Most noticeably, chromium is an important environmen-
tal contaminant (Section 7.4.4.1). In Table 7.6, the solubility
constant of chromium sulfide (CrS) is not provided, and in
Table 7.7, chromium sulfide (CrS) is listed as “dissolves”
indicating that the solubility is greater than 1 g in 1,000 g of
water. Wouldn’t this imply that strongly reducing chemically
induced sulfide precipitation could be confounded by chro-
mium exceedances, regardless if other dissolved metals were
addressed? Fortunately, even though chromium sulfide (CrS)
may not be stable under relevant in situ aquifer geochemistry,
chromium hydroxide is indeed stable. The injection of poly-
sulfide (Sx2−) can facilitate the reduction of soluble hexavalent
chromium (Cr6+) to trivalent chromium (Cr3+), and the acidity
scavenging characteristic of sulfides increases the concentra-
tion of hydroxide (OH−) in groundwater.39–43 The following
equation summarizes the process of calcium polysulfide (CaSx,
assumed to be in the pentasulfide form for simplicity [S52−])
mediated hexavalent chromium (Cr6+, in the form of chromate
[CrO42−]) reduction to trivalent chromium (Cr3+) and the subse-
quent trivalent chromium hydroxide (Cr(OH)3(s)) precipitation:
2CrO 4 2 - + 3CaS5 + 10H +
« 2Cr(OH)3(s) + 15S(s) + 3Ca 2 + + 2H 2O (7.12)
Remediation Engineering
7.3.1.1.4  Zero-Valent Iron Metal Precipitation
In  situ ZVI treatment for hexavalent chromium (Cr6+) is
believed to involve reduction of hexavalent chromium (Cr6+)
to trivalent chromium (Cr3+), coupled with the oxidation of
ZVI (Fe0) to ferrous (Fe2+) and ferric (Fe3+) iron, followed by
the precipitation of ferric (Fe3+)-trivalent chromium (Cr3+)
oxyhydroxides or hydroxides.44 Blowes et al.45 provide a sum-
mary of theory and field experience for conventional ZVI
applications. They identified two key reactions that drive
hexavalent chromium (Cr6+) removal in ZVI reactive walls: a
heterogeneous reduction reaction that is followed by precipi-
tation of the trivalent chromium (Cr3+), shown in the following
equations:
CrO 4(aq )2 - + Fe(s)0 + 8H (aq ) + ® Fe(aq )3+ + Cr(aq )3+ + 4H 2O( l )
(7.13)
( 1 - x )Fe(aq )3 + + ( x )Cr(aq )3 + + 2H 2O( l ) ® Fe(1- x )Cr( x )OOH (s) + 3H(aq)) +
 (7.14)
The net consumption of protons would be expected to raise
pH during the reaction series.
A small-scale field trial in the Eastern United States
reported by Puls et al.46 indicates that ZVI reactive barriers
can reduce dissolved chromium concentrations. In their test
of auger-installed ZVI “tubes,” the authors observed a reduc-
tion of hexavalent chromium (Cr6+) from 1 to 3 mg/L to less
than 0.01 mg/L on passage through the reactive barrier. Puls
et al.46 observed pH increases across a ZVI reactive barrier.
On the influent side, pH ranged from 5.5 to 6.1, while values
on the downgradient side ranged from 7.5 to 9.9. Mineral pre-
cipitate formation accompanies many of the ZVI consuming
reactions, so that dissolved iron concentrations on the effluent
side of a reactive barrier may be relatively low, considering
the large mass of iron deployed. Puls et  al.,46 for example,
observed ferrous iron (Fe2+) concentrations ranging from 2 to
20 mg/L in the effluent of a ZVI reactive barrier.
Furakawa et  al.47 studied the mineralogy of the barrier
described by Puls et  al.46 and an additional iron reactive
barrier near Denver, CO. Both walls had been in place for
4 years at the time of mineral sample collections. Ferrihydrite
(Fe2O3 * 0.5H2O) formation was significant, but the mineral
did not accumulate on the ZVI surfaces and therefore did not
contribute to passivation. This is contrary to laboratory batch
and column findings that showed ZVI filings developed coat-
ings of goethite (FeOOH) with trivalent chromium (Cr3+) con-
centrated at the outermost grain boundary.48 Furakawa et al.
pointed out that ferrihydrite (Fe2O3 * 0.5H2O) may be ben-
eficial, as the site of arsenate (As5+) and trivalent chromium
(Cr3+) adsorption. They observed numerous other minerals in
the reactive wall samples and concluded that the geochemical
environment within the reactive barrier was highly heteroge-
neous. The working model for hexavalent chromium (Cr6+)
removal when using ZVI (based on laboratory and field obser-
vations) is via the formation of a solid solution or by adsorp-
tion of trivalent chromium (Cr3+) onto the surfaces of iron
corrosion products.44 This is supported by the observations
In Situ Treatment of Metals
from Wilkin and McNeil, who observed adsorption onto
the ZVI surface as the initial and most rapid metal removal
mechanism for copper (Cu), cadmium (Cd), nickel (Ni), zinc
(Zn), mercury (Hg), aluminum (Al), manganese (Mn), and
arsenic (As).49
The ZVI reactive barrier investigated by Puls et al.46 was
investigated by Wilkin et  al. in 2003 and 2005, approxi-
mately 8  years after the barrier was installed, using high-
resolution mineral characterization, spectroscopy, and
microscopy.44,49 After 8  years of operation, a decrease in
the remedial performance of the reactive barrier (evidenced
by an increase in hexavalent chromium [Cr6+] concentra-
tions within or downgradient of the reactive zone) has not
been observed.44 It is estimated that approximately 33 kg of
chromium has been removed from groundwater at the time
of the publication.44 Following on the mineralogical assess-
ment by Furakawa et  al. and others, mineralogical charac-
terization of soil materials indicates the formation of calcite/
aragonite (CaCO3), iron carbonate hydroxide (FeCO3OH),
magnetite (Fe3O4), lepidocrocite (γ-FeO(OH)), ferrihydrite
(Fe2O3  *  0.5H2O), mackinawite (FeS), and carbonate green
rust ([Fe(6−x)2+Fex3+(OH)12]x+(CO32−)0.5X * yH2O) are all pres-
ent in the reactive barrier.47,49,50 By measuring the available
pore space on the upgradient and downgradient sides of the
ZVI reactive barrier, Wilkin et  al. were able to predict that
approximately 15% of the upgradient and 1% of the down-
gradient available pore space had been lost due to mineral-
ization.44 Measured mineral coverage on ZVI (Fe0) granules
ranged from approximately 30 to 150 μm thick on the upgra-
dient edge and less than 5 μm thick on the downgradient
edge.44 This reduction in pore space could be detrimental to
the reactive barrier (resulting in channeling; see Chapter 10)
or beneficial by providing additional capacity for removal of
hexavalent chromium (Cr6+) by creating sorptive iron miner-
als like ferrihydrite (Fe2O3 * 0.5H2O). Based on the mineral
characterization work in the Wilkin et  al. study, they deter-
mined a significant percentage of trivalent chromium (Cr3+)
associated with mackinawite (FeS) in field samples. This
is consistent with several studies that have demonstrated
hexavalent chromium (Cr6+) is rapidly transformed to insol-
uble trivalent chromium (Cr3+) due to reactions with iron sul-
fide surfaces.35,51,52 This is in support of the working model for
hexavalent chromium (Cr6+) treatment in the presence of ZVI
(Fe0) and demonstrates the importance of the ZVI (Fe0) cor-
rosion products to ferrous iron (Fe2+). This case study example
is further explored in Chapter 10.
Arsenic solubility is dominated by the interaction of its
oxyanions with iron and manganese minerals, particularly
through coprecipitation and adsorption into the hydrous struc-
ture of amorphous iron minerals.53 Decreases in the oxidation–
reduction potential of an aquifer or acidic pH can solubilize
iron and manganese minerals consequently releasing arsenic
that was bound to the iron and manganese minerals into the
aqueous phase. ZVI reactive barriers entail large-scale cor-
rosion of ZVI surfaces, and many iron mineral precipitates
form that may serve to trap arsenic. Su and Puls54,55 studied
arsenic immobilization in ZVI batch and column studies and
343
concluded that arsenic precipitation may be a viable mecha-
nism in field-scale iron reactive barriers. However, arsenic
sorption will be significantly influenced by variations in the
pH and oxidation–reduction potential that develop in ZVI
reactive barriers, and arsenic precipitation will not occur in
all sections of the barrier. Site-specific aquifer chemistry will
control the ability of ZVI to achieve desired arsenic treat-
ment, and pilot-scale testing is essential.
It is clear that ZVI can facilitate effective chemical reduc-
tion of oxidation–reduction potential sensitive metals and sup-
port adsorptive immobilization of sorptive metals; however,
achieving distribution of ZVI via injection remains challeng-
ing. The advances in nanoscale (nZVI) over the past 15 years
are promising and with a greater understanding of agglomera-
tion and its causes there will no doubt be a ­solution to chal-
lenging slurry injections in the future (Chapter 6). It behooves
the practioner to recognize the physical and geochemical
distribution constraints of ZVI and nZVI when selecting an
implementation method.
7.3.1.1.5  Ionic Manipulation
Certain anions maybe injected into the aquifer to force pre-
cipitation of low-solubility compounds. For example, uranium
in the oxidized form is uranyl (U(VI); UO22+) and is highly
soluble and therefore mobile in natural aquifers associated
with potential releases from mining operations. Although
chemical or biological oxidation–reduction potential cycling
is a viable treatment approach to reduce the uranyl to urani-
nite (U(IV); UO2(s)0), which precipitates out of solution under
circumneutral pH, introducing phosphate (PO43−) can produce
low-solubility uranyl phosphate compounds.
Uranyl treatment permanence through the injection of
phosphate (PO43−) has been demonstrated through field dem-
onstrations. In situ phosphate (PO43−) treatment is an emerg-
ing technology currently under evaluation for the removal of
dissolved uranium (UO22+) in groundwater. The technology
uses a phosphate (PO43−) amendment to promote uranyl phos-
phate precipitation, which immobilizes dissolved uranium
(UO22+). This technology has been used in bench and field-
scale tests by the U.S. Department of Energy and the Pacific
Northwest National Laboratory at the Hanford Site to reduce
uranium concentrations in impacted groundwater.56,57 The
technology was selected as part of the preferred alternatives
for the Hanford 300 area uranium plume.58
A source of phosphate (PO43−) is injected directly into the
aquifer, where it reacts with dissolved uranium (UO22+) to
form uranium phosphate mineral precipitates. These minerals
include the following:
• Chernikovite (H[{UO2}{PO4}] * 4H2O)
• Autunite hydrates (Ca[{UO2}{PO4}]2 * xH2O)
• Apatite (Ca5[PO4]3[F,Cl,OH])
The uranium phosphate minerals (chernikovite and autun-
ite hydrates) have low solubility under ambient aquifer con-
ditions.56 The oxidation state of uranium is not changed by
this technology. Compared to technologies that rely upon
344
transforming uranyl (UO22+) to uraninite (UO2) in situ, there
is no concern with phosphate (PO43−) precipitation relative to
reoxidation and resulting dissolution of uraninite (UO2). The
application of phosphate (PO43−) through an injection-based
approach can provide a means of in  situ groundwater treat-
ment that results in the direct precipitation of uranium, as well
as the establishment of a reactive barrier for longer-term treat-
ment as upgradient impacted groundwater moves through the
treatment zone.
Two sources of phosphate (orthophosphate [PO43−] and tri-
polyphosphate [TPP; P3O105−]) have been used in evaluations
of this technology. Orthophosphate (PO43−) is an immediately
available source of phosphate (PO43−), whereas TPP (P3O105−)
slowly hydrolyzes (reacts with water) to form orthophosphate
(PO43−), thereby providing a gradual source of phosphate
(PO43−). In the presence of excess phosphate (PO43−), addi-
tional apatite (Ca5[PO4]3[F,Cl,OH]) is formed, which provides
long-term treatment capacity as future upgradient contami-
nated water passes through the treated zone.59
A field-scale pilot test was implemented at a site in the
Western United States in 2013. The pilot test included the
installation of an injection and monitoring well network, a
preliminary tracer test to understand the volume to distribu-
tion relationship (Chapters 4 and 6), and the chemical injection
of sodium tripolyphosphate (Na5P3O10) and calcium chloride
(CaCl2) with subsequent performance monitoring for more
than 180 days postinjection. Immediate treatment of dissolved
uranium to below standards (0.16 mg/L) was observed after
the introduction of reagents, with sustained treatment through
180 days postinjection (Figure 7.11). Uranium treatment per-
sisted, even as tracers and reagents washed out of the reactive
zone, indicating that dissolved uranium was transported into
the treatment zone from upgradient areas and immobilized
by phosphate precipitates (chernikovite, autunite hydrates
and coprecipitated with apatite). Uranium that was precipi-
tated in situ remained in place after an attempt at remobili-
zation (through push pull test work that injected lower-ionic
1.2
1.0
Dissovled uranium (mg/L)
0.8
0.6
0.4
Site-specific remedial
0.2 goal
0.0
–50 0 50 100 150 200
Days elapsed since injection (days)
Dissolved uranium Injection
Total phosphorus Calcium
FIGURE 7.11  Uranium reductions in groundwater as a result of
calcium and phosphate addition.
Remediation Engineering
strength water into the treatment zone, followed by recovery
of the injected water). Results of the push pull testing show
insignificant dissolution of emplaced phosphate minerals and
uranium.
7.3.1.2  Biological Methods
In situ biological reducing zones can be created in a manner
identical to that applied for enhanced reductive dechlorina-
tion (ERD). The injection of an electron donor (carbohydrates,
oil, etc.) stimulates the naturally-occurring microbial commu-
nity. The natural flux of available electron acceptors (oxygen,
nitrate, manganese, iron, and sulfate) is depleted by the stimu-
lated microbial consumption, driving the microbial metabo-
lism into anaerobia. This floods the aquifer matrix with
reduced inorganic species and lowers the observed oxidation–
reduction potential. In particular, the availability of the sul-
fide ion (S2−) increases, and under these conditions, metals
such as chromium, cadmium, nickel, and zinc may precipitate
rapidly. A biological nickel precipitation strategy is discussed
in detail in Section 7.4.1.3.3.1.
The addition of a carbon substrate can enhance the forma-
tion of reduced, anaerobic conditions by depleting the avail-
able oxidation potential. The presence of carbohydrates serves
two purposes: microorganisms use it as their growth substrate
by depleting the available oxygen, and they use it as an energy
source for the reduction of sulfate (SO42−) to sulfide (S2−).
Theoretically, 3 mg/L of sulfate (SO42−) produces 1 mg/L of
sulfide (S2−) (Equations 7.15 and 7.16). In reality, more sulfate
(SO42−) must be reduced because two of the chemical forms of
sulfide are easily removed from solution:
SO 4 2 - + 8e - + 10H + ® H 2S + 4H 2O (7.15)
3 mg SO 4 2 - 1 mmol SO 4 2 - 1 mmol H 2S
´ 2-
´
L 96 mg SO 4 1 mmol SO 4 2 -
34 mg H 2S 1.06 mg H 2S
´ = (7.16)
1 mmol H 2S L
1000
Total phosphorus and calcium (mg/L)
100
7.3.2  Sorption/Coprecipitation
10 For some metals that are not as amenable to direct precipita-
tion, such as arsenic (As), coprecipitation can be an important
1 and necessary strategy. Coprecipitation involves the forma-
tion of a beneficial secondary solid phase that can remove
0.1 the target metal from solution by sorbing it onto its fresh sur-
faces and encapsulating it as more solid mass is precipitated
0.01 around it (this is called occlusion). The same can be achieved
250
by incorporation of the targeted metal into the structure of the
new secondary solid phase (inclusion). The coprecipitation of
metal contaminants with hydroxides (–OH) of aluminum (Al)
and iron (Fe) is one of the most common treatment approaches
used to remove metals from industrial wastewater.4,27,60 Both
aluminum (Al) and iron (Fe) are relevant to in situ remedia-
tion due to their natural abundance in soil5 (Table 7.1).
In Situ Treatment of Metals
The benefits of coprecipitation are well known and intui-
tive. Consuming acidity associated with a metal release in
an aquifer results in a several orders of magnitude increase
in the hydroxide (OH−) concentration and heavily influences
dissolved iron concentrations. As the acidity consumption/
neutralization continues, precipitated hydrous ferric oxide
(HFO) may incorporate dissolved metals into the crystalline
structure through substitution, sorption onto the surface of the
precipitate, or encapsulation/occlusion among layers of HFO
precipitation. Haphazard inclusion of target metals into HFO
will result in a decrease of the dissolved metal concentrations
and initially be viewed as successfully attaining regulatory
standards—so long as pH conditions in favor of HFO pre-
cipitation are maintained. Great examples of co-precipitation
are arsenic (As3+, As5+) incorporation into iron oxyhydrox-
ide precipitates as a result of pH neutralization and iron
(Fe2+, Fe3+) incorporation into trivalent chromium hydroxide
(Cr(OH)3) precipitation (Section 7.4.4.1). In the case of iron
incorporation into trivalent chromium hydroxide (Cr(OH)3)
precipitation, the resultant iron–chromium hydroxide pre-
cipitate is less susceptible to reoxidation and is approximately
200 times less soluble.27,61 In Section 7.3.1.1.2, a simple exam-
ple of direct chemical reduction of selenate (SeO42−) by fer-
rous iron (Fe2+) was briefly explained, which influences the
solubility of the target metal (i.e., selenium [Se]). In practice,
mobile forms of selenium (selenate [SeO42−] and selenite
[SeO32−]) are highly sorptive to ferric oxyhydroxide surfaces
(goethite [α-FeO(OH)], hematite [Fe2O3], and ferrihydrite
[Fe2O3) * 0.5H2O]),62–69 which typically results in coprecipita-
tion or at least adsorption onto mineral surfaces. This mecha-
nism reduces the mobility of selenium (selenate [SeO42−] and
selenite [SeO32−]) in situ.
Coprecipitation involving target metals that otherwise
would not naturally precipitate is referred to as encapsulation.
Coprecipitation reagents are added to generate nontarget pre-
cipitation reactions at rates that far exceed the target metal pre-
cipitation reaction. This forms a combined precipitate mass in
which the target metal is only a minor component. When the
combined precipitate dissolves, the aqueous phase concentra-
tion of the target metal remains at an acceptable level.
7.4  STRATEGIC CONSIDERATIONS
Metals generally match hydrophobic organics for their solu-
bilities in groundwater and are subject to significant adsorp-
tion to soil through the cation exchange process. However, the
source zone mass formation process for metals is different
from what is observed for hydrophobic organics. The chemi-
cal habitat in the source zone may initially prevent the precipi-
tation of metals (e.g., plating solutions are designed to avoid
precipitation), and during that time, the mass of metals stored
in the static water fraction can become large. Then, if plating
solution stabilizers dissipate or are neutralized, precipitation
can occur in the source area, infecting the source zone aqui-
fer matrix with partially soluble metal solids. The solids then
can support a long-term leaching of metals into the migratory
groundwater.
345
This section discusses through some more detailed geo-
chemical properties, as well as more applicable technology
implementations to achieve in situ metals treatment, the anal-
ysis conducted to demonstrate treatment, and some specific
considerations of routinely encountered metals (chromium
and arsenic) and a brief discussion on radionuclides.
7.4.1  Geochemistry
Metals are not destroyed in  situ, and with the potential for
high concentration source zones to exist for extended peri-
ods of time, it is necessary to define performance factors that
influence the success of in situ metal precipitation. For in situ
metal precipitation implementation, the most practical and
defensible performance factors to consider are those associ-
ated with the aquifer geochemistry because the solubilities
of metals vary with pH, ionic strength, and availability of
anions or cations. The discussion in the literature on in situ
metal precipitation demonstrates the geochemical environ-
ment in which metal precipitation strategies are deployed is
as equally important to the success of the remedy as the pre-
cipitation itself. If the targeted metal precipitate is unstable
in the ambient geochemical environment (i.e., highly aerobic,
saline, slightly acidic), then chances are low that an immobi-
lization strategy will be successful. However, if the targeted
metal precipitate will be stable under ambient geochemistry
(i.e., not a geochemistry that is influenced by a release from
a former plating operation), confirming the reestablishment
of the ambient geochemistry is a reliable performance factor.
7.4.1.1  Solubility of the Targeted Mineral
In situ metal precipitation requires that the selection of the tar-
geted mineral represent the greatest stability over the widest
range of realistic natural geochemistry. Stability in terms of
in situ metal precipitation is directly relatable to the solubility
of the resultant precipitate. The speciation of the targeted pre-
cipitating anion (sulfide [S2−], carbonate [CO32−], phosphate
[PO43−], hydroxide [OH−], etc.) in the groundwater and the
solubility product (Ksp) of the targeted metal precipitate can
be combined to predict the behavior of the solubility. Natural
factors, such as chemical weathering, influence the solubil-
ity of precipitates. Chemical weathering is generally defined
as the equilibration between groundwater and atmospheric
carbon dioxide (CO2), which speciates in the aqueous form
as carbonic acid (H2CO3) at pH below 6.3. The slight acidity
of natural groundwater dissolving ambient soils over decades
may not be a problem, but this acidity may jeopardize freshly
precipitated solids, which have yet to establish a complex lat-
tice crystalline structure.
Solubility is a critical variable in both biological and chem-
ical reactive zone systems for metals. Among the important
solubility effects relevant to in situ metal precipitation are as
follows:
• Precipitation reactions rely on low-solubility prod-
ucts to remove target compounds from the aqueous
phase. One of the important strategies applied in
346
both chemical and biological IRZ is the formation of
insoluble metal precipitates.
• Changes can be induced in the aqueous phase
chemical environment during remedial actions that
solubilize natural soil minerals and contaminant pre-
cipitates in unintended side reactions. This can lead
to the appearance of new contaminants in a reactive
zone treatment (Chapter 3).
7.4.1.1.1  Intrinsic Solubility
The intrinsic solubility with respect to metal precipitation is
defined as the solubility of the cations and anions of an ion-
izable compound at a pH where any potential precipitate is
completely dissolved. In a nickel–water system, the intrinsic
solubility would be the concentration of nickel in equilibrium
with groundwater that does not result in nickel hydroxide
(Ni(OH)2) formation. The equilibrium solubility is the con-
centration of a compound in a saturated solution when excess
precipitate is present, and the dissolved phase compound and
the precipitate are in equilibrium. Therefore, in a nickel sul-
fide–water system, the equilibrium solubility of nickel (Ni2+)
would refer to the equilibrated concentration of nickel (Ni2+) in
groundwater after nickel sulfide (NiS) precipitation occurred.
The potential for various dissolved nickel thiosulfate com-
plexes would have an established equilibrium solubility with
the precipitated nickel sulfide (NiS) as well. The precipitated
nickel sulfide (NiS) would be amorphous crystalline masses
gradually forming more stable crystal structures over extended
periods of time. Therefore, the true concentration of nickel in
groundwater would include the nickel ion (Ni2+) as well as all
of the nickel thiosulfate species (Ni x(S2O3)x). The solubility of
a metal is not simply defined by the dissolved concentration
of the free metal ion (e.g., [Ni2+]). Instead, all of the dissolved
phase complexes must be incorporated into the determination
of the metal solubility. This concept is more deeply discussed
and presented graphically with respect to metal hydroxides
(MeOH) in Section 7.4.1.3.1.
7.4.1.1.2 Complexation
Complexation reactions are important in determining the sat-
uration state of a metal in groundwater. A complex is an ion
that forms by combining simpler cations, anions, and some-
times molecules. The cation or central atom is typically one of
the metals, and the anions, often called ligands, include many
of the common inorganic species found in groundwater, such
as hydroxide (OH−), sulfide (S2−), carbonate (CO32−), sulfate
(SO42−), phosphate (PO43−), chloride (Cl−), and/or an organic
molecule such as an amino acid. In the nickel sulfide–water
system example, the nickel thiosulfate species (Ni x(S2O3)x) are
considered complexes.
7.4.1.1.3  Relevance to Treatment Goals
All of these distinctions are of critical importance when
in situ metal precipitation is discussed because the regulatory
standards for metals in groundwater and the lowest achievable
metal concentrations as a result of various precipitation mech-
anisms are different. For example, in the nickel sulfide–water
Remediation Engineering
system, the regulatory standard would be for the summation
of nickel (Ni2+) in groundwater and the nickel thiosulfate
complexes formed that could keep nickel (Ni2+) dissolved
in the groundwater. The laboratory method for the aqueous
nickel (Ni2+) concentration is indiscriminate with respect to
the dissolved nickel (Ni2+) concentration. Therefore, if the
design does not consider the potential for soluble complexes,
the potential exists to be unable to reach the regulatory stan-
dard. Fortunately, there are other mechanisms at play in an
in situ metal precipitation strategy like coprecipitation and pH
buffering (either acidity or alkalinity neutralization), and the
achievable equilibrium solubility even with the potential solu-
ble nickel thiosulfate complexes (or any metal complexes) can
achieve the regulatory standards at the appropriate pH. This
does underscore the importance of treatability bench-scale
testing to confirm the geochemical mechanism prior to field-
scale implementation, as naturally occurring organics may
also serve to solubilize metals making them unavailable for
reactions with ligands and resultant precipitation.70 It is advis-
able to incorporate a phase of treatability testing where the
freshly precipitated targeted metal is exposed to the ambient
geochemistry to fully evaluate remobilization susceptibilities
related to ancillary immobilization mechanisms (i.e., copre-
cipitation and adsorption). Such a demonstration is presented
in Figure 7.8.
7.4.1.2  Precipitate Formation and Inhibition
Metal precipitates in soil systems represent a selective accu-
mulation of at least two or more constituent ions into an orga-
nized solid matrix that is often crystalline in nature. The
process by which this selective accumulation occurs to form a
distinct solid phase is termed precipitation. A precipitate can
be considered a particulate phase that separates from a con-
tinuous medium. The fact that solid phases form in aquifers
means that the overall free energy of formation is negative for
the combined physical–chemical processes operating during
the period of formation. The actual steps leading to the for-
mation of a separate solid phase, however, must occur at the
microscale level: the joining together of the constituent ions
or molecules that will eventually be recognized as a distinct
separate phase.71,72 Under classical nucleation theory (Section
7.4.1.2.1), three steps are generally considered necessary for
those microscale processes to result in the formation of crys-
tals that will persist and survive over relatively long periods
of time: nucleus formation, crystallite formation, and crystal
(precipitate) formation.71,72
In an ideal precipitation reaction, the solid that forms is
effectively insoluble, and the target metals will be undetect-
able in groundwater. This ideal outcome sometimes cannot be
achieved, but compliance criteria can still be met. There are
two modes of successful precipitation:
1.
Thermodynamic control: Durable and insoluble
metal precipitates are formed, for which the aqueous
phase equilibrium concentration, under foreseeable
aquifer physical/chemical conditions (e.g., tempera-
ture, pH, oxidation–reduction potential, and ionic
In Situ Treatment of Metals
strength), is below the compliance criterion. This
is the ideal result for metal precipitation reactions,
and compliance will be achieved, regardless of the
groundwater velocity.
2.
Dissolution control: Limited solubility metal pre-
cipitates are formed, for which the aqueous phase
equilibrium concentration is greater than the com-
pliance criterion, but the rate of dissolution is slow,
and groundwater flux is sufficient to maintain target
metal concentrations below the compliance criterion.
Precipitation reactions of ionic solids (salts) are reversible,
and the equilibrium concentrations of dissolved ions that form
a salt can be calculated from published observations.
In the simplest cases, the dissolution of ionic solids is
described by the following chemical equation:
Dissolution
Am Bn(s) ¬¾¾¾¾ ® mA(aq ) + nB(aq ) (7.17)
precipitation
The equilibrium constant for the reaction is calculated from
chemical activities of reactants and products similar to other
chemical reactions. The activity coefficient of a pure-phase
(solid phase) reactant is equal to 1 when in equilibrium with
a dilute-aqueous species; therefore, it does not contribute to
the calculation of the equilibrium constant. Hence, the equi-
librium constant is referred to as the solubility product (Ksp)
and, assuming sufficiently dilute solutions to substitute molar
concentrations for activities, is defined as follows:
K sp = [ A]m ´ [ B]n (7.18)
The solubility product (Ksp), alone, does not adequately describe
all of the precipitation processes that occur in aquifers. For
many minerals, the pH and the oxidation–reduction potential
are critical to predictions of solubilities. Stumm and Morgan15
provide an extended discussion of mineral solubilities.
Once the solubility of the metal precipitate has been deter-
mined, combination of the ions in solution determines whether
precipitation occurs. In this way, the metal precipitate com-
pound can be referred to as undersaturated, saturated (equi-
librium), or oversaturated with respect to the dissolved phase
concentration. In an undersaturated solution (unsaturated),
the product of the molar concentration of the ions is less than
the solubility-product constant (Ksp), and ions in solution will
be dissolved to satisfy the [A+][B−] = Ksp condition. In an over-
saturated solution (supersaturated), the product of the molar
concentration of the ions is greater than the solubility-product
constant (Ksp). In this situation, precipitation is imminent
and begins to occur when internal nucleation forces (Section
7.4.1.2.1) allow formation of crystal nuclei. Precipitation will
proceed until the [A+][B−] = Ksp condition is satisfied.3
The dissolved-phase concentration of an ion at equilibrium
with a solid-phase can be calculated as follows:
K sp
[ A] = m (7.19)
[ B]n
347
For the simple salt AB, the dissolved-phase equilibrium con-
centration calculation reduces as follows:
[ A] = [ B] = K sp (7.20)
Nickel sulfide (NiS) and other metal sulfides (MeS) are rela-
tively insoluble in the groundwater, when considered in isola-
tion. The solubility product (Ksp) for amorphous nickel sulfide
dissociation (α-NiS) is 3 × 10 −21 (Table 7.5), and the dissocia-
tion equation is written as follows:
NiS(s) « Ni 2 + + S2 - K sp = 3 ´ 10 -21 (7.21)
The dissolved nickel (Ni2+) can be isolated to show its predicted
concentration as a function of sulfide ion (S2−) and the Ksp:
K sp
[ Ni 2 + ] = (7.22)
[S2 - ]
From examination of Equation 7.22, it is apparent that if a
sulfide (S2−) scavenger were present, the predicted dissolved
nickel (Ni2+) concentration increases. Such a scavenger exists
in groundwater, and the sulfide ion (S2−) is a strong base that
participates in a two-step acid–base equilibrium (Section
7.3.1.1.3.1), drawing nickel (Ni2+) from solid-phase nickel
sulfide (NiS) into solution. Salts of strong bases, such as the
sulfide anion (S2−), gain a boost in solubility due to the rapid
hydrolysis of the base anion when they enter the aqueous
solution.
The equilibria reactions in Section 7.3.1.1.3.1 can be
rewritten as base reactions, taking the inverse of the acid dis-
sociation constants (Ka). The nickel sulfide (NiS) dissolution
reaction may also be added to develop a net reaction for the
nickel (Ni2+) dissolution and sulfide (S2−) scavenging process
that enhances nickel (Ni2+) solubility, particularly at low pH:
H + + HS- « H sS K b1 = 1 ´ 107.04
H + + S2 - « HS- K b 2 = 1 ´ 1018
NiS(s) « Ni 2 + + S2 - K sp = 3 ´ 10 -21
+ 2+
NiS(s) + 2H « H 2S + Ni K net = K sp ´ K b1 ´ K b 2 = 3 ´ 10 4
 (7.23)
The concentration of nickel in solution (Ni2+) can now be cal-
culated from the aqueous hydrogen sulfide (H2S) concentra-
tion and pH:
[H 2S] ´ [ Ni 2 + ]
K net = 3 ´ 10 4 = (7.24)
[H + ]2
and
[H + ]2
Ni 2 + = 3 ´ 10 4 ´ (7.25)
[H 2S]
348
The concentration of soluble nickel (Ni2+) can be plotted as a
function of the pH and hydrogen sulfide (H2S) concentration.
Sulfide concentrations are elevated above background lev-
els during biological reducing zone and chemical treatment
operations, which can force dissolved nickel (Ni2+) to pre-
cipitate out of groundwater. Predicted dissolved nickel (Ni2+)
concentrations as a function of pH is presented in Figure 7.12,
for sulfide concentrations of 3 × 10 −3 to 3 × 10 −5 M, to show
the effects of each on nickel (Ni2+) solubility. This shows that
nickel precipitation can be promoted by the addition of the
sulfide (S2−) anion and maintenance of circumneutral pH. In
addition, it also shows that the 100 µg/L standard for nickel
(Ni2+) adopted by many state regulatory agencies is attainable
with practical increases in sulfide (S2−) in groundwater.
The long-term nickel (Ni2+) solubility is predicted by
Equation 7.12 as a function of pH, on the key assumption that
the sulfide (S2−) ions reaching the groundwater originate from
nickel sulfide (a conservative assumption), and that no con-
sumption of sulfide (S2−) ions occurs other than its redistri-
bution in acid–base reactions (a nonconservative assumption
that will be discussed in the following text). The long-term
solubility of nickel (Ni2+), however, will be based on its solu-
bility at “background” sulfide (S2−) and pH levels. To develop
a conservative estimate of nickel (Ni2+) solubility, we must
assume that nickel sulfide (NiS) is the only source of sulfide
(S2−) in the aquifer. In that case, Equation 7.24 reduces to
2+ 2
[ Ni ]
K net = 3 ´ 10 4 =
[H + ]2
and
[ Ni 2 + ] = 3 ´ 10 4 ´ [H + ]2 (7.27)
In groundwater, other precipitation reactions are likely to
intervene before nickel (Ni2+) reaches the highest dissolved
concentrations shown by these calculations. The fact that
1
0.9
0.8 100 mg/L 10 mg/L 1 mg/L
H2S H2S H2S
Ni2+ solubility (mg/L)
0.7
0.6
0.5
0.4
0.3
0.2
0.1
0
5.0 6.0 7.0
pH
FIGURE 7.12  Predicted nickel solubility in the presence of
3 × 10 −3, 3 × 10 −4, and 3 × 10 −5 M sulfide (S2−) concentration.
Remediation Engineering
many compounds interact in the dissolution and precipita-
tion of metals may explain the wide range of solubility values
available for any reaction. In groundwater, where there are
many interactions for which to account, we can be confident
of the direction in which we are influencing reactions (e.g.,
greater or lesser dissolved concentrations), but we need to be
cautious about predicting specific concentration outcomes
without site-specific testing.
Nickel can react with anions, such as hydroxide (OH−),
carbonate (CO32−), and sulfide (S2−), forming less soluble
compounds. To develop a reactive zone strategy, we exam-
ine candidate nickel salts for their solubility and determine
whether, at equilibrium, their aqueous concentrations meet
remedial objectives. The solubility product constants (Ksp) for
three nickel compounds, nickel carbonate (NiCO3), hydrox-
ide (Ni(OH)2), and sulfide (NiS) (α, β, and γ forms), are pro-
vided in Table 7.5. The solubilities of these compounds are
affected by reactions of the anions when they come into solu-
tion. Decreases in anion concentrations yield increases in the
dissolved nickel (Ni2+) concentration and is represented by
Equation 7.22.
Nickel carbonate (NiCO3) solubility increases due to acid–
base reactions of the carbonate (CO32−) anion similarly to
nickel sulfide (NiS). The carbonate acid–base reactions are
described in Chapter 6 and are summarized as follows:
H 2CO3 « H + + CO32 - K a1 = 4.5 ´ 10 -7 (7.28)
(7.26)
HCO3- « H + + CO32 - K a 2 = 4.7 ´ 10 -11 (7.29)
Inversing the carbonate equations and adding nickel carbon-
ate (NiCO3) dissolution as was done for nickel sulfide (NiS)
yields
H + + HCO3- « H 2CO3 K b1 = 2.2 ´ 106
H + + CO32 - « HCO3- K b 2 = 2.1 ´ 1010
NiCO3 « Ni 2 + + CO32 - K sp = 6.6 ´ 10 -9
NiCO3 + 2H + « Ni 2 + + H 2CO3
K net = K b1 ´ K b 2 ´ K sp = 3.1 ´ 108 (7.30)
The calculation of nickel (Ni2+) in solution, as a function of pH,
could utilize the form of Equation 7.27, which would assume
that the carbonate (CO32−) is supplied entirely by dissolution
Generally accepted
regulatory standard
of nickel carbonate (NiCO3). That assumption is far too con-
for nickel (Ni2+) in servative, and it is more appropriate to assume that the aquifer
groundwater alkalinity is the dominant source of carbonate (CO32−) to the
aquifer. Therefore, it is appropriate to make the calculation as
8.0 9.0
was done in Equation 7.24 and rely on site-specific data for the
aquifer alkalinity to supply the value for carbonic acid (H2CO3):
[H 2CO3 ] ´ [ Ni 2 + ]
K net = 3.1 ´ 108 = (7.31)
[H + ]2
In Situ Treatment of Metals
[ Ni 2 + ] = 3.1 ´ 108 ´
The solubility of nickel hydroxide (Ni(OH)2) is described by
the following reaction equation:
Ni(OH)2 « Ni 2 + + 2OH -
Nickel hydroxide (Ni(OH)2) is linked to aquifer pH through
the hydroxyl (OH−) anion, and the concentration of nickel
(Ni2+) in solution due to nickel hydroxide (Ni(OH)2) can be
calculated by Equation 7.34, which is developed as follows:
K sp = 2.8 ´ 10 -16 = [ Ni 2 + ] ´ [OH - ]2 (7.34)
and
2.8 ´ 10 -16
[ Ni 2 + ] =
[OH - ]2
The solubilities of each of the candidate nickel compounds
can be graphed as a function of pH, as shown in Figure 7.13
(nickel carbonate [NiCO3] was graphed at three alkalinities
(50, 100, and 300 mg/L), representing a range that might be
encountered in natural aquifers). Nickel sulfide (NiS) was
graphed assuming 1 mg/L sulfide (S2−), a concentration that is
reasonable in nonengineered aquifers. From these results, we
can see that nickel hydroxide (Ni(OH)2) would generate the
highest dissolved nickel (Ni2+) concentrations and is unlikely
to control nickel solubility in the presence of carbonate (CO32−)
or sulfide (S2−) anions. Nickel carbonate (NiCO3) and nickel
sulfide (NiS) were retained for additional consideration, and
100
90
NiS
80
Ni2+ solubility (mg/L)
70
60
50
40
30
20
10
0 ment for nickel (Ni2+). The initial results are likely to reflect
3.0 4.0 5.0 6.0
pH
FIGURE 7.13 Predicted dissolved-phase nickel concentra-
tions in equilibrium with each of three compounds: nickel sulfide
(NiS), nickel carbonate (NiCO3), and nickel hydroxide (Ni(OH)2).
Solubility of nickel carbonate (NiCO3) was calculated at three alka-
linities: 50 mg/L (A), 100 mg/L (B), and 300 mg/L (C), representing
low, midrange, and higher aquifer alkalinity values, respectively.
349
[H + ]2 a second graph was prepared, focusing on the pH range from
(7.32) 5.0 to 9.0, as shown in Figure 7.2.
éëH 2CO3 ùû
Some of the difficulties in determining the solubility-
controlling reactions are shown in Figure 7.2, and underscore
an important concept with respect to in  situ metal precipi-
tation. There is great variability among metals solubility in
the published literature. Thoenen presented an in-depth dis-
K sp = 2.8 ´ 10 -16 (7.33) cussion on variable and incompatible solubility limits for
nickel (Ni2+) in sulfide-rich groundwater (1 × 10 −4 M S2−).73
This study concluded that nickel (Ni2+) complexation and
precipitation may behave similarly to zinc (Zn2+) complex-
ation and precipitation, but in general was understudied. The
available solubility products (Ksp) for nickel sulfide (NiS) var-
ied by many orders of magnitude, and some databases may
include thermodynamic data predicting nickel minerals that
are exceedingly rare or high-temperature phases that are irrel-
evant to low-temperature trace concentrations of nickel (Ni2+)
in impacted groundwater. This study and remaining variabil-
ity of solubility products (Ksp) in modeling databases and the
literature appear to be a function of the specific geochemis-
(7.35)
try in which the solubility products (Ksp) were determined.
By extension, applying solubility products (Ksp) to predict
nickel (Ni2+) solubility (or any solubility product [Ksp] to pre-
dict any metal solubility) needs to be evaluated carefully to
ensure that the geochemistry and nickel (Ni2+) concentration
is comparable to the site being evaluated (Section 7.2.7). The
values for the solubility products (Ksp) for nickel sulfide (NiS)
in Table 7.5 were obtained from Weast et  al.5 (1.4 × 10 −24)
and from Kotz and Treichel (3 × 10 −21).12 The lower solubil-
ity product (Ksp), obtained at 18°C from Weast, more closely
matches expected groundwater conditions, but the variation
in dissolved (Ni2+) concentration predicted by the two sources
is disconcerting.
From the nickel (Ni2+) solubility predictions presented in
Figure 7.2, it is apparent that nickel (Ni2+) can be precipitated
from a high-concentration solution by reaction with the car-
bonate (CO32−) anion (present in most aquifers through the
calcium carbonate alkalinity system) or sulfide (S2−) anions.
NiCO3 Ni(OH)2 The sulfide (S2−) precipitates are likely to generate more
insoluble solids at aquifer temperatures typical of the mid
to high latitudes, although carbonate (CO32−) precipitates are
C B
also likely to form. An IRZ strategy that infuses the aqui-
A
fer formation with sulfide (S2−) ions and maintains neutral or
high pH through carbonate (CO32−) buffering is likely to meet
typical compliance criteria. Because the solubility data are
variable, and the predicted solubility limits only marginally
meet typical remedial criteria, bench or field trials would be
recommended before proceeding to a large-scale IRZ treat-
7.0 8.0 9.0
amorphous nickel sulfide crystal formation (α-NiS), and the
maturation of amorphous crystals to form β-NiS is accom-
panied by a 300,000-fold decrease in solubility (calculated
from the 25°C data in Table 7.5). This result suggests that it
may be necessary to sustain high-sulfide, high-pH levels over
an extended period, to accommodate the crystal maturation
process, after which the remaining nickel sulfide (NiS) pre-
cipitates would have a low solubility.
350
7.4.1.2.1 Nucleation
From an in  situ metal precipitation perspective, nucleation is
most aptly defined as the first step in a three step process of
crystal growth, which leads to precipitation. Metal precipitation
is the result of a concentration of a metal complex exceeding the
equilibrium solubility limit, and the process can be influenced
by changes to the pH, concentrations of labile ligands, and
oxidation–reduction potential. As part of the precipitation pro-
cess, the metal complex assembles “critical clusters” or nuclei.
Nucleation is the formation of these critical clusters from which
spontaneous crystal growth will eventually occur.15 The sec-
ond step of the precipitation process is critical clusters forming
crystallites. The third and final step, referred to as ripening,
involves the crystallites continuing to develop and mature to
form larger crystals. Homogeneous nucleation refers to nucle-
ation that occurs in solution, independent of a foreign surface
or substrate. Heterogeneous nucleation includes nucleation
sites on the surface of a substrate (inorganic crystals, skeletal
particles, clays, sand, and biological surfaces can all serve as
suitable substrates). Although some fundamental discussion of
homogeneous and heterogeneous nucleation is provided here,
the reader is referred to other sources for more in-depth reviews
on the principles of nucleation critical clusters and the kinetics
of precipitation and crystal growth.15,74–76
The parameter of critical importance to the discussion of
nucleation is the free energy of the formation of the nucleus, ΔGj,
which is the summation of the energy gained from making bonds
(ΔGbulk) and the energy required to create a surface (ΔGsurf):
DG j = DGbulk + DGsurf (7.36)
The ΔGbulk is always negative for metal precipitation from a
supersaturated solution and is based on a conservative assump-
tion of a spherical nucleus (variations to the spherical assumption
result in a lower ΔGbulk77). The mathematical expression of ΔGbulk
is identical for homogeneous and heterogeneous nucleation and
is the multiplicative sum of the ratio of the volume of the spheri-
cal nucleus and molecular volume (V), the rate constant (k), the
temperature (T), and saturation ratio (S):
4pr 3 a pound. The initial solids that form may be more chemically
DGbulk = - ´ k ´ T ´ ln (7.37)
3V a0
The saturation ratio (S) is the ratio of the actual concentration
(a) and the concentration at solubility equilibrium of the sol-
utes that characterize the solubility (a 0).
The ΔGsurf also assumes a spherical nucleus and is
expressed by the following:
DGsurf = 4pr 2 g (7.38)
where γ is defined as the interfacial energy. Therefore, the
free energy of formation of a spherical nucleus is expressed
as follows:
4pr 3 a ondary water quality impact perspective) to sustain the pH
DG j = - ´ k ´ T ´ ln + 4pr 2 g (7.39)
3V a0
Remediation Engineering
Of critical importance to in situ metal precipitation is the rate
at which nucleation will proceed to accomplish the targeted
precipitation. Therefore, using an adaptation of the conven-
tional Arrhenius rate theory, the rate at which nuclei form, J,
can be expressed as follows15:
J = Ae( -DG j /kT ) (7.40)
where A is a factor that is related to the efficiency of collisions
of the metal complexes targeted for precipitation. Thus, the
rate of nucleation (J) is influenced by the interfacial energy
(γ), the supersaturation (S), the collision frequency efficiency
(A), and the temperature (T).
Of the two forms of nucleation (homogeneous and het-
erogeneous), heterogeneous nucleation is the focus herein
as it is most relevant to in situ metal precipitation. A benefit
of heterogeneous nucleation driving in  situ metal precipita-
tion applications is that nucleation on a substrate reduces the
required interfacial energy (γ). This typically results in het-
erogeneous nucleation occurring at lower saturation ratios
than homogeneous nucleation.
The Ostwald step rule states that the precipitate with the
highest solubility will form first in a consecutive precipita-
tion reaction. In situ metal precipitation is highly complex
and always considered as a consecutive precipitation reac-
tion. The rule is based upon the more kinetically favor-
able nucleation of more soluble complexes. The nucleation
rate of the least stable precipitate (most soluble complex) is
faster than more stable precipitates (least soluble complex).
As nucleation proceeds for the lower stability precipitates,
referred to as precursors, nucleation of more stable pre-
cipitates proceeds using precursors as substrates.74 The
formation of precursors used as substrates and nucleation
at lower saturation ratios demonstrate that fundamentally
in  situ metal precipitation is a viable metals remediation
approach.
7.4.1.2.2  Crystallinity Maturation
Precipitation reactions often do not lead to immediate for-
mation of the most stable form of the precipitated com-
“active” than the stable precipitates that form over long dura-
tions, and these initial precipitates have higher solubilities.
An active form of the precipitate is characterized by a fine
crystalline structure with a disordered lattice. The active
precipitate may persist in metastable equilibrium with the
solution and convert (typically called aging) slowly into a
more stable “inactive” form. It is also possible to create inac-
tive precipitates immediately. Selecting ultra-stable miner-
als that only form at high temperatures, or that form over
extended periods (tens or hundreds of years), is not the basis
of an effective IRZ strategy. Kinetic rate constants for the
precipitation reactions must form durable precipitates within
minutes to hours (days to weeks at the most), because it is
often not desirable (from a cost perspective as well as a sec-
and redox conditions necessary to induce precipitation for
In Situ Treatment of Metals
extended periods. At least two factors control the rate and
sequence of precipitation reactions:
1.
Amorphous (finely divided) crystalline masses: The
high surface-area-to-mass ratios of the fine crystal
masses that form in active precipitates are more
available to aqueous phase reactions than the larger,
mature crystals that form over long time spans (inac-
tive precipitates). It may be necessary to sustain the
chemical conditions that generated the initial precip-
itate for an extended period, to allow the formation
of a stable crystal structure. Initially formed amor-
phous solids may be active or inactive and generally
undergo two kinds of changes during aging. Either
the active form of the amorphous solid becomes
inactive or a more stable amorphous solid is formed.
2.
Reaction kinetic effects: Stability calculations and
the resulting selection of precipitation strategies are
based on analysis of the chemical thermodynamics
of the target compounds and the aquifer. In many
cases, the most stable precipitate is not the one that
forms most quickly. Reaction kinetics dictate the
sequence of product formation and control the rate at
which conversions occur (Chapter 6).
This may be an important differentiator between chemically
and biologically induced IRZs. If the injected chemical reagent
is scavenged and rapidly precipitates amorphous crystalline
precipitates, the ambient flux of natural oxidants like dissolved
oxygen and nitrate may lead to reoxidation of the fresh precip-
itates (Section 7.5). Maintaining chemically reducing condi-
tions may require repeat injections, which increases the cost of
the remediation. In a biologically induced IRZ, a single injec-
tion can maintain reducing conditions for an extended period
of time, facilitating the formation of more stable precipitates. It
is also important to note that most precipitates formed in labo-
ratory or field implementations are amorphous and reactive
Influenced by carbon injection
100,000
10,000 SO4
Methane
1,000 Mn2+
Concentration (mg/L)
As
100 Fe2+
TOC
10
1 1
0.1
0.01
0.001
(a) 10/10/06 7/6/09 4/1/12 12/27/14
FIGURE 7.14  (a) Geochemical results for a monitoring well that was influenced by a carbon substrate injection. (b) Geochemical results
for a monitoring well that was downgradient of the carbon substrate injection. The total organic carbon from the injection reached the down-
gradient monitoring well, but the mobilized geogenic arsenic did not.
351
to a significantly greater degree than minerals formed over
geologic time frames. However, remedial time frames and
regulatory enforcement are not over geologic time frames, so
the amorphous precipitate stability is of considerable interest
from an in situ metal precipitation perspective. Also, because
amorphous precipitates represent the most reactive and soluble
forms of the targeted precipitates, which will decrease with
time, it presents a reasonable worst case scenario to evaluate
the short-term stability of the metal precipitates.
7.4.1.2.3  Mixed Mineral Phases
Metal precipitates may be pure solids (e.g., lead sulfide [PbS],
zinc sulfide [ZnS], chromium hydroxide [Cr(OH)3]) or mixed
solids (e.g., (Fex, Cr1−x)(OH)3, Ba(CrO4, SO4)). Mixed solids
are formed when various elements coprecipitate or interact
with aquifer materials.
An effective mechanism for arsenic (As) removal is dis-
cussed in Section 7.4.4.2. Briefly, arsenate (As5+) is amenable
to surface sorption or coprecipitation with HFO, while arse-
nite (As3+) is more mobile in groundwater. The discussion
goes on to explain that preoxidation of arsenite (As3+) to arse-
nate (As5+), often coupled with the oxidation of ferrous iron
(Fe2+) to ferric iron (Fe3+) and resultant HFO precipitation,
achieves arsenic removal from groundwater through arsenate
(As5+) adsorption to HFO and coprecipitation, encapsulation,
and occlusion as the groundwater precipitates HFO. After
maturation and aging of the crystalline structure (Section
7.4.1.2.1), the resultant precipitate is a mixed mineral of arse-
nic (As), iron (Fe), oxygen (O), and hydrogen (H). The arsenic
(As) is either substituted into the HFO mineral or incorpo-
rated into the bulk structure through adsorption and layering
of continued precipitation, and the result is a stable mineral
that sequesters arsenic from dissolving into groundwater. The
case study example presented in Section 7.4.4.2 discussing
arsenic mobilization as a result of establishing circumneutral
reducing conditions in an IRZ highlights the importance of
this mechanism (Figure 7.14). Arsenic has a primary MCL of
Downgradient of injection
100,000
10,000 SO4
Methane
1,000 Mn2+
Concentration (mg/L)
As
100 Fe2+
TOC
10
0.1
0.01
0.001
9/22/17 (b) 1/14/04 10/10/06 7/6/09 4/1/12 12/27/14 9/22/17
352 Remediation Engineering

10  μg/L (Table 7.4). Without the coprecipitation/sorption of

arsenate (As5+) into/onto ferric iron (Fe3+) precipitates, sec- TABLE 7.9
ondary water quality management would be required down- Members of the Spinel group
gradient of most reducing IRZs. Name Chemical Formula
Another example of targeted mixed mineral phases in
Aluminum spinels
in  situ metal precipitation is iron substitution into triva-
Spinel MgAl2O4
lent chromium hydroxide (Cr(OH)3) precipitation. Iron–
Chrysoberyl BeAl2O4
chromium–hydroxides in the form of CrxFe(1−x)(OH)3 are Gahnite ZnAl2O4
important for a few reasons. First, the substitution of iron Hercynite FeAl2O4
into the crystalline lattice of chromium hydroxide (Cr(OH)3) Galaxite MnAl2O4
reduces the equilibrium solubility resulting in a more stable, Pleonaste (Mg,Fe)Al2O4
less reactive precipitated form of chromium. Solubility inves-
Iron spinels
tigations summarized in the literature for chromium hydrox-
Cuprospinel CuFe2O4
ide (Cr(OH)3) and chromium–iron hydroxide (CrxFe(1−x) Franklinite (Fe,Mn,Zn)(Fe,Mn)2O4
(OH)3) suggest that iron substitution into chromium hydrox- Jacobsite MnFe2O4
ide reduces the solubility by at least an order of magnitude Magnesioferrite MgFe2O4
over the pH range of 2.0–6.0.27,61 Second, ferrous iron (Fe2+) Magnetite Fe3O4
is a primary chemical reductant of hexavalent chromium Trevorite NiFe2O4
(Cr6+) (Section 7.3.1.1.3.2) whether it is intentionally added Ulvospinel TiFe2O4
to an aquifer or generated through manipulation of the ambi- Zinc ferrite (Zn, Fe)Fe2O4
ent geochemistry. The ferrous iron (Fe2+) is oxidized to ferric Chromium spinels
iron (Fe3+) while the hexavalent chromium (Cr6+) is reduced Chromite FeCr2O4
to trivalent chromium (Cr3+), which creates the condition of Magnesiochromite MgCr2O4
trivalent chromium (Cr3+), ferric iron (Fe3+), in water typi- Zincochromite ZnCr2O4
cally at a pH that is conducive to the precipitation of chro-
mium hydroxide (Cr(OH)3) and iron hydroxide (e.g., Fe2O3). Sources: Rinne, F. Mineral., Beil.-Bd. A, 58, 43, 1928; Palache, C. et al.: The
This inherent synergy creates iron–chromium hydroxide System of Mineralogy of James Dwight Dana and Edward Salisbury
Dana Yale University 1837–1892, Vol. I: Elements, Sulfides, Sulfosalts,
(CrxFe(1−x)(OH)3) precipitates that are less soluble than chro-
Oxides. Pages 687–689, John Wiley & Sons, Inc., New York, 1944.
mium hydroxide (Cr(OH)3) precipitation alone.
Copyright Wiley-VCH Verlag GmbH & Co. KGaA. Reproduced with
Other examples of naturally occurring mixed mineral phases permission. Navrotsky, A. and Kleppa, O.J., J. Inorg. Nucl. Chem., 29,
are the mineral spinel group. A collection of known mineral 2701, 1967; Hill, R.J. et al., Phys. Chem. Miner., 4, 317, 1979; Essene,
spinel groups is summarized in Table 7.9 and discussed in more E.J. and Peacor, D.R., Am. Mineral., 68, 449, 1983; Grimes, N.W.
detail as part of a case study discussion in Section 7.4.3.2.4. et al., Proc. R. Soc. A, 386, 333, 1983; O’Neill, H.St.C. and Navrotsky,
An innovative in  situ metal precipitation s­trategy A., Am. Mineral., 68, 181, 1983; Navrotsky, A., Am. Mineral., 71,
is the targeted mixed mineral formation of autunite 1160, 1986; Princivalle, F. et  al., Mineral. Petrol., 40, 117, 1989;
(Ca(UO2)2(PO4)2  *  XH2O); however, demonstrating that O’Neill, H.St.C. and Dollase, W.A., Phys. Chem. Miner., 20, 541,
its has been formed can be difficult. This mixed mineral 1994; Hazen, R.M. and Yang, H., Am. Mineral., 84, 1956, 1999;
was discussed as part of a case study in Section 7.3.1.1.5. Lavrentiev, M.Y. et  al., Am. Mineral., 88, 1522, 2003; Papike, J.J.
et al., Am. Mineral., 90, 277, 2005.
Autunite (Ca(UO2)2(PO4)2  *  XH2O) is a desirable mineral
of uranium because of its low solubility. In thermodynamic
equilibrium studies, the solubility product (Ksp) of autunite
(Ca(UO2)2(PO4)2  *  XH2O) was experimentally determined ((UO2)3(PO4)2) may form preventing the formation of autinite
to be approximately 4.4 × 10 −49 under precise conditions,91 (Ca(UO2)2(PO4)2 * XH2O).57
with well-researched thermodynamic constants. In comparison
with metal hydroxide, metal carbonate, and metal sulfide sol- 7.4.1.2.4 Total Suspended Solids (TSS), Colloidal
ubility products (Ksp) in Tables 7.5 through 7.7, with the excep- Particles, and Facilitated Transport
tion of mercury sulfide (HgS) and copper sulfide (CuS), the Total suspended solids (TSSs) and colloids can complicate the
solubility product (Ksp) of autunite (Ca(UO2)2(PO4)2 * XH2O) removal of metals from groundwater by creating sorptive sur-
is several orders of magnitude less demonstrating the signifi- faces for metal precipitates. With negligible to slow settling
cance of autunite (Ca(UO2)2(PO4)2 * XH2O) stability. It is well rates, the sorbed metal precipitates of the targeted metal may
known that calcium–uranyl–carbonate complexes are ubiqui- appear to remain “in solution.” Intuitively, if a groundwater
tous in aquifers92 with elevated uranium concentrations and sample is collected with considerable TSS, there is a high
the pursuit of autunite (Ca(UO2)2(PO4)2  *  XH2O) formation likelihood that the acidic preservative for dissolved-phase
with the addition of polyphosphate is worthwhile. Autunite laboratory analysis will dissolve solid-phase metals, artifi-
(Ca(UO2)2(PO4)2 * XH2O) can be difficult to generate and/or cially inflating the dissolved metal concentration. The gov-
demonstrate in  situ because apatite (Ca10(PO4)6(OH)2) can erning field measurement during sample collection for metal
sorb uranyl (UO22+) and amorphous uranyl phosphate analysis to establish that a dissolved sample is being collected
In Situ Treatment of Metals
to the extent practicable is turbidity. Groundwater samples
for metal analysis are collected via purging conditions or
discrete-interval passive sampling devices (e.g., HydraSleeve
or SNAP Sampler). With discrete-interval passive sampling
devices, turbidity is reduced by allowing the sampler to sta-
bilize in  situ for approximately 2  weeks prior to retrieving
the sample. Under purging conditions, field measurements
of turbidity are collected at set time intervals to establish an
equilibrated turbidity measurement (generally targeted to be
less than 10–20 nephelometric turbidity units [NTU] for three
consecutive measurements). When evaluating metals data in
groundwater, it is good practice to simultaneously consider pH
and turbidity measurements to validate the analytical results.
If turbidity measurements cannot be equilibrated below 10–20
NTUs, filtration using readily available in-line 0.1 or 0.45 μm
filters may be required. If field filtration is employed, ground-
water samples may be acid preserved at the time of sample
collection. If laboratory filtration is selected, the groundwater
sample is sent to the laboratory unpreserved with a reduced
hold time.* As NTUs measure the scatter of light through a
sample, color associated with tannins or suspended oil drop-
lets may influence the turbidity measurement even after filtra-
tion. In these instances, it is important to qualify the turbidity
response, and ensure filtration occurs regardless.
An example of this is the site in the Southeastern United
States with zinc concentrations in groundwater that exceed
the regulatory cleanup goal of 10 mg/L. Two groundwater
samples from a particular monitoring well were submitted for
laboratory analysis of zinc, one that was filtered and one that
was unfiltered. The measured turbidity at the time the sam-
ples were collected was >2000 NTU.† One sample was dis-
pensed into the acid-preserved sample container and another
was field filtered using a 0.1 μm filter prior to sample collec-
tion. The result of the unfiltered sample was 340 mg/L and the
filtered sample was 0.044 mg/L. This observation supports
the claim that highly turbid samples may artificially inflate
dissolved metal concentrations, as it is likely the difference
in zinc concentrations in these two samples is attributable to
acidic digestion of suspended soil particles.
The classification and intricacies of colloids is a broad sub-
ject, with many components beyond the scope of this chapter.
The nature of colloids and their role in ex situ water treatment
and in situ remediation is highly developed in the literature,
and the reader is referred to Stumm and Morgan and asso-
ciated citations therein for more detailed, first-fundamental
discussion.15 A general discussion relevant to how colloids
may influence demonstrating performance associated with an
in situ metal precipitation remedial action for groundwater is
presented here.
* Hold time is defined as the maximum length of time between when the
sample is collected and the laboratory analysis should be conducted if the
sample is placed on ice and approximately less than 4°C so that chemical
and biological reactions are slow enough to ensure the sample is unaltered.
† This is a common measurement limit for field turbidity meters. While dilu-
tion factors can be applied to determine the true turbidity reading, >2000
NTU suggests considerable TSS, color, oil droplets, or something that may
influence the dissolved metal concentration.
353
Colloids are usually defined based on their size, typically
falling between the 1 nm (0.001 μm) and 1 μm. When colloids
are present in solution, the colloidal suspension is referred to
as a sol. The stability of colloids is often discussed and repre-
sents the resistance of a colloid to settle or filter out of solu-
tion. The stability of a colloids is based upon their size and
electrical properties and is affected by the chemical nature of
the colloid and the chemistry of the groundwater (e.g., ionic
strength, pH, and organic content). There are generally two
forms of colloids: hydrophobic and hydrophilic. Hydrophilic
colloids bind strongly with water, and hydrophobic colloids do
not. Hydrophobic colloids have a surface charge (either posi-
tive or negative) that is a characteristic of the colloid, though
it is influenced by the pH and ionic characterization of the
groundwater. Hydrophobic colloids are more readily removed
from groundwater than hydrophilic colloids.
Colloids are dynamic particles in that they form as a result
of precipitation and nucleation, they undergo compositional
changes, and they settle out of groundwater as their size increases
due to aggregation or attachment. Attempting to distinguish pre-
cipitate colloids from organisms, biological debris, organic mac-
romolecules, clays and oxides, etc., is unnecessary and extremely
difficult. The presence of colloids in in situ metal precipitation
applications is likely positive observations of precipitate forma-
tion, but may artificially inflate analytical results because they
may be captured into acidified groundwater analysis.
Colloidal precipitates larger than 2 μm will be removed
by sedimentation in the low flow conditions common in aqui-
fer systems. Colloidal precipitates are more often removed
mechanically in the soil matrix. Mechanical removal of par-
ticles occurs most often by straining, a process in which par-
ticles can enter the soil matrix, but are caught by the smaller
pore spaces as they traverse the matrix.
Colloidal particles below 0.1 μm will be subjected to
adsorptive mechanisms more so than mechanical processes.
Adsorptive interactions of colloids may be affected by the
ionic strength of the groundwater; ionic composition, quantity,
nature, and size of the suspended colloids; geologic composi-
tion of the soil matrix; and flow velocity of the groundwa-
ter. Higher levels of total dissolved solids in the groundwater
encourages colloid deposition.
Generally, when fine particles of colloid dimensions are
formed, coagulation/flocculation naturally occurs unless steps
are taken to prevent it. Even when the primary precipitates
are of colloid dimensions, if they form larger lumps, a stable
dispersed transport cannot take place. These larger flocs will
settle on the soil matrix.
7.4.1.2.5 Potential Interferences Associated
with In Situ Metal Precipitation
In  situ application of biological and chemical processes to
support precipitation, sequestration, and/or stabilization of
metals in groundwater has provided more effective options for
restoring groundwater quality. It has helped us achieve lower
endpoints by overcoming the physical, chemical, and kinetic
limitations of conventional treatment. However, the complex-
ity of treatment has increased because of the heterogeneous
354 Remediation Engineering

hydrostratigraphy of all aquifers and the influence of engi- attracting cations and repelling anions. Somewhere between the
neered changes in geochemistry with respect to the natural two extremes, there is a pH where a point of zero/neutral surface
mineralogical composition of the soil. charge occurs. The point of zero charge (pHpzc) for several com-
One aspect of this complexity is that when biological or mon metal oxide minerals is summarized in Table 7.10.15,93
chemical processes are applied in situ, interactions with the At extremely high or low pH, these interactions become
solid aquifer matrix are unavoidable. This interaction can irrelevant because aquifer minerals lose their stability and can
affect the stability of native minerals incorporated in the soil actually be dissolved by the excess hydrogen (H+) or hydroxyl
and can temporarily mobilize certain naturally occurring (i.e., (OH−) ions in solution. This also affects the stability of natu-
geogenic) metals (and metalloids) within the treatment zone rally occurring organic matter, which particularly at elevated
(Chapter 3). This of course extends to metals of anthropogenic pH can become mobile in the form of colloidal particles com-
origin as well and makes the geochemistry of metals mobili- plexed with metal cations.
zation an important element of in situ remediation systems.
Such collateral effects of in  situ remediation are gaining 7.4.1.2.5.2  Ionic Strength  As with pH, dissolved ion con-
more attention, particularly as they relate to the question of centrations affect both sorption interactions and intrinsic min-
bringing remediation sites to closure if the concentrations of eral solubility. The ions of metals sorbed to mineral surfaces
naturally occurring metals become elevated in groundwater can be displaced by other ions competing for sorption sites or
during the course of the remedy. However, these effects can be through the formation of soluble complexes. Preferential sorp-
successfully managed if the triggers that can mobilize naturally tion can be based on differences in electrostatic attraction or,
occurring metals during system operation are well understood. in the case of anions, differences in the strength of electron-
sharing interactions.
7.4.1.2.5.1  pH  Fluctuations in groundwater pH will affect As ionic strength continues to increase, it will eventually
the surface charge of naturally occurring metal oxide minerals decrease the activity of all the ions in solution due to the magni-
(and organic matter) in an aquifer. This in turn affects the elec- tude of the electrostatic interactions. This can actually increase
trostatic interactions by which these materials retain surface- mineral dissolution as the aqueous system attempts to balance
bound metals/adsorbed metals. At low pH, the abundance of out the constituent ions based on the solubility product constant
hydrogen ions (H+) saturates sorption sites, giving the surfaces (Ksp) of the mineral (decreased activity requires higher molarity):
a predominantly positive charge, attracting anions and repelling
cations. As pH increases, there are fewer hydrogen ions (H+) and K sp = ( g A[ A y + ])z ´ ( g B [ B z - ]) y (7.41)
the surfaces will exhibit a predominantly negative charge (OH−),
Intuitively, this relationship of activity and molarity is
commonly assumed in the opposite direction. That is often
TABLE 7.10 the activity is assumed to be unity because the molarities
Point of Zero Charge for Common Encountered are diluted enough to satisfy the equilibrium with the solu-
Minerals bility product. It stands to reason that if the molarity of
a particular ion was increased by several orders of mag-
Point of Zero
Mineral Name Mineral Formula Charge (pH)
nitude (i.e., an injection of 5% per weight ferrous sulfate
[FeSO 4] for hexavalent chromium [Cr 6+] reduction), the
Quartz SiO2 1.8
Montmorillonite (Na,Ca)0.33(Al,Mg)2(Si4O10) 3.1
assumption of an activity of 1 is no longer valid. In the
(OH2) * nH2O example of a 5% by weight ferrous sulfate (FeSO 4) injec-
Feldspar KAlSi3O8–NaAlSi3O8–CaAl2Si2O8 3.1 tion, the resultant initial in situ molarity of soluble ferrous
Kaolinite Al2Si2O5(OH)4 4.2 (Fe2+) iron (before oxidation and subsequent precipitation
Gibbsite Al(OH)3 5.0 to ferric [Fe3+] iron) is approximately 3 × 10 −1 M, compared
Manganese dioxide α-MnO2 5.1 to a typical in situ soluble ferrous (Fe2+) iron molarity on
Magnetite Fe3O4 6.5 the order of 1 × 10 −4 M.
Anatase TiO2 7.2
Goethite α-FeOOH 7.8 7.4.1.2.5.3  Oxidation or Reduction Reactions  Certain
Calcite CaCO3 8.3 metals, metalloids, and radionuclides are susceptible to
Hematite Fe2O3 8.5 changes in their valence state as a result of biological and
Aluminum oxide δ-Al2O3 9.5 chemical processes that drive electron transfer. Stability char-
Magnesium oxide MgO 12.3 acteristics for several oxidation–reduction sensitive metals,
metalloids, and radionuclides are summarized in Table 7.11,
Sources: Stumm, W. and Morgan, J.J.: Aquatic Chemistry, John Wiley &
Sons, New York, 1996. Copyright Wiley-VCH Verlag GmbH & Co.
with their thermodynamic ranking shown along with other key
KGaA. Reproduced with permission; Stumm, W.: Chemistry of the elements in Figure 7.15. As indicated, some are stable only in
Solid Water Interface, John Wiley & Sons, New York, 1992. oxidizing environments making them susceptible to reductive
Copyright Wiley-VCH Verlag GmbH & Co. KGaA. Reproduced dissolution, and just the opposite for others. Some are soluble
with permission. in any environment unless they are sorbed to or incorporated
with other minerals.
In Situ Treatment of Metals 355

important part of predesign planning and stakeholder man-

TABLE 7.11 agement. This is contemplated subsequently for both in situ
Stability of Selected Labile Elements biological and chemical metal precipitation.
Primary
Metal Valence States Stability 7.4.1.2.5.4  Biological Interferences  Reduction reactions
Arsenic (As) +3, +5 Soluble in both valence states are most relevant to in situ biologically mediated metal pre-
(anionic) cipitation. Although some acidity can be generated through
Chromium (Cr) +3, +6 +3 relatively insoluble, +6 soluble the formation of organic acids, the ideal operating range of
(anionic) pH for effective biological activity does not include extremes
Iron (Fe) +2, +3 +2 soluble (cationic), +3 that would have a significant effect on metals of environmen-
relatively insoluble tal relevance. Most organisms responsible for reducing the
Manganese (Mn) +2, +3, +4 +2 soluble (cationic), +3/+4 soluble metals to insoluble precipitates experience inhibited
relatively insoluble metabolisms at pH below 5.0. Similarly, ionic strength will
Selenium (Se) 0, +4, +6 0 insoluble, +4/+6 soluble increase due to the injected carbon substrates. However, these
(anionic)
increases are typically moderate, and the carbon substrates do
Uranium (U) +4, +6 +4 relatively insoluble, +6 soluble
not typically incorporate ions that offer strong competition for
(cationic)
sorption sites.
The reductive potential of carbon substrates depends on
the number of electrons yielded during microbial respiration.
These reactions have the greatest effect on the amorphous
For example, alcohol (C2H6O) can yield six electrons per car-
mineral fractions, with crystalline fractions generally more
bon atom, and carbohydrates (CH2O) can yield four electrons
recalcitrant.94 With respect to naturally occurring metals,
per carbon atom, as demonstrated in the following reaction
these reactions can also affect metals sorbed to or incorpo-
(assuming complete mineralization to CO2):
rated with other minerals (or organic material) by virtue of
their dependence on the stability of the sorbing material.
Understanding the degree to which the previously dis- C2H 6O + 3H 2O ® 2CO2 + 12e - + 12H + (7.42)
cussed triggers (pH, ionic strength, and oxidation or reduction
reactions) are relevant during in situ metal precipitation is an CH 2O + H 2O ® CO2 + 4e - + 4H + (7.43)

1.0 Oxidation Oxidation

state state

15
0 O2 H2O –II
0.8
V NO3– N2 0

0.6 IV MnO2 Mn2+ II 10

Propagation of reduction reactions

Propagation of oxidations reactions

VI SeO42– HSeO3– IV
VI HCrO4– Cr(OH)3 III
0.4
Eh (V) pH = 7.0

pE–pH = 7.0

5.0
IV HSeO3– Se 0
0.2
VI UO22+ UO2 IV
III Fe(OH)3 Fe2+ II
V HAsO42– H3AsO3 III
0.0 0.0

–0.2 VI SO42– H2S –II

IV HCO3– CH4 –IV
–5.0

–0.4

FIGURE 7.15  Thermodynamic ranking of selected labile elements.

356
This means that more or less of a specific carbon substrate
may be required to achieve a certain strength of reduced con-
ditions (mildly reducing vs. strongly reducing). Theoretically,
the degradability of a carbon substrate balanced against
the available electron acceptors will determine the dosing
required to achieve a specific reductive poise (not account-
ing for bacterial inefficiencies and cell growth). The size and
strength of the resulting reducing environment in conjunc-
tion with the native mineral characteristics will determine
the degree to which metals may be mobilized. This is true
regardless of the specific carbon substrate. For example, at
sites impacted with mature petroleum hydrocarbon plumes,
the geochemistry is typically strongly reducing with near
equivalent concentrations of total and soluble iron (Fe3+/Fe2+)
and manganese (Mn4+/Mn2+) as a result of indigenous bacte-
ria using the petroleum hydrocarbon as a fermentable carbon
substrate. Recent research does indicate that high dosing of
carbon substrates can facilitate more aggressive reductive dis-
solution by creating metabolites that act as electron shuttles or
chelating agents, affecting even crystalline mineral phases.95
Data from actual in  situ engineered anaerobic/reducing
environments created in normally aerobic aquifer settings
have shown iron (Fe), manganese (Mn), and arsenic (As) to
be of primary relevance. This is likely attributable to the
following:
1. Both iron (Fe) and manganese (Mn) are oxidation–
reduction potential sensitive, are soluble in their
reduced valence states (ferrous iron Fe2+ and man-
ganous manganese Mn2+), and are abundant in soil
(Table 7.1). Because they are also ubiquitous, they
are primary rungs in the ladder of alternate electron
acceptors used by microbes for respiration in anaer-
obic environments (Figure 7.15). This makes them
significant in terms of the potential for mobilization,
40,000
35,000
30,000
Manganese (µg/L)
25,000
20,000
15,000
10,000
5,000
0 0
0 500 1000
Time (days)
FIGURE 7.16  Dissolved metals data from an engineered anaerobic in situ reactive zone. Note: The monitoring well location is approxi-
mately 40 days of groundwater travel time downgradient of the injection line.
Remediation Engineering
with elevated dissolved ferrous iron (Fe2+) and man-
ganous manganese (Mn2+) typical in in situ biologi-
cally mediated metal precipitation reactive zones.
2. Arsenic is a metalloid that is soluble in all its valence
states (As3+ and As5+) unless it is adsorbed to or
incorporated with other minerals (most often those
of ferric iron [Fe3+]). Although it is not abundant
in Earth’s crust (Table 7.1), arsenic is ubiquitous in
small amounts and can be liberated by direct reduc-
tion, complexation with reactive sulfide, or reductive
dissolution of the ferric iron (Fe3+) minerals with
which it is typically associated.96
Available dissolved electron acceptors, hydrogeologic hetero-
geneities, and the complexities of solid-phase/aqueous-phase
interactions prevent rapid dissolution of these metals follow-
ing creation of anaerobic conditions in groundwater. Instead,
this process occurs slowly over time, as indicated by the data
in Figure 7.16. Some solubility control is actually possible
within the anaerobic zone due to the formation of iron and
manganese carbonate minerals as well as iron sulfides capa-
ble of incorporating some arsenic.
The dissolved concentrations of these metals can be
expected to remain elevated while the anaerobic environ-
ment is maintained. Fortunately, as indicated by the data in
Figure 7.17, there are natural processes that can control their
mobility at the boundary of the anaerobic zone. In the absence
of oxygen, it is likely that sorption mechanisms and reaction
with solid phases dominate in importance to at least initially
impart this control. Ferrous iron (Fe2+) is also susceptible
to sorption, but can also oxidize via reaction with certain
soil minerals (such as manganese dioxides [MnO2]), creat-
ing additional ferric iron (Fe3+) minerals. Similarly, arsenic
transport is likely limited by partitioning to both naturally
occurring and freshly precipitated ferric iron (Fe3+) minerals,
800
700
Iron (mg/L) and arsenic (µg/L)
600
500
Manganese 400
Iron
Arsenic 300
200
100
1500 2000 2500
In Situ Treatment of Metals
40,000 Anaerobic reactive zone
35,000
30,000
Manganese (µg/L)
25,000
20,000
15,000
10,000
5,000
0 0
–100 0 100
Location of
Upgradient
injection line
FIGURE 7.17  Dissolved metals data through and engineered anaerobic in situ reactive zone. The data presented represents conditions after
4.5 years of in situ reactive zone operation (1,640 days).
and there is evidence that it can also react with manganese
dioxides (MnO2) in a similar manner to ferrous iron (Fe2+).
Manganous manganese (Mn2+) is comparatively more mobile
than both arsenic and iron owing to the fact that the previous
reactions will contribute to its solubility at the edge of the
anaerobic reactive zone, it is less susceptible to sorption, and
it requires more strongly aerobic conditions to reoxidize and
precipitate.97
This then begs the question, “What happens at the end of
the remedy?” It is reasonable to expect that as the naturally
aerobic poise is restored, ferrous iron (Fe2+) and manganous
manganese (Mn2+) will reprecipitate. For the site that was the
source of the data presented in Figure 7.17, the ratios of dis-
solved iron to dissolved arsenic have remained consistently
high (from 200:1 to nearly 450:1). It is therefore reasonable to
expect the arsenic to coprecipitate with the iron. The rate of
dissolved oxygen and other electron acceptor recharge com-
pared to the residual reductive poise will determine the time
frame for this transition. In biological systems, this has the
potential to take a long time because once the injected carbon
substrate has been consumed, bacteria can use synthesized
cells as a source of carbon (see Chapter 6). Lengthy metal
attenuation time frames may be acceptable in the context of
a long-term remediation effort but can also be actively expe-
dited if warranted via engineered solutions.
7.4.1.2.5.5  Chemical Interferences  In  situ metal pre-
cipitation via chemical processes can influence all three (pH,
ionic strength, and oxidation–reduction sensitivities). For
the purposes of discussing interferences associated with the
reagents summarized in Table 7.8, we focus on potentially
practical chemical reagents for in  situ metal precipitation:
ZVI (Fe0), polysulfide (Sn2−), dithionite (S2O42−), ferrous (Fe2+)
iron, and sodium sulfite (Na2SO3). All forms of organic acids
357
800
Manganese 700
Iron
Arsenic
Iron (mg/L) and arsenic (µg/L)
600
500
400
300
200
100
200 300 400 500
Distance (ft) Conditions after 4.5 years
of operation (1640 days)
Downgradient
and emulsified vegetable oil ZVI are not considered because,
despite their nucleophilicity (i.e., behavior as a chemical
reductant), their reducing capacity is indistinguishable from
stimulating reducing biological processes. Chemical reagents
that are theoretically appropriate for ex  situ metals removal
(i.e., trisodium salt [TMT-15], available phosphites, and
borohydride) are not considered for in  situ metal precipita-
tion because of the impurities and potential health and safety
hazards of handling these chemical reagents in the field for
injection purposes.
The chemical interferences are not dissimilar from the
biological interferences; they are simply caused by the injec-
tion  of the chemical reagents in Table 7.8 rather than the
injection of a carbon substrate and the subsequent bacterial
response to the carbon substrate. Recall the second CaSx
case study discussed in Section 7.3.1.1.3.3 that demonstrated
slight increases in arsenic and larger increases in selenium.
The increased concentration of anions in solution (Sn2−) and
establishing strongly reducing conditions created a secondary
water quality concern for selenium (Se). Such is a chemical
interference associated with a polysulfide (Sn2−), dithionite
(S2O42−), and sodium sulfite (Na2SO3) injection, or any chemi-
cal injection that establishes these conditions.
A related issue to interferences associated with chemical
reagents injected into aquifers is the secondary water qual-
ity concerns (Chapter 3). It is noteworthy to mention how a
well-intentioned in  situ metal precipitation and acidity neu-
tralization may accidentally change the contaminant of con-
cern from metals/acidity to the associated cation or anion of
the selected chemical reagents. For example, a commercially
available form of polysulfide is sodium polysulfide (Na2Sx).
Sodium polysulfide (Na2Sx) can be desirable to the more
typical calcium polysulfide (CaSx) because the payload of
sulfide is higher (Table 7.12) and sodium polysulfide cations
358
TABLE 7.12
Typical Properties of Commonly Available Forms
of Polysulfide
Calcium Polysulfide Sodium Polysulfide
Property (CaSx) (Na2Sx)
Assay (% by weight) 27% 33%
Cation (% by weight) 6% 6%
Sulfur (% by weight) 20.5% 27%
Specific gravity (25°C) 1.25–1.29 1.35–1.39
pH 10.0–11.7 10.0–12.0
Color/odor Ruby red/hydrogen
sulfide (rotten eggs)
of sodium have a lower charge equivalence resulting in less
ion exchange with divalent metals that have sorbed in situ. In
order to optimize the distribution of reactive sulfide, it may be
desirable to add some ANC in the form of sodium bicarbonate
(NaHCO3) or sodium hydroxide (NaOH) to avoid the sulfide
being used to neutralize acidity. A 2% by weight concentra-
tion of sodium polysulfide (Na2Sx) and a 0.25% by weight con-
centration of sodium hydroxide (NaOH) result in an injected
concentration of sodium of 5,900 mg/L, which exceeds cer-
tain state specific criteria (i.e., Florida Groundwater Cleanup
Target Level of 160 mg/L). The rate of treatment area flushing
and resultant dilution of injected cations should be carefully
considered and communicated to stakeholders prior to imple-
menting the injections.
7.4.1.2.5.6   Potential for Fouling (Porosity and Permeability
Reductions)  The injection of microscale ZVI (Fe0) is ill
advised because the distribution of microscale ZVI (Fe0) is
challenged by many things; among them is chemical pas-
sivation of the reactive iron before contacting the contami-
nants. The innovations in nanoscale ZVI (nZVI) discussed
in Chapter 6 explain the relevancy of protecting against this
form of chemical interference. In an aquifer plagued by acidic
pH and elevated dissolved metal concentrations, the injec-
tion of a highly alkaline reagent (i.e., polysulfide or sodium
hydroxide) can result in rapid and voluminous precipitation
of iron oxyhydroxide minerals. For example, ferrihydrite
(Fe2O3  *  H2O) is up to 600% larger than an equal mass of
ZVI (Fe0).98 Geochemical porosity clogging can significantly
inhibit chemical reagent distribution to the targeted ROI
potentially resulting in incomplete treatment and likely poor
treatment effectiveness over a long enough time frame.
A particularly interesting form of potential porosity clog-
ging can be related to the cation or anion associated with the
chemical reagent. For example, calcium polysulfide (CaSx)
uses calcium as the cation in this particular commercially
available form of polysulfide. Calcium polysulfide (CaSx) is
a popular choice for remediation of aquifers impacted by his-
torical galvanizing operations because it can neutralize acid-
ity and create insoluble metal sulfides as discussed previously
(Section 7.3.1.1.3.3). Sulfuric acid (H2SO4) is a common acid
used in galvanizing operations, and aquifers impacted with
Remediation Engineering
acidity and elevated dissolved metals from galvanizing opera-
tions that used sulfuric acid are also likely to have elevated
concentrations of sulfate (SO42−) in groundwater. The disso-
ciation of calcium polysulfide (CaSx) into calcium ions (Ca2+)
and polysulfide anions (Sn2−) in groundwater with elevated
concentrations of sulfate (SO42−) is likely to result in massive
precipitation of calcium sulfate dihydrate (CaSO4 * 2H2O; i.e.,
gypsum), which can result in significant porosity clogging and
permeability reductions.
Another mechanism for potential fouling involves the
intentional neutralization of highly acid or alkaline ground-
water. These types of plumes are characterized by elevated
dissolved solids from chemical weathering of the native aqui-
fer minerals including elevated concentrations of dissolved
metals such as iron (Fe), aluminum (Al), and calcium (Ca)
along with elevated concentrations of dissolved silica (Si).
While the composition of acidic versus alkaline groundwater
will be different, the role of silica (Si), aluminum (Al), and
iron (Fe) is consistent given that they are the second, third,
and fourth most abundant elements in Earth’s crust, and their
common mineral forms are highly pH sensitive. The introduc-
tion of bulk acidity or alkalinity to a highly alkaline or acidic
groundwater with the intent of rapid neutralization will yield
the rapid reprecipitation of dissolved solids into a low-density
(high volume) amorphous mass, potentially clogging avail-
able pore space.
7.4.1.3  Mineral Comparisons
Dissolved heavy metals can be precipitated out of solution
through various precipitation reactions to form insoluble sul-
fide (S2−), hydroxide (OH−), carbonate (CO32−), and phosphate
(PO43−) precipitates. Theoretical behavior of solubility of
hydroxide (OH−) and sulfide (S2−) precipitation mechanisms is
shown in Figure 7.18. A divalent metallic cation is used as an
example in the following reactions:
(OH - ) precipitation: Me 2 + + 2OH - ® Me(OH)2 ¯ (7.44)
(S2 - ) precipitation: Me 2 + + S2 - ® MeS ¯ (7.45)
2- 2+ 2-
(CO3 ) precipitation: Me + CO3 ® MeCO3 ¯ (7.46)
(PO 43- ) precipitation: 3Me 2 + + 2PO 43- ® (Me)3 (PO4)2 ¯
 (7.47)
In certain cases, metal carbonates (MeCO3) are less soluble
than their corresponding metal hydroxides (MeOH). This is
true in the case of barium (Ba2+), cadmium (Cd2+), and lead
(Pb2+) (Table 7.13 and Figure 7.19).
7.4.1.3.1  Oxides and Hydroxides
Hydroxide (OH−) precipitation occurs when the pH of an
aqueous system containing dissolved metal ions is raised to
some optimum level for a specific metal. The optimum pH is
different for each metal and, often, for different valence states
of the same metal. It may vary for a specific metal ion with
In Situ Treatment of Metals 359

100
Pb+
Ag+
10

1.0 Zn2+

Solubility (mg/L)
Cd2+
0.1
Fe2+
Ni2+
Cu2+
0.01
Fe3+

0.001

0.0001
3 4 5 6 7 8 9 10 11 12
(a) pH

100
Pb(OH)2
Cu(OH)2

10
Soluble metal concentration (mg/L)

As2S3

NiS Zn(OH)2
1.0
ZnS
PbS

0.1 CdS Cd(OH)2

Ni(OH)2
0.01 NiS
ZnS
PbS
CuS
0.001
0 2 4 6 8 10 12 14
(b) pH

FIGURE 7.18  (a) Solubilities of metal hydroxides with pH. (b) Solubilities of metal hydroxides and metal sulfides as a function of solution
pH. (From Weiner, E.R., Applications of Environmental Chemistry, Lewis Publishers, Boca Raton, FL, 2000.)

the presence of other species in solution, with the oxidation– Recall Equations 7.46, 7.47, and 7.48 from Section 7.4.1.1
reduction potential, and with the aging of the hydroxide where nickel was used to demonstrate the differences in com-
(OH−). Aging effects can be explained as the slow conversion parative mineral solubility. Also, recall that hydroxide (OH–)
of an active, crystalline matrix to a more inactive amorphous and hydrogen (H+) are connected through the equilibrium
form (Section 7.4.1.2.2). constant for water (Kw). Substituting “Me” to make Equations
Much of the discussion in this chapter has focused on 7.46, 7.47, and 7.48 generic and combing them with the water
metal sulfide precipitation, and that is because metal sulfides equilibrium expression yield Equations 7.70 and 7.71:
present a reliable method of achieving regulatory cleanup
standards over a wide range of potential geochemical con- |* [ Me 2 + ] |* [ Me x + ]
K sp = + 2
or more generalized as K sp = (7.48)
ditions (via biological or chemical processes). This does not [H ] [ H + ]x
mean that metal hydroxides are not important or relevant in
|*
in situ metal precipitation. The hydroxide (OH−) and carbon- with the K sp value being equal to:
ate (CO32−) ligands are readily available in natural systems |
K sp
and as such can significantly influence the availability of dis- K *sp = (7.49)
solved ions and participate in metals immobilization. Kw
360 Remediation Engineering

TABLE 7.13
Comparison of Metal Hydroxide and Metal Carbonate Solubility Products (Ksp)
Chemical Compound Name Mineral Name Mineral Formula Solubility Product (Ksp) Source
Barium carbonate Witherite BaCO3 7 × 10−9 Weast et al.5
Barium hydroxide octahydrate Ba(OH)2 * 8H2O 2.55 × 10−4 Lide99
Cadmium carbonate Otavite CdCO3 1 × 10−12 Lide99
Cadmium hydroxide Cd(OH)2 7.2 × 10−15 UNC14
Iron carbonate Siderite FeCO3 3.13 × 10−11 Lide99
Iron hydroxide Fe(OH)2 1.64 × 10−14 Weast et al.5
Lead carbonate Cerussite PbCO3 3.3 × 10−14 Weast et al.5
Lead hydroxide Pb(OH)2 1.43 × 10−20 UNC14
Nickel carbonate NiCO3 6.6 × 10−9 Kotz et al.12
Nickel hydroxide Ni(OH)2 2.8 × 10−16 Kotz et al.12
Zinc carbonate Smithsonite ZnCO3 1.46 × 10−10 Lide99
Zinc hydroxide Zn(OH)2 1.8 × 10−14 Weast et al.5

Sources: Weast, R.C. et al., Handbook of Chemistry and Physics, 65th edn., F-146, CRC Press, Boca Raton, FL, 1984;
Kotz, J.C. et al., Chemistry and Chemical Reactivity, 5th edn., Thomson-Brooks/Cole, 2003; North Carolina
State University website, http://www4.ncsu.edu/~franzen/public_html/CH201/data/Solubility_Product_
Constants.pdf. Solubility Product Constants, accessed December 2015; Lide, R.R., Handbook of Chemistry
and Physics, 83rd edn., CRC Press, Boca Raton, FL, 2002.

1000

900
NiCO3
800 Ni(OH)2
BaCO3
700
Metal solubility (mg/L)

Ba(OH)2 * 8H2O
600 CdCO3
Cd(OH)2
500 FeCO3
Fe(OH)2
400 PbCO3
300 Pb(OH)2
ZnCO3
200 Zn(OH)2

100

0
4.0 6.0 8.0 10.0 12.0 14.0
pH

FIGURE 7.19  Solubilities of metal hydroxides and metal carbonates as a function of solution pH, assuming 100 mg/L carbonate (CO32−).

From these expressions, the dissolved metal concentration in
equilibrium with the metal hydroxide precipitate can be pre-
sented as a function of pOH or pH (Figure 7.20). Combining
Equations 7.48 and 7.49, applying a logarithmic conversion,
and rearranging to solve for the dissolved metal concentration
as a function of pH yields as follows:
log[ Me x + ] = log K sp
|
+ xpK w - xpH (7.50)
This is the linear representation supporting the lines shown in
Figure 7.20. This singular line does not fully describe the sol-
ubility of the metal hydroxide because there can be numerous
soluble complexes of metal ligands in equilibrium solubility
with the metal hydroxide solid precipitate. This was discussed
in Section 7.4.1.1.1 and is an important concept because the
laboratory analytical result for the dissolved metal will include
all of these soluble complexes (i.e., equilibrium solubility).
The true solubility is described by the available metal hydrox-
ide complexes that could form based on the valence of the
subject metal. For example, four such total s­ olubility diagrams
are presented in Figures 7.21 through 7.24, for aluminum
(Al3+), ferric iron (Fe3+), zinc (Zn2+), and trivalent chromium
(Cr3+). These diagrams are created by expressing the solubil-
ity expression in a linear manner (i.e., Equation 7.50) for each
In Situ Treatment of Metals 361

0
Co2+ Mn2+
Ca2+

–1 Cd2+
Zn2+
Fe2+
–2
Al3+

logC –3
Fe3+ Mg2+
Cu2+
Ni2+
Cr3+
–4

Pb2+
–5

–6
2 4 6 8 10 12
pH

FIGURE 7.20  Free metal-ion concentration in equilibrium with solid oxides or hydroxides, as adapted from Stumm and Morgan.15 The
occurrence of hydroxometal complexes must be considered for evaluation of complete solubility.

–2
AlOH2+
–4
Al(III)tot
–6 Al(OH)3
log[C]

–8

–10
Al3(OH)45+
–12
Al3+ Al(OH)2+
–14
Al13O4(OH)247+
–16
2 4 6 8 10 12
pH

FIGURE 7.21  Aluminum hydroxide (Al(OH)3) solubility and supporting aqueous aluminum complexes versus pH.

potential form of metal hydroxide complex. These lines are
presented in Figures 7.21 through 7.24 as gray dotted lines
behind the dark black line. The dark black line in Figures
7.21 through 7.24 represents the saturation index for the metal
hydroxide. Concentrations above or below the line will result
in precipitation or dissolution, respectively. The aluminum
(Al3+) and ferric iron (Fe3+) diagrams were selected for inclu-
sion here because these two metals represent a great potential
for coprecipitation in natural aquifers when pH neutralization
occurs (Figures 7.21 and 7.22). Notice the minimum solubility
for aluminum hydroxide (Al(OH)3(s)) is around 6.3 and ferric
hydroxide (Fe(OH)3(s)) 8.0. Despite the larger natural presence
of iron, coprecipitation with iron is often the driver in  situ
due to the lower solubility (i.e., precipitation is likely to occur
more readily for iron). Note that the minimum solubility for
aluminum (Al(III)tot) at 6.3 is approximately 4.1 × 10 −7 M
(log[Al(III)tot] ~ −6.3. Then note the corresponding concen-
tration of iron at pH = 6.3 is 4.1 × 10 −10 M (log[Fe(III)tot] ~
−9.4), which is three orders of magnitude lower that the mini-
mum solubility of aluminum (Al(III)tot). As pH neutralization
occurs from typical metal-plume contaminant pH of 3.5–4.5
to greater than 6.0, massive precipitation of available iron is
expected to coprecipitate, encapsulate, and include dissolved
metals irons into the crystalline masses of ferric iron (Fe3+)
362 Remediation Engineering

–2

–4
FeOH2+
–6

log[C] –8
Fe(III)tot
–10 Fe(OH)3

–12 Fe2(OH)24+

–14 Fe(OH)2+
Fe3(OH)45+ Fe3+
–16
2 4 6 8 10 12
pH

FIGURE 7.22  Iron hydroxide (Fe(OH)3) solubility and supporting aqueous iron complexes versus pH.

0
ZnOH+

–2
Zn(II)tot
–4 Zn(OH)2

–6
log[C]

–8 Zn2+
Zn(OH)3–

–10
Zn2(OH)3+
–12
Zn(OH)42–
Zn2(OH)62–
–14

–16
2 4 6 8 10 12
pH

FIGURE 7.23  Zinc hydroxide (Zn(OH)2) solubility and supporting aqueous zinc complexes versus pH.

hydroxide. This examination clearly shows the relevance and
importance of both aluminum and iron hydroxides (Al(OH)3(s)
and Fe(OH)3(s)) to control coprecipitation in situ.
The zinc hydroxide (Zn(OH)2(s)) system is presented in
Figure 7.23 and demonstrates why metal sulfides typically
control heavy metals removal from groundwater. From Table
7.4, the secondary MCL for zinc (Zn2+) is 5,000 µg/L (7.65 ×
10 −8 M). The minimum achievable solubility for zinc (Zn(II)tot)
using hydroxide precipitation occurs at a pH of approximately
9.8 and at a concentration of approximately 2,321,700 µg/L
(3.55 × 10 −5 M), greater than 460 times the secondary MCL.
Not only would it be impractical to sustain a natural pH at 9.8,
achieving a pH of 9.8 would not result in meeting the stan-
dard. Clearly zinc sulfide (ZnS), with a solubility difference
factor of 3 × 108 (Table 7.6) presents a more reliable and prac-
tical way to achieve regulatory standards.
Finally, trivalent chromium (Cr3+) solubility is presented
in Figure 7.24, for the distinct reason of demonstrating how
sensitive the solubility of chromium hydroxide (Cr(OH)3) is
on the acidity side of the solubility diagram. This diagram
shows that strongly acidic conditions can drive the specia-
tion of chromium, and acidity neutralization to circumneutral
or slightly alkaline conditions is an essential component of
in situ metal precipitation of hexavalent chromium (Cr6+). One
interesting exception in sulfide (S2−) precipitation is that of
chromium, which does not precipitate as the sulfide (S2−), but
as chromium hydroxide (Cr(OH)3). This is apparent based on
the available solubility products (Ksp) provided for chromium
In Situ Treatment of Metals
0
–2 Cr(OH)2+
–4
Cr(OH)3(aq)
Concentration (M)
–6
–8
Cr(OH)4–
–10
–12
–14
–16
2 4 6 8
FIGURE 7.24  Chromium hydroxide (Cr(OH)3) solubility and supporting aqueous chromium complexes versus pH.
in Tables 7.5 through 7.7. Therefore, chromium removal will
be controlled by hydroxide (OH−) precipitation, and hence by
pH. Precipitation as chromium hydroxide (Cr(OH)3) has long
been the traditional approach for treating hexavalent chro-
mium (Cr6+) laden industrial wastewater streams.
7.4.1.3.2 Sulfides
Most metal sulfide precipitates are less soluble than metal oxide
and hydroxide precipitates at the pH ranges encountered in
groundwater systems (arsenic, antimony, chromium, iron, and
tin are exceptions; Table 7.7). It is evident from Tables 7.6 and
7.7 and Figure 7.18 that metal sulfide precipitation is effective.
Regulatory compliance criteria for highly toxic metals are often
only achievable through the formation of metal sulfides because
metal sulfide solubilities are several orders of magnitude lower
than metal hydroxide precipitates through the pH range. Also,
metal sulfide solubilities are not sensitive to changes in pH.
Metal sulfide precipitation is considered the dominant mecha-
nism limiting the solubility of many heavy metals. Sulfide pre-
cipitation is particularly strong for Class B metals or soft (and
some borderline) cations such as Ag+, Cu+, Hg+/Hg2+, Cd2+, Pb2+,
and Zn2+; it is also an important mechanism for transition ele-
ments such as Cu2+, Ni2+, Co2+, Fe2+, and Mn2+.100,101
Sulfide is highly reactive in situ and easily scavenged by
acidity and oxygen. In natural aquifers that have not been
engineered for biological or chemical sulfide precipitation,
analytical results for sulfide are typically below laboratory
reporting limits to generally less than 1 mg/L. Even field
test kits can be challenged by accidental equilibration of the
groundwater sample with the ambient atmosphere. Typical
purge-based groundwater sampling methodologies are sus-
ceptible to dissolved oxygen entrainment that can make accu-
rately quantifying low concentrations of sulfide even more
challenging. No-purge sampling using passive methods (such
as discrete interval samplers) are more accurate for detecting
363
Cr3(OH)45+
Cr(III)tot
Cr3+
Cr(OH)2+
Cr3(OH)45+
10 12
pH
sulfides, so long as they do not rely on permeation into the
sampler (i.e., passive diffusion bags are incompatible with sul-
fide analysis and HydraSleeves® or SNAP Samplers® or others
are more appropriate). This leaves a logical question about the
practicality of relying on sulfide to engineer metal precipita-
tion. The following calculation will show that relatively low
concentrations of sulfide (S2−) are needed to form metal sul-
fide precipitates by reacting with hydrogen sulfide (H2S) at
typical concentrations that can be formed in an anaerobic IRZ
or in a chemical-reducing IRZ. Let us examine, for instance,
the case of ferrous iron (Fe2+). The dissociation constant for
solid ferrous sulfide (FeS(s)) from Table 7.5 is
FeS(s) ® Fe(2aq+ ) + S(2aq- ) (7.51)
[ Fe 2 + ][S2 - ] = 1 ´ 10 -19 (7.52)
Note that because ferrous sulfide (FeS(S)) is assumed to be in
the solid phase, the dissociation constant expression shown
in Equation 7.52 of products over reactants is simplified by
recognizing that pure solids and liquids are unity due to their
insensitivity to equilibrium with dissolved species.
Based on the sequential equilibrium expressions for hydro-
gen sulfide (H2S) and bisulfide (HS- ) (which were presented
in Section 7.3.1.1.3.1) and sulfide (S2- ) (presented for the first
time here), we get
H 2S(aq ) ® HS(-aq ) + H (+aq )
[HS- ][H + ]
= 1 ´ 10 -7 (7.53)
[H 2S]
HS(-aq ) ® S(2aq- ) + H (+aq )
[S2 - ][H + ]
= 1 ´ 10 -18 (7.54)
[HS- ]
364
The dissociation constant for hydrogen sulfide (H2S) may be
written as
[H 2S]
[S2 - ] = 1 ´ 10 -25 ´ (7.55)
[H + ]2
Therefore, if we substitute the expression for sulfide [S2−] form
Equation 7.55 into Equation 7.52 and rearrange algebraically,
we obtain an expression for how much ferrous iron (Fe2+) can
be precipitated from groundwater for a corresponding con-
centration of dissolved sulfide (as hydrogen sulfide [H2S]) at
a given pH:
[H + ]2 1 ´ 10 -19 [H + ]2
[ Fe 2 + ] = ´ = ´ 1 ´ 106 (7.56)
[H 2S] 1 ´ 10 -25 [H 2S]
Therefore, at a typical hydrogen sulfide (H2S) concentration
of 1 mg/L (2.9 × 10 −5 M) and a pH of 7.0 ([H+] = 1 × 10 −7 M),
approximately 19 mg/L of ferrous iron (Fe2+; 3.4 × 10 −4 M)
will be precipitated from groundwater as ferrous sulfide. Since
ferrous sulfide is one of the more-soluble sulfides (Tables 7.5
and 7.7), it can be seen that metals whose sulfides have even
lower solubility products will form even more readily at lower
H2S concentrations.
7.4.1.3.3  Case Study Comparisons
A brief case study (Site 1) in the Eastern United States is dis-
cussed here comparing nickel precipitation using biologically
generated sulfide in  situ to target nickel sulfide (NiS) pre-
cipitation and nickel hydroxide (Ni(OH)2) formation through
pH adjustment with magnesium hydroxide (Mg(OH)2) and
sodium hydroxide (NaOH). A second case study (Site 2) is
presented describing the sensitivity of nickel precipitation
to acidity. To facilitate the discussion, recall Equations 7.28
through 7.34 in Section 7.4.1.1.
7.4.1.3.3.1  Site 1  Sulfide can be added to an aquifer
through direct chemical injection (polysulfides, dithionite,
bisulfite; 7.3.1.1.3) or created in situ through indirect micro-
bial transformation. The reduction of ambient sulfate (SO42−)
occurs when sulfate-reducing bacteria (SRBs) oxidize carbon
substrates and use sulfate (SO42−) as the electron acceptor.
The net result of the process is the production of hydrogen
sulfide (H2S) and alkalinity (HCO3−). Metal sulfide precipi-
tates have been generated in laboratory experiments and at
the field-scale utilizing hydrogen sulfide (H2S) from bacte-
rial sulfate reduction.15,18,102–106 Sulfate reduction is strictly
an anaerobic process, and it proceeds only in the absence of
oxygen. The process requires a carbon substrate to support
microbial growth, a source of sulfate (SO42−), and a popula-
tion of SRBs. Dilute black strap molasses solution is an ideal
carbon substrate for this purpose since typical black strap
molasses contains approximately 20% sucrose, 20% reducing
sugars, 10% sulfated ash, 20% organic nonsugars, and 30%
water. For the Site 1, a dilute molasses solution was used and
was supplemented with Epsom salt (MgSO4 * 7H2O) as an
Remediation Engineering
additional source of sulfate. For Site 2, molasses alone was
used followed by a sodium carbonate (Na2CO3) buffer.
The geologic setting of Site 1 is stratified glacial deposits
consisting of mostly sands, silts, gravels, and boulders overlay-
ing gneissic bedrock. The depth to water is approximately 18.3
ft bgs, and the ambient sulfate concentration in groundwater
was analyzed to be 30–40 mg/L. The initial pH was measured
at 6.0, which (according to Figure 7.4) was expected to require
mature and crystalline nickel sulfide precipitation to achieve
the specified compliance criterion of 100 μg/L. Over the time
span of 2003–2006, magnesium hydroxide (Mg(OH)2) was
added via soil mixing into the top 2 ft of the saturated zone
in the source area, and two sodium hydroxide (NaOH) injec-
tions were conducted into the top 20 ft of the saturated zone
in the downgradient plume prior to the authors’ involvement
in the remediation. The sodium hydroxide (NaOH) injections
were small volumes of a 50% NaOH solution. The analytical
results of the nickel and measured pH following the hydrox-
ide additions are summarized in Figure  7.25. Breakthrough
of strongly alkaline pH appears to have occurred at Well
A, but the pH returned to near preinjection conditions after
only a few months. No pH influence appears to have been
observed at Well B. Based on the speciation of nickel hydrox-
ide (Ni(OH)2) shown in Figure 7.7, in order to reliably meet
the compliance criterion of 100 μg/L, the pH needs to consis-
tently be above 9.5. The results presented in Figure 7.25 sug-
gest that the required pH could not be achieved, and therefore,
the compliance criterion for nickel (Ni2+) was not achieved.
There are a few potential explanations for why the analytical
results did not achieve the 100 μg/L standard:
• The amount of hydroxide (OH−) added may have
been insufficient to appropriately buffer the pH.
• The distribution of injected hydroxide (OH−) may
have been inadequate due to challenging injection
hydraulics or hydroxide (OH−) consumption within
the influenced radius.
• The ambient groundwater flux may have exerted
a hydroxide (OH−) scavenging demand that was in
excess of the hydroxide (OH−) provided.
Regardless of the exact mechanism, all of the potential expla-
nations, with the exception of challenging injection hydraulics,
underscore the difficulty associated with titrating an aquifer to
a pH several units above ambient pH. When the authors became
involved in the project in 2009, a comprehensive hydrogeologi-
cal tracer study was implemented. The finding from the tracer
study was that injection hydraulics and the groundwater veloc-
ity were amenable to an in situ injection-based remedial design,
further suggesting that hydroxide (OH−) scavenging was the
limitation of the previous magnesium hydroxide (Mg(OH)2) and
sodium hydroxide (NaOH) additions. Therefore, beginning in
August 2012, a large-scale field pilot study was implemented to
test nickel sulfide (NiS) precipitation by indirect microbial sul-
fate reduction. Four injections of dilute molasses and Epsom salt
were conducted over the course of 2 years with routine perfor-
mance monitoring for pH, nickel, total organic carbon (TOC),
In Situ Treatment of Metals
Nickel ISM Mg(OH)2 NaOH Inj
1,000,000
Well A
100,000
10,000
Total nickel (mg/L)
1,000
100
Nickel criterion
10
1 2
1/14/04 10/10/06 7/6/09
FIGURE 7.25  Analytical nickel and pH data following sodium hydroxide (NaOH) injections at an influenced monitoring well (Well A)
and uninfluenced monitoring well (Well B).
sulfate, and methane. The results for three wells, as well as their
corresponding distance from the injection well within the pilot
study area, are presented in Figure 7.26. The baseline concen-
trations of dissolved phase nickel (Ni2+) were less in the three
pilot test wells than Well A and Well B. However, after some
initial porosity flushing that resulted in approximately 150–400
μg/L dissolved nickel (Ni2+) concentrations and after the estab-
lishment of strongly reducing conditions (as evidenced by the
presence of dissolved phase methane in excess of 1 mg/L) in the
presence of sulfate greatly above background concentrations,
the concentration of dissolved phase nickel (Ni2+) downgradi-
ent of the injection well is below the 100 μg/L compliance cri-
terion. The pH appears to fluctuate between 6.0 and 8.0, but
is typically closer to 6.0. This implies that the nickel sulfide
(NiS) precipitates formed as a result of the bacterial reduction
of sulfate formed crystalline nickel sulfide (NiS) precipitates
that are stable at a pH that is slightly more acidic than predicted
in Figures 7.4 and 7.7.
7.4.1.3.3.2  Site 2  Nickel that is used in plating solutions is
supplied by highly soluble salts such as nickel chloride (NiCl2,
solubility = ~40% [anhydrous] to ~72% [hexahydrate] by weight
at 20°C) and nickel sulfate (NiSO4, solubility = ~39% [anhy-
drous] to ~44% [heptahydrate] by weight at 20°C), buffered to
pH in the range of 4.0–4.5 with a boric acid buffer (H3BO3). pH
adjustment alone would not reduce the soluble fraction of nickel
(Ni2+) to acceptable levels. A lasting remedial strategy can be
designed that supplies competing anions (i.e., S2−) to react with
nickel (Ni2+), forming insoluble nickel compounds (i.e., NiS).
A nickel-containing plating solution was released to a shal-
low groundwater underneath a commercial plating facility
in the Midwestern United States creating a dissolved nickel
365
pH Nickel ISM Mg(OH)2 NaOH Inj pH
12 1,000,000 12
Well B
100,000
10 10
10,000
Total nickel (mg/L)
8 8
1,000
pH
pH
6 6
100
4 Nickel criterion 4
10
1 2
4/1/12 1/14/04 10/10/06 7/6/09 4/1/12
(Ni2+) source zone that fed a plume of more than 1,000 mg/L
Ni2+ outside of the building footprint. Migration of nickel-
contaminated groundwater reached off-site, with concentra-
tions at the site perimeter in excess of the regulatory limit of
0.1 mg/L for drinking water protection. Because nickel (Ni2+)
was observed to reach the site perimeter in excess of the reg-
ulatory limit, it is apparent that the persistent nickel (Ni2+)
source from the plating solution in this case study example
exhausted the aquifer’s ability to retard nickel (Ni2+) transport
through adsorption, cation exchange, etc. Removal of the plat-
ing solution from the release point alone would not eliminate
nickel (Ni2+) migration or the stored dissolved nickel (Ni2+)
within the immobile fraction of the aquifer (additional dis-
cussion of contaminant source distribution and migration pat-
terns can be found in Chapter 4).
A biological reactive zone was established to remove dis-
solved nickel (Ni2+) from the groundwater, by forming durable
precipitates. Carbon substrate injections (i.e., molasses) were used
to provide a carbon source to facilitate the requisite anaerobic
metabolism and to supply sulfate (SO42−) that supports SRBs.
In combination, this reagent provides a low oxidation–reduction
potential, and a high-sulfide chemical environment, in which
nickel sulfide (NiS) can precipitate. Nickel sulfide (NiS) is an
insoluble salt with equilibrium concentrations far below 1 mg/L at
neutral aquifer pH. Because the sulfide anion (S2−) is a strong base
(Section 7.3.1.1.3.1), sulfide scavenging occurs at low pH, drawing
nickel sulfide (NiS) into solution. Therefore, as with most in situ
metal precipitation strategies, acidity neutralization is a key to
instill permanence of the metals removal from groundwater.
The biological reactive zone injections succeeded in
providing the low oxidation–reduction potential and avail-
able sulfide required to precipitate nickel sulfide (NiS).
366 Remediation Engineering

AOW-01I, 7 ft from AIW-01I

NJDEP Ni criterion Nickel pH
Injection #1 Injection #2 Injection #4 10
400
350 Injection #3
8

Total nickel (µg/L)

Field pH (s.u.)
300
250
6
200
150
100 4
50
0 2
0 50 100 150 200 250 300 350 400 450 500 550 600

100,000 TOC 20
Sulfate
10,000

TOC and sulfate (mg/L)

Methane 15

Methane (mg/L)
1,000
10
100
5
10

1 0
0 50 100 150 200 250 300 350 400 450 500 550 600
Elapsed time (days)
(a)

AOW-05I, 7 ft from AIW-01I

NJDEP Ni criterion Nickel Field pH

Injection #1 Injection #2 Injection #4 10

400
350 Injection #3
Total nickel (μg/L)

Field pH (s.u.)
300
250 6
200
150
100 4
50
0 2
0 50 100 150 200 250 300 350 400 450 500 550 600

100,000 20
TOC
TOC and sulfate (mg/L)

10,000 Sulfate
15
Methane (mg/L)

Methane
1,000
10
100
5
10

1 0
0 50 100 150 200 250 300 350 400 450 500 550 600
Elapsed time (days)

(b)

FIGURE 7.26  At-a-glance charts for field data from a carbon substrate injection to facilitate nickel sulfide (NiS) formation at various dose
response wells located downgradient of a single injection well. (a) through (c) show the different responses and contaminant trends from
different dose response wells. (Continued)
In Situ Treatment of Metals 367

AOW-03I, 33 ft from AIW-01I

NJDEP Ni criterion Nickel Field pH
Injection #1
4000 Injection #2 Injection #4 10
3500

Total nickel (μg/L)

Injection #3
3000 8

Field pH (s.u.)
2500
2000 6
1500
1000 4
500
0 2
0 50 100 150 200 250 300 350 400 450 500 550 600

100,000 20

TOC and sulfate (mg/L)

TOC
10,000
Sulfate 15

Methane (mg/L)
1,000 Methane
10
100
5
10

1 0
0 50 100 150 200 250 300 350 400 450 500 550 600
Elapsed time (days)

(c)

FIGURE 7.26 (Continued)  At-a-glance charts for field data from a carbon substrate injection to facilitate nickel sulfide (NiS) formation
at various dose response wells located downgradient of a single injection well. (a) through (c) show the different responses and contaminant
trends from different dose response wells.

The production of organic acids due to incomplete oxidation
of the carbon substrate created acidity in the early phases of
the reactive zone development. This generated partial dis-
solution of nickel sulfide (NiS). This was evidenced by an
increase in dissolved nickel (Ni2+) concentrations each time
the pH declined, as seen in Figure 7.27, which shows nickel
(Ni2+) concentrations in groundwater immediately outside the
plating building footprint. Sodium carbonate (Na2CO3) buffer
10,000
Nickel concentrations (mg/L)
was added along with molasses during reactive zone injec-
tions after day 1,200. Notice in Figure 7.27 the sharp rise in
pH and simultaneous marked decrease in dissolved nickel
(Ni2+). This stabilized the pH and allowed the durable nickel
sulfide (NiS) precipitate to form.
7.4.1.4  The “Matrix Effect”
Oxidation–reduction processes can induce strong acidifica-
tion or alkalinization of soils and aquifer systems. Oxidized
components are more acidic (sulfur as sulfate [SO42−] and
8.0
nitrogen as nitrate [NO3−]) than their reduced counterparts
6.0 (sulfur as hydrogen sulfide [H2S] and nitrogen as ammonia

1,000
[NH3]). As a result, alkalinity and pH tend to increase with
4.0 reduction and decrease with oxidation. Carbonates (CO32−)
100 are efficient buffers in natural aquifer systems in the neutral
pH range. Many processes can cause changes in the oxidation-
pH

10 reduction conditions in an aquifer. Infiltration of water with

high dissolved oxygen concentration, natural fluctuations in
1 the groundwater elevation, introduction of contaminants that
pH are readily degradable and the resultant increased microbial
Nickel
activity, and the deterioration of soil structure can impact the
0.1
0 200 400 600 800 1000 1200 1400 1600 oxidation–reduction conditions in the subsurface. However,
Elapsed time (t) there is an inherent capacity to resist oxidation–reduction
changes in natural aquifer systems. This inherent capacity (or
FIGURE 7.27  Strong dependence of nickel (Ni2+) precipitation “the matrix effect”) depends on the availability of naturally
on pH. pH is shown by black squares and nickel is shown in triangles. occurring oxidized or reduced species. Oxidation–reduction
368
buffering is provided by the presence of various electron
donors and electron acceptors in the aquifer.
In  situ metal precipitation is designed to consider how
manipulating oxidation–reduction reactions will influence
ambient conditions, in addition to immobilizing the targeted
contaminants within the applicable residence time. The matrix
effect is an important predesign consideration to understand
the permanence of the targeted metal precipitate as well as
the required reagent dose to achieve the targeted geochemis-
try while minimizing lingering secondary water quality con-
cerns. Furthermore, careful evaluation is necessary regarding
the selectivity of the injected reagents toward the target con-
taminants and the potential to react with other compounds
or aquifer materials. Short-term and long-term monitoring is
used to determine whether the natural equilibrium conditions
can be restored at the end of the remediation process. In some
cases, modified biogeochemical equilibrium conditions may
have to be maintained over a long period of time to prevent the
rebound of contaminant concentrations. This consideration is
a differentiator between chemical and biological in situ metal
precipitation strategies (Section 7.4.1.2.2).
Metal precipitates resulting from an IRZ may move in
association with colloidal particles or as particles themselves
of colloidal dimensions (Section 7.4.1.2.4). The transport of
contaminants as colloids may result in unexpected mobil-
ity of precipitates thought to be insoluble post-treatment. It
is important to remember that the transport behavior of col-
loids is determined by the physical/chemical properties of
the colloids as well as the soil matrix. Concerns of potential
colloidal transport of targeted metal precipitates can be man-
aged through factual communication of colloidal transport
with stakeholders and bench-scale treatability testing using
columns.
In aquifer systems with high iron concentrations, the amor-
phous HFO can be described as an amphoteric ion exchange
media. As pH conditions change, it has the capacity to offer
hydrogen ions (H+) or hydroxyl ions (OH−) for a cation or an
ion exchange, respectively. Adsorption behavior is primar-
ily related to pH (within the typical range of 5.0–8.5), and at
typical average concentrations in soil, the iron in a cubic yard
of soil is capable of adsorbing from 0.5 to 2 lb of metals as
cations or metallic complexes. This phenomenon is extremely
useful for the removal of arsenic (As), selenium (Se), and
chromium (Cr).
In  situ treatment with a chemical reductant will change
the aquifer mineralogy composition and create new miner-
als that may contribute to metal removal from groundwater.
Typically, the most important matrix minerals are the forma-
tion of iron sulfide (FeS) and pyrite (FeS2). Transition met-
als (Cd, Cr, Pb, Ni, Zn) have a high affinity to iron sulfide
(FeS) minerals. This affinity can result in the removal of dis-
solved phase metals through sorption, coprecipitation, and/or
ion exchange with iron sulfide (FeS) minerals. Formation of
iron sulfides (FeS) have been used previously for metals treat-
ment in anoxic sediments107,108 and other anaerobic conditions
where formation of these minerals is favorable.18 Along with
iron sulfides (FeS), the formation of aluminum hydroxide
Remediation Engineering
(Al(OH)3) and carbonate (CO32−)/sulfate (SO42−) minerals can
enhance the sorption capacity of the aquifer materials.
7.4.1.5 Hydration
Another aspect of the behavior of dissolved metals in ground-
water systems is that metal cations attract a hydration shell
of water molecules by electrostatic attraction to the positive
charge of the cation. This happens because the water mol-
ecules are polar, and the following reaction is an example of
Lewis acid/base interaction (metal cation is the Lewis acid
and water is the Lewis base).
H2 O
Me n + ® Me(H 2O)nx + (7.57)
where x = 6 for most metals.
Hydrated metal ions behave as acids by donating protons
(H+) to H2O molecules, forming the acidic H3O+ hydronium
ion. The process can continue stepwise up to n times to make
a neutral metal hydroxide. For example, with Fe3+ it takes
three proton transfer steps to form ferric hydroxide109:
Fe(H 2O)33+ + 3H 2O ® Fe(OH)3 ¯ + 3H 2O + (7.58)
With each step, the hydrated metal is progressively deprot-
onated, forming polyhydroxides and becoming increasingly
insoluble. Eventually, the metal precipitates as a low solubility
hydroxide.
7.4.2 Technology Type
Before implementing an in situ metal precipitation approach,
it is important to understand the limits of what is achievable
by determining the solubility of the precipitated solids. In
addition, the compatibility of the reactions with the ambi-
ent environment should also be evaluated to avoid potential
adverse impacts. The solubility profiles for crystalline nickel
carbonate (NiCO3), nickel hydroxide (Ni(OH)2), and nickel
sulfide (NiS) are presented in Figure 7.7. The solubility pro-
files indicate that the aqueous nickel concentration will vary
significantly depending on the pH and the solid-phase con-
trolling solubility. Furthermore, the pE–pH stability diagram
for the nickel–carbon–sulfur–water system is presented in
Figure 7.7, and suggests that the oxidation–reduction potential
also influences the resultant precipitation reactions. Failure
to consider these crucial parameters prior to targeting one of
these precipitate forms can lead to an incorrect remedy and an
unfavorable outcome (Section 7.4.1.3.3.1).
The implementation of in  situ metal precipitation occurs
in the aquifer, and the success of the strategy is based on
understanding the precipitation chemistry and effectively dis-
tributing the injected reagent (Chapter 6). From a chemical
treatment perspective, the extent of the IRZ is typically lim-
ited to the engineered IRZ, with clean water flushing extend-
ing downgradient. From a biological treatment perspective,
the injection of an organic carbon substrate may cause an
expansion of the engineered IRZ downgradient, depend-
ing on the solubility of the substrate. For both strategies,
In Situ Treatment of Metals
an appreciation of the hydrogeological heterogeneities and
anisotropies is critical. For physical removal/flushing strat-
egies (i.e., groundwater extraction or dynamic groundwater
recirculation [DGR]), the distribution of an amended reagent
will be more heavily influenced by injection and extraction,
but achieving distribution/hydraulic control will still be influ-
enced by the hydrostratigraphy.
7.4.2.1  Reactive Zones
A reactive zone is defined here as achieving in situ metal precip-
itation in the influenced portion of the aquifer. In other words,
the immediate ROI around the injection points where the chemi-
cal reagent or organic carbon substrate was injected. The estab-
lished or engineered IRZ is characterized by relatively extreme
geochemistry compared to the ambient aquifer. It is important to
distinguish chemical from biological reactive zones.
As treated groundwater begins to leave the engineered IRZ,
a clean water front will develop and downgradient dilution
may occur. For chemically induced IRZs, the total length of
the IRZ and clean water flushing is less than the IRZ and clean
water flushing length associated with a biologically induced
IRZ that uses a soluble organic carbon substrate. Secondary
water quality concerns associated with in situ metal precipi-
tation will generally follow this clean water flux; however,
many of the secondary water quality concerns will attenuate
over this distance as ambient geochemistry is reestablished.
The overall duration of the in situ metal precipitation strategy
and the required number and frequency of injections depends
on the stored contamination (in the immobile fraction of the
aquifer) and any upgradient impacts becoming available for
treatment. In other words, the mobile fraction is typically
treated first during injection (for chemically induced IRZs) and
postinjection (for biologically induced IRZs). Over time, equil-
ibration between the mobile and immobile fractions can cause
an increase in the measured groundwater concentrations, but
actually represents an overall reduction of stored contamina-
tion. Subsequent injections can be timed to match the time to
realize maximum equilibrated contaminant concentrations.
7.4.2.1.1  Chemical Reactive Zones
The injection of chemical reagents and the associated acid-
ity/alkalinity neutralization or metal precipitation typically
occurs instantaneously. Unstable geochemical reactions seek
equilibrium in as little as time as possible—often times barely
measureable in a laboratory setting.18 Additionally, second-
ary scavenging reactions (typically with oxygen) are also
characterized by rapid kinetics. Therefore, it is impractical to
assume that the injection of chemical reagents will influence
anything significantly greater than the furthest extent of dis-
tribution achieved during the injection. Aside from the rapid
kinetics associated with the targeted reactions, the typical
chemical reagents selected for in situ metal precipitation are
consumed by ancillary geochemical reactions with the natu-
ral groundwater and soil. For example, if ferrous iron (Fe2+)
is injected to facilitate the reduction of hexavalent chromium
(Cr6+) to trivalent chromium (Cr3+) in groundwater that is
mildly oxidizing, a significant portion of the injected ferrous
369
iron (Fe2+) may be scavenged by associated chemical and bio-
logical reactions. If reactive sulfide (S2−) is selected to induce
metal sulfide precipitation in an acidic source release from
a former metals galvanizing operation, the sulfide (S2−) will
be scavenged by the acidity, which will significantly reduce
the achieved sulfide (S2−) within the injected ROI. For some
chemical reagents, preparatory mixing and ex  situ dilution
to achieve the design injection concentration may adversely
influence the achievable loading. For example, polysulfides
(Sn2−) are unstable in water at low concentrations, and the sul-
fide (S2−) can be immediately oxidized to elemental sulfur (S0),
which precipitates out of solution as a yellow precipitate. This
means trying to dilute polysulfides (Sn2−) ex situ for injection
is impractical, and it results in a significant loss of the reac-
tive sulfide (S2−) prior to the injection. One potential method
for injection of polysulfides (Sn2−) the authors have used is to
inject the design determined mass of polysulfide (Sn2−) in the
concentrated and nondiluted form (as a low volume) and then
chase the polysulfide (Sn2−) with potable water to achieve the
design determined injection volume. This approach achieves
the greatest percentage of delivered reactive sulfide (S2−), but
may be compromised by poor distribution at the maximum
extents of the targeted ROI. This method is effective with
closely spaced injection points, which target a lower injection
volume per injection point to achieve the targeted distribution.
Therefore, it is important to understand that the radial extent
of a chemically focused in  situ metal precipitation strategy
(regardless of the deployment strategy) is limited to aquifer
influenced during the application. An example of a chemical
reactive zone is discussed here.
Dissolved hexavalent chromium (Cr6+) can be precipitated
as chromium hydroxide (Cr(OH)3) in a chemically reducing
reactive zone by the injection of a ferrous sulfate (FeSO4) solu-
tion at appropriate concentrations. Ferrous sulfate (FeSO4) is
safe to use, is cost comparable, and often produces additional
benefits by co precipitating other heavy metals. Hexavalent
chromium (Cr6+) exists as chromate (CrO42−) under neutral
or alkaline conditions and dichromate (Cr2O72−) under acidic
conditions. Chromate (CrO42−) interaction with ferrous ion
(Fe2+) is summarized in several potential reactions in Section
7.3.1.1.3.2 (Equations 7.7 through 7.10). A potential reaction
mechanism for dichromate (Cr2O72−) is shown under acidic
conditions in the following equation:
2- 2+ + 3+ 3+
Cr2O7 + 6Fe + 14H ® 2Cr + 6Fe + 7H 2O (7.59)
Both trivalent chromium (Cr3+) and ferric iron (Fe3+) ions are
relatively insoluble under natural conditions of groundwater
(neutral pH or slightly acidic or alkaline conditions).
Using ferrous sulfate heptahydrate (FeSO4 * 7H2O) to pre-
cipitate hexavalent chromium (Cr6+) in a chemically reducing
reactive zone may create acidic conditions, as predicted by the
more holistic reaction in the following equation:
3(FeSO 4 * 7H 2O) + CrO 4 2 - ® Cr(OH)3 + 3(Fe(OH)3 )
+ 3SO 4 2 - + 13H 2O + 4H + (7.60)
370
This reaction includes the dissociation of ferrous sulfate hepta-
hydrate (FeSO4 * 7H2O) into water, the reduction of hexavalent
chromium (Cr6+) to trivalent chromium (Cr3+), the oxidation of
ferrous iron (Fe2+) to ferric iron (Fe3+), and the formation of
separate chromium hydroxide (Cr(OH)3) and iron hydroxide
(Fe(OH)3). Note the separate chromium hydroxide (Cr(OH)3)
and iron hydroxide (Fe(OH)3) compounds in Equation 7.60
differ from the chromium–iron–hydroxides predicted by
Patterson et al.35 in Equations 7.9 and 7.10 (4[Cr0.75Fe0.25](OH)3
and 4[Cr0.25Fe0.75](OH)3, respectively). The chromium hydrox-
ide (Cr(OH)3) and iron hydroxide (Fe(OH)3) are separate in
Equation 7.60 only to avoid the implication of one chromium–
iron hydroxide forming over another as Patterson et al. sug-
gest the predominant formation is associated to pH. Although
Equation 7.60 shows some acidity is generated (4  mol H+),
nothing is known about the buffering capacity of this example
aquifer. It is, however, noteworthy to mention that if consider-
able ferrous sulfate heptahydrate (FeSO4 * 7H2O) is neces-
sary due to high hexavalent chromium (Cr6+) concentrations,
soda ash (Na2CO3) or sodium hydroxide (NaOH, caustic soda)
may be necessary to neutralize the pH to circumneutral con-
ditions and helpful in forming whichever chromium–iron
hydroxides form.
7.4.2.1.2  Biological Reactive Zones
Biologically engineered IRZs are generally separated into sol-
uble and sparingly soluble carbon substrates (Chapter 6). More
soluble carbon substrates (e.g., molasses, lactate, alcohols) are
readily distributed throughout the aquifer as forms of dis-
solved TOC, and then propagate downgradient postinjection.
The typical half-life associated with dissolved TOC observed
by the authors ranges from 20 to 40  days, and with typical
achieved TOC dosing concentrations ranging from 100s to
1,000s mg/L, it is not unrealistic to expect carbon propagation
approximately 50 days of groundwater travel time downgradi-
ent (approximately tens to hundreds of feet). Less soluble (i.e.,
sparingly soluble) carbon substrates (e.g., soybean oil, mulch/
compost, chitin) are somewhat similar to chemical reagents as
the distribution of the substrate is achieved during placement,
and there is minimal to little downgradient propagation of dis-
solved TOC downgradient. Biological IRZs (both soluble and
sparingly soluble substrates) differ from chemical reagents
because the achievable residence time of the organic carbon
substrate is significantly longer. Soluble substrates (based on
the rate of groundwater flux) may sustain carbon for months to
quarters, and sparingly soluble substrates may sustain carbon
for several years. The ITRC cites approximately 8  years of
treatment of permeable reactive barriers (PRBs) using biolog-
ical substrates.110 Considerable detail and lessons learned on
organic carbon substrate injection is presented in Chapter 6.
An additional benefit of biological IRZs for in situ metal pre-
cipitation is the geochemical cycling (particularly of iron)
that occurs as a result of establishing strongly reducing con-
ditions. Geochemically reduced iron (in the form of ferrous
iron [Fe2+]) can be used as a chemical reductant for oxidation–
reduction potential sensitive metal precipitation reagents (e.g.,
hexavalent chromium [Cr6+] to trivalent chromium [Cr3+],
Remediation Engineering
uranyl [UO22+] to uraninite [UO2] ). Therefore, the potential
for metal precipitation occurs not only from enzymatic bacte-
rial reactions but also from an imposed capacity for chemical
reduction. Moreover, as the soluble ferrous iron (Fe2+) travels
with groundwater downgradient, it may be oxidized back to
ferric iron (Fe3+) as the ambient geochemistry is reestablished,
creating sorption sites for soluble arsenic or other metals that
are substituted into the iron oxyhydroxide mineral structure.
In  situ biological reduction of hexavalent chromium
Cr(6+) to trivalent chromium (Cr3+) yields significant reme-
dial benefits because trivalent chromium (Cr3+) is less toxic,
comparatively insoluble in groundwater, and thus immobile
and precipitates out of groundwater, typically as chromium
hydroxide (Cr(OH)3). Intrinsic biological reduction via natu-
ral attenuation of hexavalent chromium (Cr6+) to trivalent
chromium (Cr3+) within an aquifer is a viable groundwater
remediation strategy, so long as numerous lines of geochemi-
cal evidence support hexavalent chromium (Cr6+) removal
from groundwater. Many facultative anaerobes are capable
of reducing hexavalent chromium (Cr6+) to trivalent chro-
mium (Cr3+) under the appropriate conditions. Chromium-
reducing bacteria belong to a variety of genera such as
Achromobacter, Aeromonas, Agrobacterium, Bacillus,
Desulfovibrio, Enterobacter, Escherichia, Micrococcus, and
Pseudomonas.111 Although hexavalent chromium (Cr6+)-
reducing bacteria are widespread, high cell densities are
required for significant hexavalent chromium (Cr6+) reduction
to occur. The oxidizing potential of hexavalent chromium
(Cr6+) may present a source of toxicity to bacterial cells. In
addition to the enzymatic mechanism of hexavalent chromium
(Cr6+) reduction, at high concentrations, hexavalent chromium
(Cr6+) may directly interact with various intracellular reduc-
ing agents once it has penetrated the cells.
The mechanisms of hexavalent chromium (Cr6+) reduction
under the induced reducing conditions can be
1. A bacteria-mediated reduction process involving
hexavalent chromium (Cr6+) as a terminal electron
acceptor for the metabolism of the carbon substrate
2. An extracellular reaction with by-products of sulfate
(SO42−) reduction such as hydrogen sulfide (H2S)
3. Abiotic oxidation of the organic compounds includ-
ing the soil organic matter such as humic and fulvic
acids112
A successful case study example of in situ biological reduc-
tion of hexavalent chromium (Cr6+) is discussed here. A site
in the eastern United States was impacted with hexavalent
chromium (Cr6+) concentrations in bedrock groundwater
>10,000  μg/L extending off-site, accounting for more than
90% of the total chromium (Crtot) in the source area. The site
hydrogeology is characterized by overburden materials from
ground surface to approximately 6–20 ft below ground sur-
face, consisting primarily of reddish-brown silty sand and
sandy clayey silt—similar to till material. Groundwater is
first encountered within the bedrock underlying the overbur-
den material to the maximum depths explored. The bedrock
In Situ Treatment of Metals
is described as alternating layers of reddish-brown, highly
fractured siltstones and white to tan sandstones exhibiting
variable competency. The permeability and contaminant stor-
age within the bedrock formation is controlled by fractures,
bedding planes, joints, and other secondary porosity features.
The sedimentary beds strike northeast and dip between 7°
and 12° to the northwest. In bedrock systems, groundwater
flow is typically along strike, and the groundwater flow direc-
tion at this site was along strike to the northeast.
In situ biological reduction of hexavalent chromium (Cr6+)
was implemented in phases across the site, beginning in
February 2006 with the installation of three injection wells
immediately off-site and approximately monthly injections
of a 0.5% by volume molasses solution to stimulate naturally
occurring bacteria and establish reducing conditions. Twelve
injections were implemented from February 2006 until May
2007. Injection events lasted approximately 1 week and
included approximately 7,000 gal of 0.5% molasses solution
into each injection well. A progression of the hexavalent chro-
mium (Cr6+) plume is shown in Figure 7.28, and representative
off-site and on-site wells are presented as time series plots
in Figure 7.29. The difference in the baseline and 8 months
hexavalent chromium (Cr6+) distribution is attributed to the
injections off-site. Note in Figure 7.29 that the preinjection
total chromium (Crtot) and the hexavalent chromium (Cr6+) are
nearly identical, and after injection, the hexavalent chromium
(Cr6+) decreases to below the laboratory detection limit of
10 μg/L. The total chromium also decreases, but not to below
laboratory detection limits and not as abruptly as hexavalent
chromium (Cr6+) due to slightly soluble trivalent chromium
Baseline
~600 ft
Cr(VI) in groundwater
20 Months
Active remediation
completed in ~24 months
Injection wells
FIGURE 7.28  Hexavalent chromium plume progression over a 7-year operation and maintenance of an in situ reactive zone.
371
(Cr3+) hydroxide complexes. For example, Rai et al.113 discov-
ered that trivalent chromium (Cr3+) carbonate complexes are
significant across a wide range of pH (3.0–13.0), particularly
in the forms of Cr(OH)(CO3)22− and Cr(OH)4CO33−. The dis-
tinguishable difference between hexavalent chromium (Cr6+)
and total chromium (Crtot) reductions provides evidence that
the hexavalent chromium (Cr6+) reduction is attributable to
in situ biological reduction and not dilution/displacement. If
the hexavalent chromium (Cr6+) were merely diluted or dis-
placed, there would be a similar marked decrease in total
chromium (Crtot). Moreover, after the dilution effect dissi-
pated, the hexavalent chromium (Cr6+) would be expected to
increase (i.e., “rebound”). This is not observed, and, without
an injection event in over 7 years, the hexavalent chromium
(Cr6+) concentration remains below laboratory detection lim-
its. The second time series plot in Figure 7.29 represents an
on-site well and injections of 0.5% molasses that were con-
ducted beginning in 2008. Similar results were observed on-
site, and the 20-month and 7-year hexavalent chromium (Cr6+)
plume distribution is shown in Figure 7.28 as a result of con-
ducting on-site injections.
Finally, in Figure 7.30, the geochemical response is shown
for the representative off-site well. The injection events, the total
chromium (Crtot), and the hexavalent chromium (Cr6+) have been
grayed to emphasize the geochemical response. Geochemical
parameters were monitored over the course of injections during
off-site injections to garner regulatory support of broader imple-
mentation. The data show a classic response to carbon substrate
injections, with dissolved manganese (assumed to represent
manganous manganese [Mn2+]), dissolved iron (assumed to
8 Months
Reduced
groundwater
Biologically
active zone
7 Years
Currently in MNA under
restricted RAO
372 Remediation Engineering

10,000 Off‐site well

Chromium concentration (μg/L)

1,000

100

10

1
11/9/04 3/24/06 8/6/07 12/18/08 5/2/10 9/14/11 1/26/13

(a) Total Cr CrVI Injection

10,000 On‐site well

Chromium concentration (μg/L)

1,000

100

10

1
2/22/08 7/6/09 11/18/10 4/1/12 8/14/13

Total Cr CrVI Injection event

(b)

FIGURE 7.29  (a) Off-site hexavalent (Cr6+) and total (Crtot) chromium concentrations in response to in situ reactive zone (IRZ) injections.
(b) On-site hexavalent (Cr6+) and total (Crtot) chromium concentrations in response to IRZ injections.

represent ferrous iron [Fe2+]), and TOC all showing an increase
over the course of the injection. Alkalinity is presented with
slight increases, likely as a result of the injected carbon being
mineralized to bicarbonate (HCO3−), and confirms adequate
carbonate species to contribute to trivalent chromium (Cr3+)
carbonate complexes. Sulfate (SO42−) shows an order of mag-
nitude decrease suggesting sulfate-reducing conditions may
have been established; however, hexavalent chromium (Cr6+)
was observed to below laboratory detection limits prior to
sulfate-reducing conditions confirming the author’s experience
that iron-reducing conditions are adequate for hexavalent chro-
mium (Cr6+) reduction. This case study demonstrates the rapid,
effective, and permanent remedial benefits of in situ biological
reduction of hexavalent chromium (Cr6+).
Another site showing effective in situ biological reduction
of hexavalent chromium (Cr6+) is presented in Figure 7.31
from a deep aquifer in the Western United States. The geology
at this site is characterized as fluvial deposits with grain size
can vary from course to fine over short distances laterally and
vertically. The depth to groundwater is approximately 80 ft
below ground surface. The analytical data presented in Figure
7.31 were collected from within the IRZ in the source zone,
approximately 30 ft from the injection wells. The baseline con-
centration of hexavalent chromium (Cr6+) was ~1,000  µg/L.
TOC, the surrogate dissolved phase signature of the 60% by
weight sodium lactate solution injected to establish reduc-
ing conditions, began to influence this monitoring location
approximately 1.5 months after injections began. In this case,
In Situ Treatment of Metals
10,000
Chromium concentration (μg/L) 1,000
100
10
1
5/28/2005 12/14/2005
FIGURE 7.30  Off-site geochemical response to implementation of in situ reactive zone for hexavalent chromium treatment.
distribution of TOC to the monitoring location 30  ft from
the injection point was achieved by continuous extraction of
groundwater from downgradient, amendment with sodium
lactate, and reinjection. Hexavalent chromium (Cr6+) shows an
inverse relationship to TOC concentration, which is indicative
of effective treatment. Geochemical parameters monitored
over the same time frame show increases in dissolved man-
ganese (assumed to be manganous manganese [Mn2+]) and
dissolved iron (assumed to be ferrous iron [Fe2+]) as well as
a stable decrease in nitrate (NO3−) and sulfate (SO42−). These
typical changes in ambient geochemistry are consistent with
the onset of reducing conditions and support that the hexava-
lent chromium (Cr6+) reductions observed here were related to
in situ biological reduction.
Hexavalent chromium (Cr6+) is known to be reduced both
aerobically and anaerobically in different bacterial systems. In
anaerobic systems, membrane preparations reduce hexavalent
chromium (Cr6+), and hexavalent chromium (Cr6+) has been
shown to serve as a terminal electron acceptor. Aerobic reduc-
tion of hexavalent chromium (Cr6+) has been found to be asso-
ciated with soluble proteins. The enzymatic basis for aerobic
hexavalent chromium (Cr6+) reduction is not known, but it has
been proposed that hexavalent chromium (Cr6+) may be reduced
by a soluble reductase enzyme with a completely unrelated pri-
mary physiological role. Based on the diversity of hexavalent
chromium (Cr6+)-reducing microorganisms in soil, provision of
a suitable electron donor (such as a carbon substrate) may be
sufficient, and strongly anaerobic and reducing conditions like
during ERD applications are not necessary.114,115 The experience
of the authors at many chromium precipitation sites indicates
that denitrifying or iron-reducing conditions are appropriate for
hexavalent chromium (Cr6+) reduction (e.g., Figure 7.30).
7.4.2.2  Permeable Reactive Barriers
This section discusses in  situ metal precipitation strate-
gies implemented as barriers or PRBs. Reactive barriers as
373
Off‐site well
Total Cr
CrVI
Injection
Alkalinity
Diss Fe
Diss Mn
SO4
TOC
7/2/2006 1/18/2007 8/6/2007 2/22/2008
a concept, with special attention to hydrogeology, are more
deeply developed in Chapter 10. A PRB is a specified length,
width, and depth of reactive treatment reagent, constructed
perpendicular to the groundwater flow direction. A PRB is
typically constructed as an excavated trench that is backfilled
with treatment reagent and clean backfill for structural pur-
poses. It is important to note, however, that a PRB could be
constructed as a transect of injection points, from a horizontal
injection well, as a consecutive series of large diameter auger-
mixed boreholes, or any deployment strategy that results in
a “barrier” perpendicular to the groundwater flow direction.
Over time, the metal-contaminated groundwater naturally
fluxes through the PRB and the targeted chemical/biological
reactions occur resulting in metal precipitation. Biological
PRBs are gaining popularity because recharging the organic
carbon substrate can be completed cost efficiently. Injection
wells can be used to reestablish strongly anaerobic and reduc-
ing conditions when geochemical indicators suggest the ini-
tial carbon substrate application is exhausted. Additionally,
soluble components of carbon substrate can travel downgradi-
ent extending the treatment width of biological PRBs. This
has an added benefit for in  situ metal precipitation specifi-
cally, because there are more reactive species of ferrous iron
(Fe2+) to facilitate metal reduction, and, as the ambient geo-
chemistry is restored downgradient, more sorption sites on
freshly precipitated ferric iron (Fe3+) oxyhydroxides. Reactive
barriers using chemical reagents can be regenerated as well,
but the regeneration is typically more expensive.
A popular chemical reagent for barrier treatment is granu-
lar and microscale ZVI. When installed as a barrier, ZVI can
be emplaced through surgical mixing or backfill replacement
of an excavated trench, which accounts for the difficulty in
achieving distribution through injection. The difficulties of
injecting ZVI were discussed in Chapter 6, but because of
the reasonable cost and high effectiveness of ZVI treatment,
using it in a barrier form is advantageous. A consideration
374 Remediation Engineering

1200

1000

Hexavalent chromium and TOC (mg/L)

Cr6+
TOC
800 Injection begins

600

400

200

0
(a) 8/6/07 11/14/07 2/22/08 6/1/08 9/9/08 12/18/08 3/28/09 7/6/09

50 800

45
700
40
600
Iron,  manganese, nitrate (mg/L)

35

500
30

Sulfate (mg/L)
25 400

20
300
15
200
10
100
5

0 0
8/6/07 11/14/07 2/22/08 6/1/08 9/9/08 12/18/08 3/28/09 7/6/09

(b) Fe2+ NO3– Injection begins Mn2+ SO42–

FIGURE 7.31  (a) Hexavalent chromium (Cr6+) response to an injection of a carbon substrate. (b) Geochemical response to an injection of
a carbon substrate.

of the ambient geochemistry is important when designing a
ZVI PRB because passivation may lead to reduced treatment
performance. Passivation is defined as a mineral or biological
coating over the surface of the ZVI that reduces the treatment
effectiveness by limiting the contact of metals with the ZVI
media. Considerable precipitation buildup will occupy the
available porosity and may lead to channeling of groundwater
through the PRB. Over extended time frames, channeling may
increase the groundwater velocity through the PRB. Since
PRB design is built around maintaining a groundwater flux
through the PRB that achieves a designed contact residence
time, increasing the groundwater velocity will result in a
decreased contact residence time. Additionally, the channel-
ing will focus groundwater through isolated intervals inhibit-
ing groundwater from contacting the full treatment interval. It
is clear that in situ passivation of ZVI in a PRB will adversely
impact the treatment effectiveness, and it is costly to unearth
the reactive media to regenerate treatment capacity. The
authors have implemented an acidic solution circulation to
dissolve away the passivation with some success, though it
was determined that this approach was not cost feasible for
a full-scale application. Although over a long enough time
In Situ Treatment of Metals
frame some degree of passivation will occur, careful evalu-
ation of the overall ambient geochemistry during the design
phase is essential to minimizing operation and maintenance
concerns over the operable time frame of the PRB. Wilkin
et al. demonstrated that the passivation of the subject PRB to
their study experienced more passivation on the upgradient
side than the downgradient side and that passivation reduced
the effective porosity by a maximum of 15% after 8 years of
operation (Section 7.3.1.1.4).44 This relatively minor porosity
reduction suggests the ambient geochemistry and microbiol-
ogy were amenable to the PRB technology.
7.4.2.3 Stabilization
In situ stabilization is primarily a remediation technology for
soils, sediment, and sludge and usually involves mixing the
soils, sediments, and/or sludge. It is commonly referred to as
in situ soil mixing (ISM). Because of the established equilib-
rium between soil and groundwater metal concentrations in a
typical aquifer, it is unnecessary and impossible to separate
the influence of stabilizing soils from decreases in ground-
water concentrations. However, for a large dilute plume that
is primarily associated with the groundwater, there are typi-
cally more cost-effective strategies for in situ metal precipita-
tion than stabilization or ISM. Therefore, this discussion is
focused on in situ stabilization for metals in vadose zone and
shallow saturated zone soil. In in situ soil stabilization/solidi-
fication implementations using chemical reagents, the ISM
influences only the mixed monolith. Many components of the
CSM dictating soil stabilization/solidification as the selected
remedy (i.e., low permeability, unsaturated impacts, insoluble
chemical reagents [i.e., ZVI]) are generally associated with
localized treatment. Additionally, solidification agents can
encapsulate the reagents within the monolith. A more thor-
ough discussion of the in situ stabilization and in situ solidifi-
cation technology is provided in Chapter 9.
Two case studies will be presented and discussed to high-
light the design details associated with in  situ stabilization
and metal precipitation. Both case studies include ferrous iron
(Fe2+) reduction of hexavalent chromium (Cr6+) to trivalent
chromium (Cr3+); however, there are many differences.
Site A was the result of a historical wood treatment system
that used a chromium solution as part of production opera-
tions. Expectedly, the occurrence of chromium concentrations
above cleanup goals is closely associated with storage and
processing areas of the facility. The facility was closed in the
mid-1990s, and remediation related to the chromium impacts
in deep vadose zone soil were conducted in 2014. Based on
historical investigations to determine the nature and extent
of hexavalent chromium (Cr6+), ISM was determined to be
appropriate to achieve the cleanup goals. A delineated volume
of 5,750 yd3 extending over an area of 11,750 ft2 with variable
depths (12.5–37.5 ft bgs) was proposed for ISM. Geologically,
the vadose zone soil is characterized as poorly drained loam,
with thick indurated impermeable hardpan/caliche inclusions.
Areas of the site are classified as interbedded alluvial deposits
generally composed of clay, silty clay, silt, and silty sand. The
depth to water at Site A is generally greater than 40 ft bgs,
375
and in  situ soil stabilization conducted was implemented in
the vadose zone. The established cleanup goal for Site A was
10 μg/L measured using the California Waste Extraction Test
using deionized water (DI-WET) for hexavalent chromium.
In support of this in  situ stabilization implementation, a
phased treatability study was implemented. The first phase
(Phase I) of the treatability study was to test multiple concen-
trations of two forms of available iron: ZVI (Fe0) and ferrous
iron (Fe2+) in the form of ferrous sulfate (FeSO4). The second
phase (Phase II) of the treatability study was to determine if
iron was necessary (i.e., if Portland cement alone could sta-
bilize hexavalent chromium [Cr6+]) and if the mixing needed
to be implemented in stages if iron was necessary (i.e., first
mix the iron and then remix with the Portland cement for
strength). The results of Phase I and Phase II are presented
in Figures 7.32 and 7.33, respectively. The comparison of the
two forms of iron is summarized in Figure 7.32. The control
is shown for day 0 (immediately after mixing), day 3, and day
7 to demonstrate the comparative reductions in the hexava-
lent chromium (Cr6+) concentrations in the leachate associ-
ated with the different percentages of iron added. The cleanup
goal of 10 μg/L is shown as a horizontal line. The sam-
pling frequencies for the two forms of iron differed slightly.
Hexavalent chromium (Cr6+) reductions associated with fer-
rous iron (Fe2+) addition was anticipated to be faster than ZVI
(Fe0), and therefore, trials for ferrous iron (Fe2+) were sampled
at days 0, 3, and 7. Hexavalent chromium (Cr6+) reduction
associated with ZVI (Fe0) trials was sampled at days 0, 3, and
14. A few general conclusions from the data are apparent:
1. Neither ferrous iron (Fe2+) nor ZVI (Fe0) at 0.05%
by weight loading was successful at achieving the
cleanup goal of 10 μg/L. This is likely the result of
insufficient contact of the iron with the hexavalent
chromium (Cr6+) due to the respective concentrations
of the iron being too low.
2. The 0.5% and 1% by weight loading of ferrous iron
(Fe2+) successfully achieved the cleanup goal a few
hours after addition. The actual laboratory results
were below reporting limits. This demonstrates
the high rate of hexavalent chromium (Cr6+) reduc-
tion to trivalent chromium (Cr3+) by ferrous iron.
Based on the size of the volume delineated for ISM
(5,750 yd3), the difference in cost of the ferrous iron
(Fe2+) between the 0.5% and 1% by weight loading
was determined to be approximately $70,000, which
was 3.5 times the cost of the treatability test.
3. The only concentration of ZVI (Fe0) that consis-
tently achieved the goal of 10 μg/L for hexavalent
chromium (Cr6+) was 2% by weight. The 0.5% by
weight ZVI (Fe0) achieved the goal initially after
mixing and after 3 days, but the result of a 14-day
test demonstrated a hexavalent chromium (Cr6+) con-
centration that was an order of magnitude above the
cleanup goal. This observation may be attributable to
the surface adsorption of hexavalent chromium (Cr6+)
onto the ZVI (Fe0) as predicated by Wilkin et al. as
376 Remediation Engineering

Phase I treatability test results

1000

DI wet hexavalent chromium (μg/L)
100

10

0.1
0 2 4 6 8 10 12 14
Elapsed days (days)

Control 0.05% Fe2+ 0.5% Fe2+ 1% Fe2+

0.05% Fe0 0.5% Fe0 2% Fe0 Cleanup goal

FIGURE 7.32  Treatability test results for Phase I of an in situ soil mixing design showing various concentrations of ferrous iron (Fe2+) and
ZVI (Fe0) sampled over a two week period.

Phase II treatability test results

100
DI wet hexavalent chromium (μg/L)

10

1
0 7 14 28
Elapsed days (days)

Control 7.5% PC and 0.5 Fe2+ 7.5% PC and 0.5% Fe0

7.5% PC 6% PC and 0.5% Fe2+ Cleanup goal

FIGURE 7.33  Treatability test results for Phase II of an in situ soil mixing design comparing various Portland Cement (PC) doses to
equivalent ferrous iron (Fe2+) and ZVI (Fe0) doses.

a primary ZVI (Fe0) mediated hexavalent chromium that Portland cement would assist in encapsulating adsorbed
(Cr6+) reduction mechanism.44 Another plausible hexavalent chromium (Cr6+), the 0.5% by weight ZVI (Fe0) was
explanation is passivation of the iron surface due carried on to Phase II. The major objectives of Phase II were
to entrained oxygen during the mixing process. As to determine if iron was actually necessary (i.e., if Portland
Phase I of the treatability test was implemented with- cement could sufficiently encapsulate the hexavalent chro-
out Portland cement, it was hypothesized that ZVI mium [Cr6+] without chemical reduction by iron) and if staged
(Fe0) and Portland cement could still be an effective mixing would be required if iron was necessary. The concen-
formulation. trations of hexavalent chromium (Cr6+) in the leachate were
lower in Phase II than Phase I and is likely a result of variabil-
The results from Phase I suggest that ferrous iron (Fe2+) out- ity in the targeted ISM soil as samples for the treatability test
performed ZVI (Fe0); however, because ZVI was slightly less came from Site A soils during delineation. Regardless of the
expensive than ferrous iron (Fe2+) and it was hypothesized lower hexavalent chromium (Cr6+) concentration, the results
In Situ Treatment of Metals 377

presented in Figure 7.33 suggest that the 7.5% by weight
Portland cement was unsuccessful achieving the cleanup goal
of 10 μg/L without iron. Additionally, the hypothesized syn-
ergy of Portland cement and ZVI (Fe0) was not confirmed.
Therefore, based on the results from Phase II of the treatabil-
ity study and Unconfined Compressive Strength (UCS) testing
on cured cylinders, the treatment reagent formulation of 6%
by weight Portland cement and 0.5% by weight ferrous iron
(Fe2+) was selected for implementation. The soil was treated
in early 2015. In-field testing confirmed the added iron con-
centration and postimplementation UCS testing on represen-
tative cured cylinders confirmed that field conditions matched
the treatability test conditions. Regulatory acceptance and
closure was granted in mid-2015.
The second case study, Site B, was an innovative approach
to the in situ stabilization of chromite ore processing residue
(COPR) in the Eastern United States. Chromate (CrO42−)-
impacted solid material can be a long-term source of hexava-
lent chromium (Cr6+) to groundwater and can be difficult
to treat, particularly in the case of COPR. COPR is the by-
product of historical chromate (CrO42−) production and was
commonly used as fill material due to its favorable structural
quality as a granulated material.43 Materials with significant
concentrations of COPR are characteristically alkaline (pH >
12.0) due to the slow hydration of the primary oxide minerals
comprising the COPR and can exhibit significant cementation.
The elevated hexavalent chromium (Cr6+) concentrations
and pH characteristic of COPR can impede stabilization by
inhibiting microbial activity and limiting the effectiveness of
direct chemical treatment processes. Microbial reduction of
hexavalent chromium (Cr6+) from COPR may be inhibited by
both the elevated pH and the fact that the COPR material may
not be watersaturated (which challenges stimulating anaero-
bic activities and maintaining trivalent chromium (Cr3+) min-
erals).116 Various methods have been explored to treat COPR.
Freese et al. provide a comprehensive and current review of
potential remediation methods and some historical discussion
of previous treatment methods, and a table from their work is
included as Table 7.14. The most common approaches docu-
mented in the literature have involved the use of chemical
reductants, acids, and organic solids. Generally these methods
fall short because of insufficient mineral weathering (leav-
ing enough residual unstable mineral phases to support pH
rebound and long-term heaving potential), ineffective reduc-
tion of hexavalent chromium (Cr6+) to trivalent chromium
(Cr3+) due to scavenging of reducing agents, lengthy treatment
times, and posttreatment reoxidation of trivalent chromium
(Cr3+) to hexavalent chromium (Cr6+).
The innovative approach presented here is a patent pend-
ing multistep process that can achieve permanent and com-
plete biogeochemical stabilization of chromate-impacted
solids, including COPR. The bench-scale treatability study
focused on COPR-impacted soils, with the initial step involv-
ing the addition of a mineral acid (sulfuric acid [H2SO4]).
This achieved an initial drop in pH from ~12.0 to 9.0, accel-
erated weathering of primary oxide minerals (responsible
for cementation, bulking and buffering elevated pH) and
displaced hexavalent chromium (Cr6+) from the solid phases

TABLE 7.14
Partial Comparison of the Chromite Ore Processing Residue Treatment Technologies
Initial Percentage
Technology In Situ Ex Situ Concentration Reduction Advantages Disadvantages
Chemical xa x 95 mg/L <33%, 24 h • Applicable to wide range of • pH buffering can decrease
reduction: contaminant levels efficiency
(FeSO4) 4000 mg/kg 75% • Can treat water and soil • Cr6+ rebound when Fe2+
scavenged
• Requires excess FeSO4
Zero valent x 3.79 g/L 2% (69.3 mg) • Can treat leached material • Only applicable for groundwater
iron (Fe0) • Relatively high rate • Requires small particle size
Chemical x x 7210 >99% • Applicable to soil and water • Only effective at high dosages
reduction: • Can achieve needed
CaSx reductions in 24 h
Pyrolysis x 3400 mg/kg 99%, T > 400°C • Permanent reduction of Cr6+ • Can only be done ex situ
• Not applicable to water
5100 mg/kg 99%, T > 600°C • Lower residence time • Leaves soil nonviable
Biological x x 1917 mg/kg 70%, 24 h anaerobic • Environmentally friendly • Longer treatment times
compared to chemical reduction
40 mg/L 40%, aerobic • Reduce Cr3+ more stable • Highest efficiency with
anaerobic environment
468 mg/kg 90%, anaerobic • Effective for both soil and —
water

Source: Freese, K. et al., Curr. Environ. Eng., 1, 82, 2014.

a An x symbolizes whether the listed technology is applicable in situ or ex situ (or both).
378
making it available for treatment. The second step involved
the addition of ferrous iron (Fe2+) in the form of ferrous sul-
fate (FeSO4) and a fermentable source of organic carbon. In
60  days, the resulting biogeochemical environment reduced
hexavalent chromium (Cr6+) from approximately 21,000 to 35
mg/kg (and toxicity characteristic leaching procedure [TCLP]
from approximately 350 to 3 mg/L), showing that the condi-
tions were persistent enough to support treatment of entrained
hexavalent chromium (Cr6+). This was likely further sup-
ported by oxidation–reduction cycling of the added iron, and
the creation of reduced iron minerals, and additional neutral-
ization of pH to near 7.0 through acidity yielded by fermen-
tation of the carbon source. Testing of the treated materials
4 years after completion of the bench-scale treatability study
shows that the neutral pH remained stable with no rebound
of hexavalent chromium (Cr6+) and little to no bulking of the
samples. Based on the results of the bench-scale treatability
study, a small field-scale pilot study was designed and imple-
mented in 2011.
The small field-scale pilot study was constructed using a
cement-grout slurry wall enclosure that was 30 ft long by 20 ft
wide by 15 ft deep. Within this wall enclosure, a smaller test
cell was actually mixed, measured at 20 ft long by 17.75 ft
wide by 15 ft deep. The top 3 ft was excavated and disposed
of off-site so mixing occurred over a depth of 12 ft. Therefore,
the actual volume of soil mixed was approximately 160 yd3 or
an approximate mass of 237 tons, assuming 1.5 ton per yd3.
The soil within the test cell was characterized as green-gray
mud (lime-rich green dense silt, with minor amounts of fine
sand and clay), COPR (reddish brown coarse- to fine- grained
gravel, with varying amounts of sand and silt), and mixed fill/
COPR (COPR and artificial fill including cinders, brick, glass,
metal, and cement fragments). The gravelly COPR portion of
the matrix is typically defined as nodules from the chromium
manufacturing process that range in size from 1/8 to 3/4 in.
in diameter. The pH of the soil within the test cell was highly
alkaline (pH > 11.0) as would be expected with a high per-
centage of COPR, with high potential for hexavalent chro-
mium (Cr6+) leachability.
Three soil samples were submitted for baseline analysis
of target analyte list metals, hexavalent chromium (Cr6+),
TOC, pH, synthetic precipitation leaching procedure (SPLP),
TCLP, and volatile and semivolatile organic compounds.
Each sample was a composite representation of three dis-
tinct intervals (shallow, middle, and deep). Baseline samples
were also submitted for specialized characterization analyses
including x-ray diffraction (XRD), automated mineralogy
electron-beam analyses (quantitative evaluation of minerals
by SCANning electron microscopy [QEMSCAN]), bulk x-ray
absorption near-edge structure (XANES) spectroscopy, and
micro-x-ray absorption spectroscopy (micro-XAS). A more
in-depth discussion of these different characterization meth-
ods is discussed in Section 7.4.3.
The field-scale pilot study involved four distinct amend-
ments: 50% sulfuric acid (H2SO4), ferrous sulfate hepta-
hydrate (FeSO4 * 7H2O), and two amendments to simulate
microbial activity: (dextrose [C6H12O6; fermentable sugars]
Remediation Engineering
and corn silage [fermenting bacteria]). Results from the
bench-scale treatability study provided the basis for the ini-
tial dosing determinations. The targeted dosing of each of the
amendments was as follows:
1. 50% sulfuric acid (H2SO4): 10 mL per 100 g of soil.
Based on this demand, approximately 5,600 gal of
50% sulfuric acid (H2SO4) was used to treat the
237 tons of soil, translating to an applied dose of 9.8
mL per 100 g of soil.
2. Ferrous sulfate heptahydrate (FeSO4  *  7H2O):
Three moles of ferrous iron (Fe2+) are required to
reduce one mole of hexavalent chromium (Cr6+) to
trivalent chromium (Cr3+) (Equation 7.60). Due to
the expected iron cycling anticipated as part of the
treatment process, the ferrous iron (Fe2+) was inten-
tionally decreased. This observation was recently
documented in the literature.117 In the bench-scale
treatability study, a ratio of 0.5:1 ferrous iron (Fe2+)
to hexavalent chromium (Cr6+) was used and the
results were successful. For the field-scale pilot study,
approximately 6 tons of ferrous sulfate heptahydrate
(FeSO4 * 7H2O) was used, which has a molar ratio of
approximately 0.25:1 ferrous iron (Fe2+) to hexava-
lent chromium (Cr6+).
3. Dextrose (C6H12O6): The minimum dextrose dos-
ing was determined based on reducing equivalents
required for dextrose to reduce the ferric iron (Fe3+)
and hexavalent chromium (Cr6+) present in the Site
B soils, which were the predominant sources of
demand. Approximately 45 kg of dextrose per cubic
meter was added to the treatment cell to target a
TOC concentration of 9,400 mg/kg. Approximately
6 tons of dextrose was added to the treatment cell.
4. Both iron-reducing bacteria (IRBs) and fermenting
bacteria were required to create the reducing con-
ditions required to cycle the oxidation state of iron.
Additionally, SRB reduce the added sulfate (added as
both the ferrous sulfate [FeSO4 * 7H2O] and sulfuric
acid [H2SO4]) to sulfide (S2−), which added another
mechanism for hexavalent chromium (Cr6+) treatment
as sulfide (S2−) has the ability to reduce hexavalent
chromium (Cr6+) to trivalent chromium (Cr3+), at
a pH at or below 7.0.118 As part of the bench-scale
treatability study, qualitative biological indication
tests on retained samples both before and after treat-
ment showed that both IRBs and SRBs were present.
Once stimulated by the addition of iron, sulfate, and
organic carbon, these bacteria were expected to flour-
ish. As such, only fermenting bacteria were added.
During the bench-scale treatability study, corn silage
inoculum was used as a source of fermenting bacteria
and was added as the bioammendment for the field-
scale pilot study. In the study, 100  lbs of inoculum
were used. This number was based upon the amount
of corn silage inoculum to digest a similar volume of
silage, with a safety factor of 2.
In Situ Treatment of Metals 379

North west North east

3. Bio-stimulation process pass: Addition of dextrose
4 ft (C6H12O6) and corn silage inoculum to initiate and
South west South east further enhance the microbial reduction

1 4 ft The sulfuric acid (H2SO4) was added in a controlled and step-

12 ft
20 ft
FIGURE 7.34  In situ soil stabilization treatment cell divided into
three depths and four quadrants.
In order to be as purposeful and systematic as possible, the
treatment cell was divided into three depths and four quad-
rants as shown in Figure 7.34. This provided 12 locations for
consistent measurements of pH and temperature throughout
the addition of sulfuric acid (H2SO4) and reference to loca-
tions for comparison to performance monitoring data post-
implementation. The ISM used a long-stick excavator and
consisted of the following treatment steps:
1. Initial process pass: Homogenize the soils within the
test cell and understand the mixing
2. Neutralization process pass: Addition of sulfu-
ric acid (H2SO4) to lower the pH in the soils, fol-
lowed by the addition of ferrous sulfate heptahydrate
(FeSO4 * 7H2O) to promote the chemical reduction
of hexavalent chromium (Cr6+)
wise fashion, beginning with a small dose of approximately
50 gal, at which point the acid was mixed immediately with
2 4 ft the excavator bucket. The reaction was observed, and tem-
perature and pH samples were taken. Because the first reac-
tion was controlled, a larger volume was added in the second
3
17.75 ft addition. Once the response of the soil was understood, a
more constant volume of sulfuric acid (H2SO4) was added
and mixed throughout the test cell. The pH and temperature
response observed at different locations throughout the test
cell during sulfuric acid (H2SO4) addition are presented in
Figures 7.35 and 7.36 along with the chronological organi-
zation of the mixing activities. The pH response shown in
Figure 7.35 is exactly what would be expected when adding an
acid to highly alkaline soil, and the pH was observed to con-
sistently become more neutral over the course of sulfuric acid
(H2SO4) addition. The pH was observed to exhibit some buff-
ering capacity with a noticeable decrease in pH and slightly
larger fluctuations in pH after day 14. The buffering capac-
ity was feared to have been significantly overcome with a pH
response of 2.84 at the end of acid addition, but this was likely
only due to incomplete mixing. Mixing was continued to cool
the temperature and the final stabilized pH was observed to be
approximately 5.8. Heat was generated from the exothermic
neutralization reaction between the sulfuric acid (H2SO4),
the alkaline groundwater, and alkaline minerals in the soil.
Cooling was driven by heat loss to the atmosphere and the
surrounding aquifer matrix. Temperature was monitored both
during and after the acid addition, as presented in Figure 7.36.

pH neutralization with addition of 50% sulfuric acid

14.0 0.14

12.0 0.12
Acid dosing (mL acid/g soil)

10.0 0.10

8.0 0.08
pH (s.u.)

6.0 0.06

4.0 0.04

2.0 0.02

0.0 0.00
–2 0 2 4 6 8 10 12 14 16 18 20
Days elapsed

Mobilization Process pass Acid addition begins

pH Acid addition ends Ferrous iron addition
Corn silage and dextrose addition Acid dosing

FIGURE 7.35  Response of pH measurements during corresponding sulfuric acid (H2SO4) addition to the treatment cell.
380
Temperature increase with addition of 50% sulfuric acid
50
45
40
35
Temperature (°C)
30
25
20
15
10
0
–2 0 2
Mobilization
Temperature
Corn silage and dextrose addition
FIGURE 7.36  Response of temperature measurements during sulfuric acid (H2SO4) addition to the treatment cell.
The maximum temperature observed of 43.8°C was 34.2°C
greater than the ambient temperature. In addition to heat gen-
eration, suspected carbon dioxide (CO2) gas was also released
through the reaction between the acid and carbonate minerals
present in the soil. Foaming was observed at the surface, but
acid dosing was managed such that unsafe conditions were
not created by gas generation. In addition, the mixing was
conducted within an exclusion zone, and workers within the
exclusion zone were equipped with Level B personal protec-
tive equipment (i.e., supplied air through a full-face respira-
tor, full-body chemical resistant suit, chemically resistant
steel-toed boots, chemically resistant elbow-length gloves,
and chemically resistant aprons). Oxygen and carbon dioxide
levels in the work area were monitored during the titration
process, and careful observations were made regarding foam-
ing and evidence of heat generation to regulate the rate of acid
addition. The biostimulation process pass was not initiated
until the temperature was below 45°C. This is the temperature
below which mesophilic bacteria can thrive. Approximately
continuous mixing and periodic temperature checks for
2 days conducted to ensure the temperature was appropriate
for the addition of dextrose and corn silage. Temperature was
measured with an infrared thermometer from the sidewalls of
the treatment cell and by a thermocoupler with temperature
probes at three distinct depths (Figure 7.36). The test cell was
at 18°C when the biostimulation process pass was initiated
and 13°C when it was finished.
Performance monitoring postimplementation was com-
pleted at 1, 4, 7, 10, and 12 months after treatment, and the
results are presented in Figures 7.37 through 7.42. Additional
samples were collected during the final performance monitor-
ing sampling event for specialized characterization analysis to
compare to the baseline characterization (XRD, QEMSCAN,
Remediation Engineering
4 6 8 10 12 14 16 18 20
Days elapsed
Process pass Acid addition begins
Acid addition ends Ferrous addition
XANES, and micro-XAS). During this process, 27 samples
were collected to be analyzed for pH, TOC, total iron, total
chromium (Cr(T)), hexavalent chromium (Cr6+), and moisture
content. Samples were collected by advancing angled borings
and collecting samples at 7–9 ft bgs (shallow), 9–11 ft bgs
(middle), and 11–14 ft bgs (deep). Additional testing included
leachate analysis (SPLP and TCLP). Samples were visually
examined for presence of COPR nodules. Samples were
screened to determine the percent of COPR nodules, if any,
remaining after treatment. The percentage of soil as COPR
nodules was reduced from a baseline of 23.58% to 16.01%
based on sieve analysis. This suggests that nodules were
weathered by the addition of the sulfuric acid (H2SO4). The
following is a brief discussion of the performance monitoring
results:
• Analytical results indicate that the average baseline
hexavalent chromium (Cr6+) concentration in soil
from 0 to 15 ft bgs was 410 mg/kg, approximately
20  times the treatment goal (direct contact nonresi-
dential soil cleanup criterion of 20 mg/kg). More spe-
cifically, hexavalent chromium (Cr6+) concentrations
in soil from the shallow and middle intervals (those
intervals visually determined in the field to con-
tain the majority of COPR nodules) were 1,070 and
155 mg/kg, respectively (Figure 7.37). Results from
posttreatment sampling indicate that all samples
from all intervals contained hexavalent chromium
(Cr6+) in soil below 1 mg/kg. In contrast, the average
baseline total chromium (Cr(T)) concentration from 0
to 15 ft bgs was 10,397 mg/kg and remained elevated
above 5,000 mg/kg throughout the performance
monitoring period (Figure 7.38). The posttreatment
In Situ Treatment of Metals 381

Hexavalent chromium in soil following field‐scale pilot study

1000

Hexavalent chromium in soil (mg/kg)

100

10

0
2/26/11 6/6/11 9/14/11 12/23/11 4/1/12

Shallow soil Cr6+ Middle soil Cr6+ Deep soil Cr6+

Amendments added Treatment goal

FIGURE 7.37  Hexavalent chromium (Cr6+) in soil following in situ soil stabilization with sulfuric acid (H2SO4), ferrous sulfate heptahy-
drate (FeSO4 * 7H2O), and inoculant and dextrose (C6H12O6).

Total chromium in soil following field‐scale pilot study

100,000
Hexavalent chromium in soil (mg/kg)

10,000

1,000
2/26/11 6/6/11 9/14/11 12/23/11 4/1/12

Shallow soil CrT Middle soil CrT

Deep soil CrT Amendments added

FIGURE 7.38  Total chromium (Crtot) in soil following in situ soil stabilization with sulfuric acid (H2SO4), ferrous sulfate heptahydrate
(FeSO4 * 7H2O), and inoculant and dextrose (C6H12O6).

total chromium (Cr(T)) concentrations were essen- • SPLP analysis is designed to determine the mobil-
tially unchanged from baseline, and the decrease in ity of both organic and inorganic analytes present in
hexavalent chromium (Cr6+) concentrations to less liquids, soils, and wastes left in situ (within or on top
than 1 mg/kg indicates that the hexavalent chromium of the ground surface) when exposed to simulated
(Cr6+) in the test cell was successfully reduced to tri- acidic rainfall and is applicable to determine the
valent chromium (Cr3+). By decreasing the hexava- mobility of chromium. Chromium is most mobile
lent chromium (Cr6+) soil concentrations to below in the hexavalent (Cr6+) oxidation state and is spar-
the treatment goal (20 mg/kg), the first objective the ingly soluble in the trivalent (Cr3+) oxidation state.
field-scale pilot study was achieved. A decrease in chromium leached by SPLP following
382 Remediation Engineering

treatment can demonstrate that the treatment suc- hexavalent chromium (Cr6+) above the method detec-
cessfully immobilized the chromium and suggests tion limit of 10 μg/L (Figure 7.39).
that hexavalent chromium (Cr6+) was reduced to • The baseline pH of the soil ranged from 10.3 to
trivalent chromium (Cr3+) by the treatment process. 11.4 (Figure 7.40). Over time, the weathering of the
The SPLP results for hexavalent chromium (Cr6+) COPR nodules by natural acidity present in rainfall
in the baseline sample were 9,300 μg/L in the shal- recharge (as simulated by the baseline SPLP analy-
low interval and 18,200 μg/L in the middle interval. sis) can lead to the leaching of hexavalent chromium
After treatment, the 1 month SPLP results suggested (Cr6+) above regulatory standards for groundwater.
a marked decrease in hexavalent chromium (Cr6+) The key purpose of the acid addition was to accel-
to 20 μg/L in the shallow interval and 38 μg/L in erate the leaching of the hexavalent chromium
the middle interval. Subsequent SPLP results had no (Cr6+) by dissolving the COPR nodules that contain

Hexavalent chromium in SPLP following field‐scale pilot study

100,000
Hexavalent chromium in soil (mg/kg)

10,000

1,000

100

10

1
2/26/11 6/6/11 9/14/11 12/23/11 4/1/12

Shallow SPLP C6+ Middle SPLP Cr6+

Deep SPLP Cr6+ Amendments added

FIGURE 7.39  Total chromium (Crtot) in synthetic precipitation leaching procedure leachate following in situ soil stabilization with sulfuric
acid (H2SO4), ferrous sulfate heptahydrate (FeSO4 * 7H2O), and inoculant and dextrose (C6H12O6).

pH in soil following field‐scale pilot study

14.0

12.0
pH of soil (standard units)

10.0

8.0

6.0

4.0

Shallow soil pH Middle soil pH

2.0 Deep soil pH Amendments added

0.0
2/26/11 6/6/11 9/14/11 12/23/11 4/1/12

FIGURE 7.40  pH in soil following in situ soil stabilization with sulfuric acid (H2SO4), ferrous sulfate heptahydrate (FeSO4 * 7H2O), and
inoculant and dextrose (C6H12O6).
In Situ Treatment of Metals
hexavalent chromium (Cr6+), thus making it avail-
able for treatment. During the weathering process,
alkalinity in the soil and COPR nodules was released
and neutralized, resulting in a decrease in size of the
COPR nodules. This explains the buffering capac-
ity of the test cell and why the pH increased from
an average of 5.7 on March 24, 2011, to an approxi-
mate average of 6.9 on March 13, 2012 (Figure 7.40).
Reducing the pH from approximately 11.0 was also
necessary to facilitate biological and chemical treat-
ment, which can be inhibited at pH values higher
than circumneutral. Over the course of the posttreat-
ment monitoring, the pH values increased as noted,
but any hexavalent chromium (Cr6+) liberated dur-
ing this additional weathering was obviously treated.
The pH did not return to pretreatment conditions and
remained relatively stable over the year of perfor-
mance monitoring. The stability of the pH indicates
that the sulfuric acid (H2SO4) had sufficiently weath-
ered the COPR minerals responsible for sustained
alkaline pH.
• Total iron concentrations generally did not change
between baseline and post treatment samples, apart
from being homogenized (Figure 7.41). This was
expected, as the amount of iron added as part of the
remedy only increased the iron in the test cell by
approximately 5% by weight, and the hope was to
increase the dissolved iron fraction, which would not
be detected in a total iron soil sample. There was an
attempt made to collect a water sample from the test
cell with a temporary angled well, but the cell did not
produce sufficient water to produce a sample.
140,000
130,000
120,000
110,000
Total iron in soil (mg/kg)
100,000
90,000
80,000
70,000
60,000
50,000
40,000
2/26/11
FIGURE 7.41  Iron in soil following in situ soil stabilization with sulfuric acid (H2SO4), ferrous sulfate heptahydrate (FeSO4 * 7H2O), and
inoculant and dextrose (C6H12O6).
383
• Baseline TOC shows stratified concentrations biased
high by the potential for some manufactured gas plant
related petroleum compounds in the deep interval
(Figure 7.42). The baseline TOC concentrations were
4,490, 11,200, and 73,800 mg/kg for the shallow, mid-
dle, and deep intervals, respectively. Approximately
45 kg of dextrose per cubic meter of soil was added
to the cell as part of the biostimulation pass. Dextrose
is approximately 37% as TOC, and therefore, an
approximate TOC dose of 17 kg per cubic meter of
soil was expected. The calculated homogeneous
TOC concentration after the biostimulation pass was
expected to be approximately 39,000 mg/kg. The per-
formance monitoring data summarized in Figure 7.42
show that the postmixing TOC concentration was an
average of 15,100 mg/kg. This difference is attributed
to the significant increase in water during mixing and
the 48% by weight solubility of dextrose, resulting in
the majority of TOC present in the dissolved phase.
Although an attempt was made to install a prepack-
aged screened well within the treatment cell dur-
ing the performance monitoring period to collect a
groundwater sample, sufficient water could not be
recovered to submit a groundwater sample for labora-
tory analysis of TOC.
Specialized characterization analyses were conducted to show
mineralogical changes due to treatment, including changes
in chromium-bearing mineral phases, the alkalinity-bearing
mineral phases, and mineral phases that will provide residual
hexavalent chromium (Cr6+) reducing capacity, such as sulfide
(S2−) minerals. These results are discussed in more detail in
Total iron in soil following field‐scale pilot study
6/6/11 9/14/11 12/23/11 4/1/12
Shallow soil total iron Middle soil total iron
Deep soil total iron Amendments added
384 Remediation Engineering

Total organic carbon in soil following field‐scale pilot study

100,000

90,000

80,000

Total organic carbon (mg/kg)

70,000

60,000

50,000

40,000

30,000

20,000

10,000

0
2/26/11 6/6/11 9/14/11 12/23/11 4/1/12

Shallow soil total organic carbon Middle soil total organic carbon
Deep soil total organic carbon Amendments added

FIGURE 7.42  Total organic carbon in soil following in  situ soil stabilization with sulfuric acid (H2SO4), ferrous sulfate heptahydrate
(FeSO4 * 7H2O), and inoculant and dextrose (C6H12O6).

Section 7.4.3 in the context of a more detailed discussion on (As3+) to arsenate (As5+); however, if groundwater extraction
these specialized characterization analyses. is a beneficial or required aspect of the remedy, this represents
In summary, the two case studies discussed here present an example of aboveground metal precipitation.
treatment mechanisms (hexavalent chromium [C6+] reduced A physical flushing strategy, like DGR (Chapter 5), may
to trivalent chromium [Cr3+]) but were implemented in com- involve both the injection and extraction of groundwater.
pletely different ways. Such variability with the implementa- Without special precaution, extracted groundwater is sub-
tion of in situ stabilization highlights the adaptability of the jected to atmospheric oxygen through diffusion,119 and the
technology and demonstrates why it can be so effective. In situ dissolution of atmospheric oxygen into strongly reducing
soil stabilization and/or solidification for metal precipitation groundwater can be rapid. For instance, if extracted ground-
is a blossoming technology that will see further innovation in water is used to dilute a soluble organic carbon substrate
the future as regulatory cleanup goals are reduced and practi- for distribution throughout an aquifer, the potential exists
tioners search for more cost-effective technologies. to eventually extract groundwater with a geochemical-
reducing signature. The photo in Figure 7.43 was taken from
7.4.2.4 Extraction
Sequential in situ treatment mechanisms are most easily con-
ceptualized as separate ex situ reactors, and all of the chemi-
cal and biological forms of in situ metal precipitation can be
implemented ex situ in appropriately designed reactors. The
reactors need to be designed to support the metal precipita-
tion mechanism (i.e., aerobic and oxidizing or anaerobic and
reducing). From an ex  situ perspective, metal precipitation
may be the selected form of above ground groundwater treat-
ment or a requisite conditioning step because of changes in
oxidation–reduction potential. For example, arsenic dissolved
in groundwater as arsenite (As3+) is less amenable to removal
from groundwater via sorption onto iron oxyhydroxides as the
more oxidized form of arsenic, arsenate (As5+). Therefore, if
reduced groundwater was first oxidized to convert arsenite
(As3+) to arsenate (As5+) and then mixed with iron oxyhy-
droxides, this represents a viable mechanism for removal that
could occur sequentially (Section 7.4.4.2). Obviously, these FIGURE 7.43  Geogenic manganese scale formation within a pipe
two steps could occur simultaneously in situ with precipita- that conveyed circulated groundwater from an engineered anaerobic
tion of ambient ferric iron (Fe3+) during oxidation of arsenite in situ reactive zone.
In Situ Treatment of Metals
a conveyance line of an organic carbon DGR system where
dissolved manganous manganese (Mn2+) in groundwater
was oxidized to manganic manganese (Mn4+) in the convey-
ance line over time and precipitated as manganese dioxide
(MnO2). The system ran somewhat continuously for sev-
eral months resulting in considerable scaling of the geo-
genic manganese in the conveyance line. For a strategy that
involves extracting groundwater with the potential to precipi-
tate oxidation–reduction potential sensitive metals (most sig-
nificantly iron and manganese), intentional precipitation via
oxidation–reduction reaction or pH neutralization in a pre-
treatment aboveground tank prior to treating (or dosing) the
groundwater for reinjection or disposal may reduce operation
and maintenance costs.
7.4.2.4.1  Source Mass Approximation
Metal contamination source zones can contain large masses
of metals, especially when undiluted plating solutions
remain at the spill point. Plating solutions may contain
more than 350 g/L of dissolved metal (e.g., Ni2+), with pH
and redox buffers that resist alteration of the fluid chemis-
try. If the source zone received multiple aliquots of plat-
ing solution, precipitated metal may also be present in the
aquifer matrix. Because plating solutions are miscible with
groundwater (although density flows are possible), pump-
ing withdrawal does not face the same limitations of pump-
ing for nonaqueous phase liquid removal, and a significant
mass of contaminant can be removed by pumping from
the source area. We have recovered thousands of liters of
plating solution by pumping withdrawal from a spill point,
removing hundreds of kilograms of dissolved metals from
the aquifer matrix.
A large number of variables would have to be specified to
determine the maximum mass of a metal that could be accu-
mulated in a source zone, and therefore, remedial time frames
based on “contaminant mass estimates” for metals should
be considered with some skepticism. It is possible, however,
to approximate the mass that could be infused, in the aque-
ous phase, into the static water (i.e., immobile fraction of the
aquifer). This approximation of mass would represent the con-
tinued source of metals to groundwater long after the actual
release occurred. Let’s take, for example, a nickel-plating
solution, which contains 170 g/L nickel (Ni2+; 170,000 mg) at
pH 4. If that solution were spilled into an aquifer with a 0.86
static water fraction and a 300 L/m3 total porosity, the source
zone nickel (Ni2+) storage capacity would be 4.4 × 107 mg Ni2+
per m3 aquifer matrix:
170, 000 mg Ni 2 + 300 L groundwater 0.86
´ ´
L 1 m 3 aquifer 1 water velocity represents the “center of mass” movement of
4.4 ´ 107 mg Ni 2 +
= contaminant source as opposed to the transport (or seepage)
1 m 3 aquifer
In a single pore volume of a reasonable areal extent of a
release (20 ft in length and 20 ft in width) with a saturated
385
thickness of 20 ft, this could equate to greater than 6,500 lb of
nickel in the associated source zone:
1 m3 4.4 ´ 107 mg Ni 2 +
(20 ft ´ 20 ft ´ 20 ft ´ 0.3) ´ ´
35.3 ft 3
1 m 3 aquifer
1 lb
´ ~ 6, 590 lb Ni 2 +
453, 592.4 mg
If this is compared to a typical nickel (Ni2+) groundwater
cleanup goal (0.1 mg/L; CA, FL, NJ),
0.1 mg Ni 2 + 300 L groundwater 0.86 25.8 mg Ni 2 +
´ ´ =
L 1 m 3 aquifer 1 1 m 3 aquifer
1 m3 25.8 mg Ni 2 +
(20 ft ´ 20 ft ´ 20 ft ´ 0.3) ´ 3
´
35.3 ft 1 m 3 aquifer
1 lb
´ ~ 3.9 ´ 10 -3 lb Ni 2 +
453,592.4 mg
It is clear that the release of acidic high dissolved metal
concentrations into an aquifer can deposit significant mass
that will require lengthy attenuation time frames or active
in  situ remediation. Additionally, if the aquifer matrix is
capable of initially or continually neutralizing the pH from
the release, nickel may be removed from groundwater natu-
rally (either by adsorption, precipitation, or coprecipitation
with iron oxyhydroxides49,120). This prevents the groundwa-
ter from reaching the nickel solubility limit, and continual
loading of nickel (Ni2+) within this pore volume from sub-
sequent releases of plating solution is possible. Cyclical
release and neutralization can build large in  situ source
zone masses of nickel (Ni2+), acidity, and other plating solu-
tion metals. The acidity associated with the releases may
eventually consume the natural buffering capacity locally,
resulting in the source zone metals dissolving and diluting
into the natural groundwater flux at concentrations above
regulatory standards.
7.4.2.4.2  Pore Flushing Approximation
To provide an appreciation of the attenuation lifetimes asso-
ciated with metal releases such as the nickel-plating solution
example earlier, we can apply a simple pore flushing approxi-
mation. More complex principles associated with immobile
to mobile contaminant advection and other facets of remedia-
tion hydraulics are discussed in Chapter 4 and summarized in
considerable detail elsewhere.36 In the example nickel-plating
solution release, let’s assume the average groundwater veloc-
ity is 50 ft per year (0.14 ft per day). The average ground-
the contaminant plume describing the bulk movement of the
velocity, which represents the leading edge of the dissolved
plume. To consider holistic flushing of the pore volume, it
is more appropriate to focus on the average groundwater
velocity.
386
Let’s also assume that contaminant retardation is sig-
nificantly influenced by the mobile to immobile interaction,
defined by the following equation:
qi
Rfq = 1 + (7.61)
qm
where θm and θi are the mobile and immobile fractions of the
total porosity, respectively. If the total porosity is assumed to
be 30%, and 10% of the total porosity contributes to mobil-
ity, the retardation coefficient is determined to be 3. Ignoring
sorption-based retardation is a justifiable assumption in
this instance as Dzombak and Morel demonstrated that the
adsorption of nickel (Ni2+) to a representative HFO was negli-
gible at pH less than 5.0.121 The following is a brief description
of sorption-based retardation specific to metals.
Sorption-based retardation is defined by the following
equation:
rb
RfKd = 1 + ´ Kd (7.62)
qtot
where
ρb is the soil bulk density
θtot is the total porosity
Kd, a partitioning coefficient, is complicated by aquifer and
metal-specific characteristics
Sorption-based retardation is significant for metal transport under
circumneutral pH, as both the aquifer pH and metal adsorption
onto organic matter, oxyhydroxides, and clays strongly dictate
metals transport through porous media. Adsorption is often
described in terms of isotherms, which show the equilibrated
relationship between the aqueous concentration of the adsor-
bate (i.e., what’s doing the adsorbing) and the amount adsorbed
to the adsorbent (i.e., What’s doing the adsorbing) at constant
temperature.15 In the example of the nickel-plating solution, dis-
solved nickel (Ni2+) is the adsorbate and the soil surface is the
adsorbent. The most common isotherm expression for metals is
the Freundlich isotherm (Equation 7.63):
Cs = mCwn (7.63)
where
Cs is the concentration of adsorbate associated with the
adsorbent (mol/kg)
Cw is the concentration of the adsorbate in solution (mol/L)
m is the Freundlich constant (or the partitioning coefficient
[Kd])
n is the measure of nonlinearity
The Freundlich isotherm is nonlinear, as sorption locations
are limited to the surface area of the adsorbent, and at high
concentrations of adsorbate the sorption curve plateaus to
account for the increased concentration of metals and limited
adsorption sites, and the partitioning coefficient (Kd) progres-
sively decreases.122 Under low concentrations of  adsorbate,
Remediation Engineering
the Freundlich isotherm can be simplified to be linear, in which
case the “n” in Equation 7.63 becomes 1, and the Freundlich
isotherm can be presented as the Langmuir Isotherm in the
following equation (substituting Kd in for m):
Cs = K d Cw (7.64)
This equation is a convenient way to conceptualize metals
sorption in  situ, but should be applied with caution and for
low concentrations of dissolved metals.
The partitioning coefficient (Kd) of a metal is site specific
and variable and is analytically determined or geochemi-
cally predicted through modeling based on the properties of
the soil and the subject metal as well as observed transport
of the metal in groundwater. All aquifers are heterogeneous
and anisotropic at every scale,36 and, therefore, it stands to
reason that partitioning coefficient (Kd) for metals likely vary
within different locations and depths of a particular site. A
summary of partitioning coefficients (Kd) from approximately
245 studies, amassing a total of 1,170 individual partition-
ing coefficients (Kd), was summarized by the USEPA Office
of Solid Waste in a publication in 1999,123 and a portion of
their results relevant to groundwater aquifers is summarized
in Table 7.15. Quick inspection of the results (which present
logarithmic transformation of the partitioning coefficients
[Kd]) demonstrates a high degree of variability. For example,
for zinc (Zn2+), of the 21 determined/predicted partitioning
coefficients (Kd) summarized in Table 7.15, there is a range
of six orders of magnitude. Differences in partitioning coef-
ficients (Kd) are even observed based on the oxidation state
of the metal, and note that, for chromium the median par-
titioning coefficient (Kd) varies by two orders of magni-
tude (~7,943 L/kg for trivalent chromium [Cr3+] and ~13 for
hexavalent chromium [Cr6+]). Assuming the range of partition
coefficients (Kd) for nickel (Ni2+) presented in Table 7.15 (10
to ~6,310 L/kg), the potential range of sorption-based retar-
dation for this example is approximately 60–37,861. Gross
generalizations of partitioning coefficients (Kd) for metals are
not recommended, and therefore, for this simple pore flush-
ing approximation under strongly acidic conditions for nickel
(Ni2+) sorption-based retardation is ignored.124
The number of pore volumes necessary to flush through
the source area and dilute the in  situ nickel concentration
from 170,000 to 0.1 mg/L is described by the product of a
logarithmic ratio of the concentrations and the porosity driven
retardation coefficient (previously determined to be 3):
æC ö
NF = ln ç i ÷ ´ Rfq (7.65)
è Cf ø
where
NF is the number of pore volume flushes
Ci is the initial concentration of nickel (Ni2+) in groundwa-
ter (170,000 mg/L)
Cf is the regulatory standard for nickel (Ni2+) in groundwa-
ter (0.1 mg/L)
This results in approximately 43 pore flushes.
In Situ Treatment of Metals 387

Therefore, the length of time for a single pore volume flush

TABLE 7.15 of just the 20 ft long by 20 ft wide source area is approxi-
Summary of Metals Partitioning Coefficients mately 43  days, and to complete the requisite, 43 pore vol-
from the Literature ume flushes is approximately 1,850 days (>5 years). This pore
volume flushing example does not consider the transport of
Metal Soil/Water Metal Soil/Water
metals downgradient from the source area (initially estimated
Ag CH3Hg to be greater than 590 lb of nickel [Ni2+]/day [170,000 mg/L
Median 2.6 Median 2.8
­multiplied by the groundwater flux rate of 420 gal/d]) and the
Range 1.0–4.5 Range 1.3–4.8
propagation of a dissolved nickel (Ni2+) plume downgradi-
N 21 N 11
ent. It also does not account for the storage capacity of met-
As Mo
als based on the cyclical neutralization and release discussed
Median 3.4 Median 1.1
earlier. It does demonstrate that high dissolved metal concen-
Range 0.3–4.3 Range (−0.2)–2.7
N 22 N 8
trations in releases to the aquifer can require considerable
Be Ni
attenuation time frames. The time frame to naturally flush
Median 3.1 Median 3.1 the small source area and the potential for considerable nickel
Range 1.7–4.1 Range 1.0–3.8 (Ni2+) migration downgradient would likely necessitate active
N 2 N 18 in situ remediation, which would likely employ immobiliza-
Cd Pb tion via direct and coprecipitation and acidity neutralization.
Median 2.9 Median 4.2
Range 0.1–5.0 Range 0.7–5.0
7.4.3 Analytical
N 41 N 33
Co Sb When an in  situ remedial strategy for chlorinated volatile
Median 2.1 Median 2.4 organic compounds is implemented, there are numerous metrics
Range (−1.2)–4.2 Range 0.1–2.7 that can be monitored to directly attribute the reductive dechlo-
N 11 N 6 rination to the engineered treatment (Chapter 6). For example,
Cr(3+) Se typical chlorinated compounds tetrachloroethene (C2Cl4) and
Median 3.9 Median 2.1 trichloroethene (C2HCl3) are dechlorinated to less chlorinated
Range 1.0–4.8 Range −0.3–2.4 products such as cis-1,2-dichloroethene (C2H2Cl2) and vinyl
N 43 N 23 chloride (C2H3Cl) and eventually to completely dechlorinated
Cr(6+) V
end products ethene (C2H4) and ethane (C2H6) within an engi-
Median 1.1 Median
neered IRZ. These incremental changes can be measured via
Range (−0.7)–3.3 Range 0.6–2.7
laboratory analysis and confirm that the targeted pathway has
N 24 N 1
been achieved or positively influenced through an engineered
Cu Zn
Median 2.7 Median 3.1
strategy. With in situ metal precipitation, the ultimate metric of
Range 0.2–3.6 Range (−1.0)–5.0
decreased concentrations in groundwater may be observed, but
N 20 N 21 may also be a result of adsorption, precipitation, or coprecipita-
Hg CN tion regardless of the designed immobilization mechanism. In
Median 3.8 Median 3.0 order to definitively prove that the engineered IRZ is function-
Range 2.2–5.8 Range 0.7–3.6 ing as intended, more detailed esoteric analytical techniques
N 17 N 3 may be required. From an in situ metal precipitation perspec-
tive, esoteric analyses include mineral characterization, spec-
Source: Robert B. Ambrose Jr., P.E. U.S. Environmental Pro­
troscopy, or high-resolution microscopy of mineral species, and
tection Agency Office of Research and Development,
these techniques are discussed in this section. These analyses
Athens, GA, Partition coefficients for metals in surface
water, soil, and waste, June 22, 1999.
can be costly and difficult to explain to stakeholders without
a specialized level of understanding. Therefore, more often
than not, decreases in metal concentrations in groundwater are
For the subject aquifer in the nickel-plating solution release, assumed to be associated with the engineered IRZ, and bench-
the pore volume in the release area is scale treatability testing and literature documentation is used
7.48 gal to substantiate this reasoning. For a typical implementation of
20 ft ´ 20 ft ´ 20 ft ´ 0.3 ´ ~ 18, 000 gal in situ hexavalent chromium (Cr6+) treatment of groundwater,
1 ft 3
decreases in the hexavalent chromium (Cr6+) concentration
The groundwater flux rate is the cross-sectional area perpen- under geochemical conditions consistent with hexavalent chro-
dicular to groundwater flow (20 ft wide × 20 ft deep) multi- mium (Cr6+) conversion to trivalent chromium (Cr3+) generally
plied by the average groundwater velocity: suffice for proof of concept. As will be discussed in detail in
this section, for more innovative in  situ remedial strategies
ft ft 3 7.48 gal gal (Section 7.4.2.3) sophisticated spectroscopy and microscopy
20 ft ´ 20 ft ´ 0.14 = 56 ´ ~ 420
day day 1 ft 3 day help definitely prove the concept.
388
7.4.3.1  Dissolved Metal Analysis
Dissolved analysis for metals is of primary importance
because often a decrease in the concentration of a metal
in groundwater represents the objective of an in situ metal
precipitation strategy. The dissolved phase analysis is a
representation of the engineered adsorption, precipitation,
or coprecipitation strategy because as the designed mecha-
nism takes place, the metal is removed from groundwater.
The USEPA analytical method for metals in groundwater
is method 6010B125 and uses inductively coupled plasma
atomic emission spectroscopy (ICP-AES). The groundwa-
ter is acidified (i.e., digested) to dissolve microscopic sus-
pended solids, such as colloids. The optical spectrum of an
element is a characteristic trait that is used to identify the
metal and quantify it. The laboratory analysis of method
6010B may experience interferences related to overlapping
spectra, background influences, naturally occurring organic
matter, ionization effects, complexation, evaporation of the
sample, and even changes in the viscosity or surface tension
of the sample. A detailed review of the potential interfer-
ences associated with this method is beyond the scope of this
discussion, but it is relevant to understand that these inter-
ferences may exist. Upon review and evaluation of metals
data, questionable or surprising results should be discussed
with the laboratory as geochemical conditions of an estab-
lish IRZ may require more significant dilution. Most of the
interferences associated with this method can be minimized
through sample dilution.
Dissolved analysis of groundwater for metals can provide
information about the oxidation–reduction potential of an aqui-
fer. Qualitatively, large differences between total (unfiltered)
and dissolved (filtered) metal concentrations for oxidation–
reduction sensitive metals (i.e., iron, manganese, selenium,
chromium, and molybdenum) may indicate more aerobic and
oxidizing conditions, and negligible differences may indicate
more anaerobic and reducing conditions. Conceptually, at cir-
cumneutral pH and slightly aerobic and oxidizing conditions,
the dissolved concentrations of oxidation–reduction sensitive
metals would be expected to be low, while reducing conditions
would drive these metal into solution. Quantitatively, this is
not necessarily the case because a percentage of the dissolved
oxidation–reduction sensitive metals could be in the more oxi-
dized form sorbed to colloids or finely divided crystals that
have yet to settle from the groundwater and pass through the
filter. Therefore, while qualitatively it may be sufficient to
classify the oxidation–reduction potential of an aquifer based
on comparisons of total (unfiltered) and dissolved (filtered)
metals concentrations, laboratory analytical methods exist
for speciated metals. For example, US EPA method 7196A is
specific to hexavalent chromium (Cr6+). This analysis is par-
ticularly important as it has been demonstrated that trivalent
chromium (Cr3+) may be soluble under slightly aerobic cir-
cumneutral pH conditions and could represent a portion of
the dissolved chromium analysis (Figure 7.24). Additionally,
ferrous iron (Fe2+) has a specific laboratory analytical method
(SM3500) to appropriately speciate iron.
Remediation Engineering
Groundwater samples collected for metal analysis are sus-
ceptible to false positives if the turbidity is high and samples
have high suspended solids. Federal and state groundwater
sampling guidance documents are available and generally
suggest turbidity less than or equal to 10–20 NTU.126
7.4.3.2  Solid Metal Analysis
Groundwater monitoring associated with any in situ treatment
approach provides superficial evidence of treatment. In other
words, the data are blind to the mechanisms responsible for
the observed dissolved-phase trends. While we can anticipate
those mechanisms, in some cases (not all), solid-phase analy-
sis might be desired to confirm or document them.
The same methods can possibly also provide insight into
changes in the precipitated solid phases over time. The meth-
ods available for acquiring these data can be broken down
into categories based on what they can tell us about the form
of the precipitated metal that was targeted for treatment
(USEPA 2007)127:
• Operationally defined forms: This involves evalu-
ation of metal form based on the conditions under
which it can be mobilized and is accomplished
through sequential selective extractions at increasing
strengths.
• Structurally defined forms: This involves evaluation
of metal form through elemental and structural (spa-
tial) relationships. There are a number of analytical
techniques that fit in this category, including XRD,
x-ray photoelectron spectroscopy, Fourier-transform
infrared spectroscopy, scanning electron micros-
copy (SEM)/energy dispersive x-ray spectroscopy,
and XAS.
In conducting these types of analyses, it is important to be
aware of limitations associated with the amount of precipitate
mass that may be present compared with the sensitivity of the
method/instrument. The spatial resolution of some techniques
can make identification like looking for the proverbial needle
in a haystack, so that samples require prescreening based on
the other analyses. Immobilization of 10 mg/L of dissolved
metal onto a granular aquifer matrix equates to about 2 mg/kg
or 0.0002% by weight, which, even if it can be located, may
not be discernable from background depending on the metal.
7.4.3.2.1 Elemental
Total elemental analysis of soil is typical for most in situ metal
precipitation sites and reflects the amount of metals in the aqui-
fer soil. The USEPA test method for total elemental analysis
of soil is method 3050B,128 and involves a nitric acid (HNO3)
acid and hydrogen peroxide (H2O2) digestion followed by
ICP-AES or inductively coupled plasma mass spectrometry
(ICP-MS) depending on the metal (Table 7.16). Hydrochloric
acid (HCl) is added to the digestate (the soil mixture after
nitric acid [HNO3] and hydrogen peroxide [H2O2] digestion)
as an additional digestion. Examples of analytical results for
In Situ Treatment of Metals
TABLE 7.16
Recommended Determinative Techniques for Elements
ICP-AES ICP-MS
Aluminum Magnesium Arsenic
Antimony Manganese Beryllium
Barium Molybdenum Cadmium
Beryllium Nickel Chromium
Cadmium Potassium Cobalt
Chromium Silver Iron
Cobalt Thallium Lead
Copper Vanadium Molybdenum
Iron Zinc Selenium
Lead Thallium
Vanadium
total elemental analysis are presented in Figures 7.37 and 7.38
for hexavalent chromium (Cr6+) and total chromium (CrT).
7.4.3.2.2 Structural
Some of the available structural (mineralogical) analysis (i.e.,
characterization analysis) available will be discussed in this
section, specifically those that are used in the in situ remedia-
tion industry frequently enough to warrant a discussion (x-ray
powder diffraction [XRD], SEM with energy dispersive x-ray
spectroscopy, and XAS). This is not intended to be an exhaus-
tive review of available characterization analysis, and the
reader is referred to the works of Pansu and Gautheyrou,129
Rollinson,130 and Egerton131 (and references therein) for more
detailed information on analysis presented here and others.
As the characterization analysis are presented and dis-
cussed in this section, example results and graphics will be
connected back to the in  situ stabilization case study from
Site B discussed in detail in Section 7.4.2.3. The authors
would like to acknowledge Canadian Light Source Inc.,
SGS Mineral Services, Dr. Jeff Gillow, and the Brookhaven
National Laboratory for conducting the specialized character-
ization. Recall from Section 7.4.2.3 that 237 tons of treatment
cell soil  consisting primarily of COPR nodules at elevated
hexavalent chromium (Cr6+) and alkaline pH was weathered
with 5,600 gal of sulfuric acid (H2SO4) and then mixed with
6  tons of ferrous sulfate heptahydrate (FeSO4  *  7H2O) and
6 tons of dextrose (C6H12O6). The purpose of the demonstra-
tion was to accelerate leaching of hexavalent chromium (Cr6+)
from the COPR nodules and subsequently chemically reduce
leached hexavalent chromium (Cr6+) to trivalent chromium
(Cr3+). The carbon substrate was provided to biologically
reduce leached hexavalent chromium (Cr6+) on a longer time-
line and cycle the oxidation–reduction potential to regenerate
ferrous iron (Fe2+), which has been shown in the literature to
be a highly reactive chemical reductant.132–137
7.4.3.2.3 XRD
XRD is a nondestructive analytical technique useful for
phase identification of crystalline material. X-rays are
389
generated and filtered to produce monochromatic radiation,
which is then concentrated and directed toward a sample.
The interaction of the incident x-rays with the sample pro-
duces a diffracted x-ray under certain conditions. These dif-
fracted x-rays are then detected, processed, and counted.
Depending on the anisotropy of the sample, XRD can be
considered semiquantitative as the relative intensity of the
diffractions is approximately proportional to the number of
crystals present (assuming low anisotropy).129 Conversion of
the diffraction peaks to lattice spacings allows identifica-
tion of minerals because each mineral has a set of unique
lattice spacings. Mineral identification and interpretation
involve matching the diffraction pattern of the sample to
patterns of single-phase reference materials. The reference
patterns are compiled by the Joint Committee on Powder
Diffraction Standards—International Center for Diffraction
Data (JCPDS-ICDD) and released on software as a data-
base of powder diffraction files.138 XRD can be combined
and supplemented with geochemical and isotopic analyses,
thermal analyses, and analyses that enable evaluation of
interatomic or intermolecular binding energies and order-
disorder relations, high-resolution transmission electronic
microscopy, and SEM.129 In the case study example dis-
cussed in Section 7.4.2.3, the XRD results were combined
with scanning electron microscopy, and the results are dis-
cussed in Section 7.4.3.2.4.
Uranium in the plus six oxidation state (U6+), typically in
the form of uranyl (UO22+), is soluble and mobile in ground-
water. Among complexation strategies (Section 7.3.1.1.5),
one method to remove uranyl (UO22+) from groundwater is
through biological reduction to uranium in the plus-four oxi-
dation state (U4+), typically in the form of uraninite (UO2).
The first published demonstration of biological reduction of
uranyl (UO22+) to uraninite (UO2) was conducted by Lovely
et  al.139 An example of XRD pattern for uraninite (UO2)
is shown in Figure 7.44, and was created as a verification
that an observed black precipitate in anaerobic laboratory
microcosms incubated with uranyl acetate (UO2(C2H3O2)2)
and sodium lactate (NaC3H5O3) was indeed uraninite (UO2).
The uraninite (UO2) measured in Figure 7.44 was generated
biologically by carefully cultured Shewanella oneidensis
strain MR-1 under two conditions, fast (a cell count of 2 × 108
cells/mL and a temperature of 37°C) and slow (a cell count of
1 × 108 cells/mL and a temperature of 20°C)140–142 in a 30 mM
sodium bicarbonate (NaHCO3) buffer at concentrations of
1  × 10 −3 M uranyl (UO22+), 2 × 10 −3 M acetate (C2H3O2−),
and 5 mM sodium lactate (NaC3H5O3). The uraninite (UO2)
generated under fast conditions is shown in the darker shaded
line, and the uraninite (UO2) generated under slow conditions
is shown in the lighter shaded line. Beneath the XRD pat-
terns are reference patterns, generated from software from
the JCPDS-ICDD. The reference patterns that most closely
matched the dark and light XRD patterns were Uraninite-Q
(U3O7) and Uraninite-C (UO2), which confirms that soluble
uranyl (UO22+) was biologically reduced to uraninite (UO2)
under both fast and slow conditions.
390
[U_BS.raw]
[U_BF.raw]
300
250
Intensity (counts)
200
150
100
50
0
10 20
FIGURE 7.44  X-ray diffraction patterns for uraninite (UO2) reduced under “fast” and “slow” conditions in 30 mM sodium bicarbonate (NaHCO3)
with 1 × 10−5 uranyl (UO22+), 2 × 10−3 acetate (C2H3O2−) and 5 mM sodium lactate (C3H5NaO3). “Fast” conditions (2 × 108 cells/mL and 37°C) are
shown in the darker shaded line. “Slow” conditions (1 × 108 cells/mL and 20°C) are shown in the lighter shaded line. The two reference spectra
Uraninite-Q (U3O7) and Uraninite-C (UO2) are the two closest matching spectra. (Courtesy of Dr. Hui Tan for the x-ray diffraction patterns.)
7.4.3.2.4 Scanning Electron Microscopy and
Energy Dispersive X-Ray Spectroscopy
QEMSCAN is an abbreviation for quantitative evaluation of
minerals by SCANning electron microscopy. QEMSCAN
uses a fully automated SEM-based analysis system to derive
quantitative mineralogical and textural data. The instru-
ment includes an electron-beam platform equipped with four
energy dispersive x-ray spectrometers (EDS) for mineral
identification and proprietary software for automated data
acquisition, summary, and presentation. An electron beam is
applied to a sample, which results in low-count energy dis-
persive x-ray spectra that are counted and compared to the
amount of energy needed to create them. Since each element
heavier than beryllium has an existing EDS, the EDS from the
SEM can be compared to identify individual elements. The
software allows for automated stepping of the electron beam
across samples at a user-defined pixel resolution (individual
points, lines, or map of an entire surface). At each pixel, the
system collects a backscatter electron (BSE) signal and an
energy dispersive x-ray spectrum. A mineral or phase identi-
fication is made on the basis of the BSE value and elemental
intensities.143
The QEMSCAN system used to characterize COPR from
the case study discussed in Section 7.4.2.3 was paired with the
XRD data, and it was sensitive enough to track transforma-
tions in COPR minerals through treatment. The QEMSCAN
data demonstrated notable changes in the chromium contain-
ing spinels indicating that there was a fundamental change
Remediation Engineering
00-015-0004> Uraninite-Q - U307
00-041-1422> Uraninite-C- U02
30 40 50 60 70 80 90
2θ (°)
of the mineralogy of the site soil and COPR nodules. The
spinel group are those naturally occurring and abundant
compounds following the molecular formula of A2+(B3+)2O4,
where A and B represent cations in the plus two and three oxi-
dation state, respectively. A summary of notable compounds
in the spinel group are listed in Table 7.9. Of note is magne-
tite (Fe3O4), which is the most abundant member of the spinel
group.145 The chemical formula does not appear to follow the
A2+(B3+)2O4 form; however, because one of the iron elements
is ferrous iron (Fe2+) and the other two are ferric iron (Fe3+),
the formula for magnetite could be written as Fe2+(Fe3+)2O4.
This discussion of the spinel group is important because
numerous occurrences of chromium, iron, magnesium, and
aluminum spinels were observed in the QEMSCAN results
from Site B.
Pre-treatment and posttreatment homogenate SEM-EDS
images are presented in Figures 7.45 and 7.46. The images
presented in Figures 7.45 and 7.46 have been marked with
the energy dispersive x-ray spectra that correspond to the
table below the image for ease of reference. The occurrence
of chromium in close proximity to calcite (CaCO3) is noted
in Figure 7.45 by a red arrow. In addition, numerous loca-
tions of various chromium iron magnesium aluminum spi-
nels (Cr Fe Mg Al Spinel, Cr Fe Al Mg Spinel, and Cr Fe
Mg Al Spinel Ca) are shown to be surrounded by iron-rich
spinels (Fe Mg Al Spinel). This represents chromium (either
as hexavalent chromium [Cr6+] or trivalent chromium [Cr3+])
associated with minerals susceptible to weathering. At highly
In Situ Treatment of Metals 391

1 7
14

13
3

11
9 12
8
17
5

16
10
15

200 μm Electron image 1

(a)

Spectrum Mineral O Na Mg Al Si Ca Ti Cr Fe S V
1 Cr Fe Mg Al spinel 34.4 11.3 8.8 0.5 0.5 34.1 10.5
2 Cr Fe Mg Al spinel 35 0.9 10.1 8.2 0.6 33.2 11.9
3 Cr Fe Al Mg spinel 32 1.3 8.3 8.5 34.9 14.9
4 Cr Fe Mg Al spinel 35.4 10.1 8.7 0.4 33 12.4
5 Cr Fe Al Mg spinel 33.9 1.2 7.3 8.2 33.3 16.1
6 Cr Fe Mg Al spinel Ca 37.8 11.2 6.1 2.3 6.2 22.4 14
7 Cr Fe Al Mg spinel 36.1 1.3 7.9 8.7 0.5 32.7 12.8
8 Cr Fe Mg Al spinel 33.9 1.4 10.5 8.7 33.3 12.2
9 Calcite 54.8 45.2
10 Fe Mg Al spinel Ca 46.3 11 4.2 5.2 2.9 0.6 28.4 0.9 0.5
11 Fe Mg Al spinel Ca 35.2 13.5 6 5.2 6.1 1.2 31.2 1.6
12 Fe Mg Cr Al spinel 33.9 13.5 3.1 0.6 4 44.9
13 Fe Mg Cr Al spinel 32.8 15.3 2.4 0.7 8.5 40.3
14 Fe Mg Cr Al spinel 35.6 14.3 4.3 0.6 0.7 7.9 36.5
15 Fe Mg Cr Al spinel 34.7 13.4 2.3 0.8 10.2 38.7
16 Fe Mg Cr Al spinel 40.4 15.2 4.2 0.4 7.3 32.4
17 Fe Mg Cr Al spinel 35 12.1 4.2 1.4 1.5 3.9 41.4 0.5
(b)

FIGURE 7.45  (a) Scanning electron microscopy–energy dispersive x-ray spectrometry (SEM-EDS) image of a pretreatment homogenate
from a chromite ore processing residue site in the Eastern United States (Site B in Section 7.4.2.3). Spectra #1–8 show various Cr-rich spi-
nels rimmed by Fe-rich spinels (spectra #14, 16, 17). Altered Cr spinel forms mixtures with calcite (spectra #9) as shown by the red arrow.
(b) Associated semiquantitative mineral chemistry percentages for the SEM-EDS image. Each spectrum shown in the SEM-EDS image is
comprised of the indicated percentage of the specified element.

alkaline pH, it is not surprising that chromium would form
chromium hydroxide compounds, and the issue with COPR
(and its characteristic highly alkaline pH) is that it presents
a long-term reserve for potential hexavalent chromium (Cr6+)
leaching as slightly acidic rainfall infiltration or ambient
groundwater interacts with COPR nodules. By accelerating
this process dramatically with 50% sulfuric acid (H2SO4),
a large change in mineralogy would be expected. Indeed,
the SEM-EDS image presented in Figure 7.46 for the post-
treatment homogenate demonstrates species of silicas (talc
Mg3Si4O10(OH)2 and kaolinite Al2Si2O5(OH)4) not detected
in numerous pretreatment homogenate SEM-EDS images
392 Remediation Engineering

3
4

12

7
8 1

5
6

10

11

100 μm Electron image 1

(a)

Spectrum Mineral O Na Mg Al Si Ca Cr Fe S Mn
1 Talc 44.4 17.6 5.4 20.4 7.1 5.1
2 Kaolinite 51.7 20.8 25.2 2.3
3 Chlorite 48.1 9.6 7.0 20.8 12.1 2.4
4 Fe Mg Cr Al spinel 33.5 13.5 2.9 0.6 3.7 44.7 1.1
5 Cr Mg Al Fe spinel 38.1 14.0 8.2 32.5 7.2
6 Fe Mg Cr Al spinel 32.5 13.7 2.7 0.5 11.6 39.0
7 Fe Mg Cr Al spinel 34.1 13.1 2.5 0.8 4.9 44.6
8 Calcite 57.3 1.5 41.2
9 Fe Mg Al spinel 32.6 13.5 2.3 1.0 1.1 48.3 1.2
10 Fe Cr Mg Al spinel 34.7 12.9 2.7 0.8 18.7 30.2
11 Cr Mg Fe Al spinel 35.0 13.3 7.6 0.4 34.4 9.3
12 Fe Mg spinel 41.8 10.3 3.4 6.6 0.5 35.4 2.0
(b)

FIGURE 7.46  (a) Scanning electron microscopy–energy dispersive x-ray spectrometry (SEM-EDS) image of a posttreatment homogenate
from a chromite ore processing residue site in the Eastern United States (Site B in Section 7.4.2.3). Spectra #5 and 11 show Cr-rich spinels
rimmed by Fe-rich spinels (spectra #6 and 10) and Fe–Cr–Mg spinels (spectra #4, 7, 9). Note less calcite (spectrum #8) and the increased
presence of silicates (i.e., serpentine/talc, spectrum #1; kaoline spectrum #2). (b) Associated semiquantitative mineral chemistry percentages
for the SEM-EDS image. Each spectrum shown in the SEM-EDS image is comprised of the indicated percentage of the specified element.

and significantly less chromium iron magnesium aluminum
spinel associated with calcium. This is demonstrated color-
fully in Figure 7.47, where four representative particle maps
are compared. Recall that QEMSCAN has the ability to map
particle surfaces if the electron beam is specified to do so. The
colorful images in Figure 7.47 represents the agglomerations
of the specified minerals over the surfaces of soil grains in
the sample. The pretreatment homogenates are presented as
A and B, and the posttreatment homogenates are presented as
C and D. Qualitatively, the biggest color differences between
pre- and posttreatment homogenate particle maps are the dis-
appearance of light blue (calcite [CaCO3]) and yellows (cal-
cium iron oxide [Ca Fe Oxide low Mg Si] and iron calcium
magnesium oxide [Mg Fe Oxide low Ca Si], diminished black
(Altered Cr-Spinel [Ca]), and increased purples (gypsum
[CaSO4 * 2H2O] and quartz [SiO2]) and oranges (Fe-Sulfate
and Fe-Sulfate Mg, Al, Si Mix). These mineralogical changes
are all consistent with a weathered COPR nodule and rep-
resent how powerful the graphical presentation of the data
can be.
In Situ Treatment of Metals 393

(a) (b)

(c) (d)

Fe-oxides Fe-sulfate Mg, Al, Si mix

Cr Fe Mg Al spinel Periclase/magnesite
Altered Cr-spinel (Ca) Calcite
Fe Mg Cr Al spinel Quartz
Al-Ox/hydrox Feldspar
Ca Fe oxide low Mg Si Epidote
Mg Fe oxide low Ca Si Amph/pyrox
Fe Ca Mg oxide low Si Micas/clays
Gypsum Sulfur/sulfies
Fe-sulfate Other

FIGURE 7.47  Quantitative evaluation of minerals by SCANning electron microscopy particle maps for pretreatment (a) and (b) and post-
treatment (c) and (d) homogenate from a chromite ore processing residue site in the Eastern United States (Site B, Section 7.4.2.3). The par-
ticle maps represent locations of minerals over the surface of the soil material, corresponding to the color key. The pretreatment homogenate
(a) and (b) show calcite and Fe Mg Cr Al spinel throughout, with altered Cr spinel (Ca) agglomerations closely associated with Ca Fe oxide
and Mg Fe oxide material. Finally, agglomerations of Cr Fe Mg Al spinel are observed throughout. The posttreatment homogenate (c) and
(d) show gypsum and Fe–sulfate/Fe–sulfate Mg, Al, Si mix throughout, with no apparent calcite. The altered Cr spinel (Ca), Fe Mg Cr Al
spinel, and Cr Fe Mg Al spinel observed in the pretreatment homogenate (a) and (b) is observed at similar percentages in the posttreatment
homogenate (c) and (d).

Another way of visualizing the QEMSCAN data is
through column graphs that compare changes in mineral
mass percentages. This may be more useful in a practical
in  situ remediation scenario where data must be presented
and explained to audiences of various backgrounds. The
QEMSCAN data (and XRD) show that there was a signifi-
cant decrease in the alkaline minerals based on mineral
reductions on a weight basis (Figure 7.48). For example, iron
calcium magnesium oxide (Fe Ca Mg oxide) decreased from
accounting for 14.6% of the mineral mass to 0.62%; calcite
(CaCO3) decreased from 3.59% to 0.43%; an altered chro-
mium spinel associated with calcium decreased from 9.19%
to 1.70%; and a calcium iron oxide (Ca Fe oxide) decreased
from 15.3% to 0.12%. These are represented by the first four
columns in Figure 7.48. Chromium iron magnesium alumi-
num spinel (Cr Fe Mg Al Spinel) and iron magnesium chro-
mium aluminum spinel (Fe Mg Cr Al Spinel) were observed
to remain relatively unchanged accounting for 8.47% and
32.0% of the mineral mass before treatment and 8.11%
and 35.8% of the mineral mass after treatment. These are
represented by the fifth and sixth columns in Figure 7.48.
Following treatment, there was a notable increase in gyp-
sum (CaSO4 * 2H2O; 0.18%–19.3%), iron sulfate silica, mag-
nesium or aluminum minerals (Fe–sulfate Mg, Al, Si mix,
0.19%–8.88%), iron sulfate (1.33%–5.4%), and quartz (SiO2;
3.31%–8.88%), indicating that silica and calcium were liber-
ated and reacted with the reagents. These are represented by
columns 7–10 in Figure 7.48. These reductions in mineral
394
100
Mineral mass percentage (%)
10
1 Cr Fe Mg Al spinel
0.1
Pre‐treat
FIGURE 7.48  Quantitative evaluation of minerals by SCANning electron microscopy mineral mass percentages of pretreatment and post-
treatment chromite ore processing residue.
mass percentages are easily visualized in Figure 7.48, and
support the observations earlier of the more intricate SEM-
EDS images and particle maps.
Finally, the numerous outputs of QEMSCAN can be
combined to provide powerful conclusions. For example, as
demonstrated by the mineral mass percentage evaluation the
chromium iron magnesium aluminum spinel (Cr Fe Mg Al
Spinel) and the iron magnesium chromium aluminum spinel
(Fe Mg Cr Al Spinel) did not change significantly between the
pretreatment and posttreatment sample (Figure 7.48). Based
on this observation, the only chromium-bearing mineral that
was affected by the treatment was the altered chromium spi-
nel associated with calcium. The pretreatment homogenate
SEM image presented in Figure 7.48 shows these altered
chromium spinels were colocated with calcite (CaCO3) within
the soil particles and nodules. These data combined indicated
that the altered chromium spinel associated with calcium is
likely the most accessible form of chromium and the source of
chromium likely to leach to groundwater. By removing almost
all of the calcite (CaCO3) and reducing the leached hexavalent
chromium (Cr6+) to trivalent chromium (Cr3+) in the sample,
the leachable chromium was significantly reduced and likely
eliminated.
Another useful form of SEM is transmission electron
microscopy (TEM), although this typically gets significant
more attention in academic applications. Whereas SEM uses
an electron beam to measure EDS response from a surface,
TEM uses the electron beam to pass through an ultra-thin
specimen and measures the interaction as the beam passes
through the sample. The benefit of a TEM image is the
enhanced resolution compared to other microscopes, and
allows for examination of fine details. An example of the
superior TEM image resolution is provided for the extracellu-
lar uraninite (UO2) precipitation discussed in Section 7.4.3.2.3
versus an SEM image141,142 (Figure 7.49). The top image is an
SEM image and the bottom two images are TEM. The white
Remediation Engineering
Fe Ca Mg oxide (low Si)
Ca Fe oxide (low Mg Si)
Altered Cr‐spinel (Ca)
Calcite
Fe Mg Cr Al spinel
Gypsum
Fe‐sulfate
Fe‐sulfate Mg, Al, Si mix
Quartz
Post‐treat
material in the SEM image and the black material in the TEM
image represent the uraninite (UO2) precipitate.
7.4.3.2.5  X-Ray Absorption Spectroscopy
XAS utilizes a high-energy x-ray source (generated in a syn-
chrotron) to provide element-specific information for hetero-
geneous samples. The synchrotron can be conceptualized as a
polygon-shaped tube under ultrahigh vacuum (~10 –11 mm Hg)
where subatomic particles are circulated at near light speed
through the assistance of bending magnets.146 An x-ray field
is then produced like a flat fan within the polygon-shaped
circulation of these particles. Then, a characteristic x-ray
absorption spectrum is generated for x-rays tuned to elec-
tron binding energies for specific elements. Because x-rays
will interact with any electron when the x-ray energy exceeds
the binding energy of the electron, and since binding ener-
gies of electrons are element specific, a spectrum of x-ray
energy absorption generated by XAS can be matched to a
specific element in a specific oxidation state. The spectrum
provides information about the association of elements in a
sample and their chemical form (e.g., oxidation state). From
an in situ metal precipitation perspective, for metals that are
oxidation–reduction potential sensitive (e.g., chromium, ura-
nium, selenium, arsenic, iron), this characterization technique
can confirm the oxidation state, which can prove immobiliza-
tion through chemical or biological processes. The technique
is nondestructive and is an excellent tool for determining
chemical speciation and the local electronic structure of the
absorbing element.
X-ray Absorption Near Edge Structure (XANES) or X-ray
Absorption Fine Structure (XAFS) is that part of the absorp-
tion spectrum near the x-ray absorption edge, the region
where the absorbance rapidly increases. It is noteworthy to
mention that typically bulk XAS is a general method of XAS
and XANES and extended x-ray absorption fine structure
(EXAFS) are more specific to the local structure and bonding
In Situ Treatment of Metals 395

(a)

2 μm 0.5 μm

(b) (c)

FIGURE 7.49  A comparison of scanning electron microscopy (SEM) (shown as (a)) versus transmission electron microscopy (TEM)
(shown as (b) and (c)) images of biogenic uraninite (UO2) precipitates. The photographed samples were collected from the same incubation
of carefully cultured Shewanella oneidensis strain MR-1 under slow (cell count, 1 × 108 cells/mL, and temperature, 20°C) conditions in
a 30 mM sodium bicarbonate (NaHCO3) buffer at concentrations of 1 × 10 −3 M uranyl (UO22+), 2 × 10 −3 M acetate (C2H3O2−), and 5 mM
sodium lactate (NaC3H5O3). (Courtesy of Dr. Gang Ning for the SEM image and Alice Dohnalkova for the TEM images.)

XANES (with pre‐edge) EXAFS

of the absorbing element.147–150 XANES and EXAFS are the
techniques that require a tunable x-ray source (i.e., the syn-
chrotron). The sudden increase in absorption at the absorption
edge is due to the excitation of a photoelectron out of the inner
electron orbitals of an element and into the continuum. As the
x-ray energy is increased and the x-ray absorption stabilizes,
this is referred to as extended x-ray absorption fine structure
(EXAFS). The pre-edge XANES and EXAFS regions of an
XAS spectrum contain information on the electronic state of
X‐ray absorption

the absorbing element and its symmetry and are summarized

conceptually in Figure 7.50. XANES and EXAFS graph-
ics from the aforementioned biologically mediated uranyl
(UO22+) reduction to uraninite (UO2) in Section 7.4.3.2.3 are
presented in Figure 7.51.141,142 The data show a close linear fit
to the uraninite (UO2) pattern; however, the deviation suggests
some percentage of uranium as uranyl (UO22+). Observations X‐ray energy
such as this underscore the great potential of XAS to inform
geochemical mechanism determinations. FIGURE 7.50  Conceptual depiction of the x-ray absorption spec-
The analytical results of chromium analysis described in troscopy pattern.
Section 7.4.2.3 demonstrated that hexavalent chromium (Cr6+)
was present in soil prior to treatment at 1,070 mg/kg (with total chromium (Cr3+); however, hexavalent chromium (Cr6+) was
chromium present at 10,397 mg/kg). Hexavalent chromium not detected in soil prior to and after treatment. Following the
(Cr6+) was therefore present at <0.1% of the total sample mass bulk XAS data results, samples of the untreated and treated
and at ~10% of the total chromium content. Although XAS soil were analyzed using microprobe x-ray fluorescence
was attempted on the pre- and posttreatment homogenates, the (μXRF) and x-ray adsorption near-edge structure (μXANES).
technique was unable to detect hexavalent chromium (Cr6+) in Similar to the bulk XAS analysis, this uses a focused beam of
either sample. Soil samples showed the presence of trivalent x-rays to determine the presence, distribution, valence state,
396
Normalized x-ray absorption
1.5
1.0
0.5
0.0
17,150 17,200
X-ray energy (eV)
Normalized x-ray absorption
1.5
1.0
0.5
0.0
17,150 17,200
X-ray energy (eV)
FIGURE 7.51  Example x-ray absorption near-edge structure
and extended x-ray absorption fine structure graphs for biogenic
uraninite (UO2). The “fast” and “slow” trials used carefully cul-
tured Shewanella oneidensis strain MR-1 under fast (cell count,
2 × 108 cells/mL, and temperature, 37°C) and slow (cell count, 1 ×
108 cells/mL, and temperature, 20°C) conditions in a 30 mM sodium
bicarbonate (NaHCO3) buffer at concentrations of 1 × 10 −3 M uranyl
(UO22+), 2 × 10 −3 M acetate (C2H3O2−), and 5  mM sodium lactate
(NaC3H5O3). The blue circles represent the raw data, the red line is a
linear combination fit (LCF), and the blue and black lines are refer-
ence standards for uranyl (UO22+) and uraninite (UO2).
and form of different elements at high resolutions (down to
10 μm). The focused beam provides better sensitivity to trace
concentrations of individual chromium species. Samples for
the μXANES analysis were prepared by splitting a COPR
nodule and pressing the exposed face on a piece of Kapton
tape. This allowed for analysis of a cross section of the nod-
ules before and after treatment. The μXRF cross section maps
and corresponding sectioned pretreatment and posttreatment
nodules are presented in Figure 7.52. The μXRF cross section
maps presented in Figure 7.52 are somewhat influenced by the
three-dimensional surface of the nodule that was presented
onto the Kapton tape for imaging; however, there is noticeable
difference in the primary location of hexavalent chromium
(Cr6+) between the pretreatment and posttreatment nodules.
These data demonstrated that hexavalent chromium (Cr6+)
Remediation Engineering
was present in the nodules both before and after treatment,
NaHCO3 “fast” supported by both the XRD and QEMSCAN results. This
LCF
is not surprising as the enhanced weathering induced by the
U(VI) component
U(IV) component
addition of sulfuric acid (H2SO4) decreased the nodule size,
but did not penetrate the entirety of the nodules. In the pre-
treatment nodules, hexavalent chromium (Cr6+) appears to be
present around the outer edge of the nodule. In the posttreat-
ment nodules, hexavalent chromium (Cr6+) appears to be more
central to the nodule. This is consistent with the weathering of
the nodules with the sulfuric acid (H2SO4) and suggests that
hexavalent chromium (Cr6+) associated with calcite (CaCO3)
and altered chromium spinel was liberated and subsequently
17,250 reduced to trivalent chromium (Cr3+).
7.4.3.3  Operational (Functional) Analysis
A common unknown with in situ metal precipitation strate-
NaHCO3 “slow” gies is whether or not the targeted mechanism is responsible
LCF
for the observed reductions in metal concentrations in ground-
U(VI) component
U(IV) component
water. If a chemically induced sulfide precipitation strategy
is implemented and metal concentrations in groundwater are
observed to decrease, the intuitive assumption is that metal
sulfides are precipitating and creating a solid mineral that has
a solubility that is sufficiently less than the targeted cleanup
goal. But what if the acidity scavenging nature of sulfide (S2−)
is resulting in acidity neutralization and HFO is precipitating
creating sorption sites for metals? This is equally effective in
that the metal concentration in groundwater is reduced; how-
17,250 ever, the permanence of the remedial strategy is not the same
as a low solubility metal sulfide. In the absence of mineral
characterization, spectroscopy, or microscopy, operational
analysis, such as selective extraction, can help determine if the
targeted remedial mechanism is responsible for the observed
metal reductions.
Selective extraction analysis includes incremental extrac-
tion of treated soil with different rinsates designed to incre-
mentally inform on metals immobilization strategies. The
rinsate from an extraction is analyzed using ICP-AES for the
targeted metal. For example, suppose a remedial strategy was
implemented to reduce selenium in the oxidized forms of sele-
nate (SeO42−) or selenite (SeO32−) to the more reduced forms of
elemental selenium (Se0) or selenide (Se2−). However, because
selenate (SeO42−) and selenite (SeO32−) are oxyanions (similar
to arsenate [AsO43−] and arsenite [AsO33−]), there is a poten-
tial for sorption to HFO. An initial extraction with distilled
water would confirm that the selenium is not dissolved and
is  the first of several extractions and is the mildest. A second
extraction with a phosphate (PO43−) solution may result in the
displacement of sorbed selenate (SeO42−) or selenite (SeO32−)
due to the respective ionization strengths of the different oxy-
anions. If this is observed, that is definitive evidence that sel-
enate (SeO42−) and selenite (SeO32−) were simply sorbed onto
the soil particles instead of reduced to elemental selenium
(Se0) or selenide (Se2−). If, after the phosphate (PO43−) solu-
tion extraction, still not selenate (SeO42−) or selenite (SeO32−)
is observed in the rinsate, that is an indication that precipi-
tation did occur. A final extraction with hydrochloride acid
(HCl) or nitric acid (HNO3) that results in selenate (SeO42−)
In Situ Treatment of Metals 397

(a) (b)

116
6
115

Y distance (mm)
114
Y distance (mm)

4
113

112
2
111

110
0
63 64 65 66 67 68 69 0 1 2 3 4 5
(c) X distance (mm) (d) X distance (mm)

FIGURE 7.52  (a) Pretreatment nodule sliced in half for the generation of a cross-sectional microprobe x-ray fluorescence (μXRF) map.
(b) Posttreatment nodule sliced in half for the generation of a cross-sectional μXRF map. Note green circles indicated the mapped surface on
the nodules. (c) Pretreatment nodule cross-sectional μXRF map. (d) Posttreatment nodule cross-sectional μXRF map. Note white locations
indicate high concentrations of hexavalent chromium (Cr6+). (Courtesy of Dr. Jeff Gillow for the images.)

and selenite (SeO32−) in the rinsate would further confirm ele-
mental selenium (Se0) or selenide (Se2−) precipitation during
treatment and subsequent oxidation and dissolution during the
selective extraction analysis.
7.4.4  Characteristics of Specific Metals
This section is included to discuss specific components of
some routinely encountered metals and radionuclides in
in situ remediation.
7.4.4.1 Chromium
Chromium belongs to group VIB of the periodic table
(page  ii). It has three valence states that are environmen-
tally relevant, Cr2+, Cr3+, and Cr6+, but trivalent chromium
(Cr3+) and hexavalent chromium (Cr6+) are the most common.
Hexavalent chromium (Cr6+) is acidic, forming chromates
(CrO4)2− and dichromates (Cr2O7)2−, while the other valence
states are basic. Hexavalent chromium (Cr6+) is highly soluble
in groundwater, across the range of naturally occurring pH
and oxidation–reduction conditions. Oxidation–reduction
transformation, precipitation/dissolution, and adsorption/
desorption reactions control the fate of chromium in natu-
ral aquifers.151 Chromate (CrO42−) and bichromate (HCrO4−)
are among the commonly observed ions of hexavalent chro-
mium (Cr6+) across natural aquifer geochemistry. Chromic
acid (H2CrO4) and the dichromate ion (Cr2O72−) may also
be observed at strongly acidic pH. A log C–pH graph for
an equilibrated chromate system is presented in Figure 7.53
based on a total chromate concentration of 1 × 10 −2 M, at
25°C and demonstrates that chromate (CrO42−) and bichro-
mate (HCrO4−) are the predominant species over a broad
range of natural pH level. Dichromate (Cr2O72−), characteris-
tic of an orange color when dissolved in water, may speciate
according to the following reaction provided by Felmy et al.
with a pKa of −1.54152:
HCrO 4 - + HCrO 4 - ® Cr2O72 - + H 2O (7.66)
398 Remediation Engineering

0 in water and makes it possible to achieve drinking water and

pKA1 = 0.86 pKA2 = 6.51 groundwater regulatory standards (Table 7.4). Even though
–1
[H2CrO4] [HCrO4–] [CrO42–] the federal MCLs summarized in Table 7.4 do not have a stan-
–2
dard for hexavalent chromium (Cr6+), it is of primary concern
–3
due to the higher solubility and mobility in groundwater. At
–4 the state regulatory level, typical standards that have been set
log[C]

–5 [H+] [OH–] for hexavalent chromium (Cr6+) range from as low as 10 to as

–6
high as 110 µg/L.
Precipitation strategies for chromium remediation entail
–7
two principal elements: reduction of hexavalent chromium
–8 (Cr6+) to trivalent chromium (Cr3+) and availability of a reac-
–9 tive anion that will form a durable precipitate with trivalent
–10 chromium (Cr3+). The reduction of hexavalent chromium
0 2 4 6 8 10 12 14 (Cr6+) may be achieved by reductants that can be expected in
pH groundwater of low oxidation–reduction potential. Hydrogen
sulfide (H2S) is one such example and has received attention
FIGURE 7.53  Speciation of 1 × 10 −2 M chromate (CrO42−). as one of the major reduced inorganic species that is associ-
ated with reduction of aquifer matrices. A speciation diagram
The solubilities of typical hexavalent chromium (Cr6+) com- for the chromium–H2O system is presented in Figure 7.54 and
pounds in aerobic aquifers are high: potassium chromate shows that trivalent chromium (Cr3+) is the primary oxidation
(K2CrO4) Ksp = 1.87 × 102, potassium dichromate (K2Cr2O7) state under slightly oxidizing to reducing conditions over a
Ksp = 2.52 × 10 −1, and calcium chromate (CaCrO4) Ksp = 2 × broad range of pH level.
10 −2. Accordingly, removal of hexavalent chromium (Cr6+)
7.4.4.2 Arsenic
ions from groundwater must be accomplished indirectly,
through conversion of hexavalent chromium (Cr6+) to triva- Arsenic, although not abundant in Earth’s crust, is widely
lent chromium (Cr3+) and subsequent precipitation as a chro- distributed around Earth in more than 150 arsenic-bearing
mium hydroxide (Cr(OH)3). The trivalent chromium (Cr3+) minerals. It is ubiquitous in small amounts, with average
precipitates are comparatively insoluble and readily form concentrations ranging from 7 to 11 mg/kg in American
compounds such as chromium hydroxide (Cr(OH)3) and chro- soils.96 Arsenic is actually classified as a nonmetal or met-
mium iron hydroxide ((Cr, Fe)(OH)3).27,61 The low solubility alloid, although it is grouped with the metals for most envi-
of these chromium hydroxide compounds limits chromium ronmental purposes. Bissen and Frimmel53 and Smedley and
Kinniburgh96 provide extended reviews of arsenic geochem-
istry and mobility.
20
Arsenic can occur in several valence states, but most
commonly occurs as an oxyanion (i.e., A xOyz−) of trivalent
15 arsenite (As3+; AsO33−) or pentavalent arsenate (As5+; AsO43−)
HCrO4–
(Figure  7.55). Under strongly reducing conditions, elemen-
10 tal arsenic (As0) and its gaseous form arsine (As3−) may also
Cr3+ CrO42– be possible, though these are not relevant in natural systems
5
related to in situ metal precipitation. Thermodynamics pro-
pE

CrOH2+
0 vides useful insight into the equilibrium chemistry of inor-
Cr(OH)3(s, am)
ganic arsenic species. In oxygenated waters, arsenate (As5+)
Cr(OH)4–

–5 is dominant, existing in anionic forms of either dihydro-

–10
–15
0 2 4 6 8 10
pH
FIGURE 7.54  pE–pH stability diagram for the chromium-water
system. Under oxidizing conditions and a broad range of pH,
hexavalent chromium (Cr6+, speciating as chromic acid [HCrO4−]
and chromate [CrO42−]) predominates. Notice the broad range of tri-
valent chromium (Cr3+), especially at circumneutral pH—support-
ing the abiotic and biotic reductive in  situ remediation strategies.
This pE–pH stability diagram was calculated assuming a tempera-
ture of 25°C and a chromium concentration of 1.9 × 10 −6 M. This
figure was made using MINTEQ with the wateq database.
gen arsenate (H2AsO4−), hydrogen arsenate (HAsO42−), or
the arsenate ion (AsO43−) over the pH range of 5.0–12.0,
which covers the range encountered in natural groundwa-
12 14 ter (Figure 7.56). Under anoxic conditions, arsenite (As3+) is
stable, with nonionic arsenious acid (H3AsO3) and anionic
dihydrogen arsenite (H2AsO3−) species dominant below and
above pH 9.22, respectively (Figure 7.57). A stability diagram
for the arsenic–water system is presented in Figure  7.58.
Because arsenic is labile, oxidation–reduction potential (EH)
and pH are the most important factors controlling its specia-
tion and chemical form. This makes arsenic susceptible to
biogeochemical reactions in the subsurface.
In the subsurface, the solubility/mobility of geogenic
arsenic is typically controlled by sorption to other minerals.
In Situ Treatment of Metals 399

Nonmetals:
Form anions and/or oxyanions
14 2 15 2 16 2
8 8 8
4 5 6
Si P S Oxyanions tend to be
more mobile in the
Silicon Phosphorus Sulfur environment
28.0855 30.973762 32.065

32 2 33 2 34 2
Arsenic primarily found as
8 8 8
18 18 18 oxyanion/oxyacid of:
Ge 4 As 5 Se 6
Pentavalent arsenate (As5+)
Germanium Arsenic Selenium Trivalent arsenite (As3+)
72.63 74.92160 78.96

50 2 51 2 52 2
8 8 8
18 18 18 Other valence states:
Sn 18 Sb 18 Te 18 Semi‐metallic/elemental
4 5 6
arsenic (As3+)
Tin Antimony Tellurium Arsine (As3+)
118.710 121.760 127.60

Metals:
Form cations

FIGURE 7.55  Properties of arsenic.

0 0
pKA1 = 2.26 pKA2 = 6.76 pKA3 = 11.29
pKA1 = 9.29
–1 –1
[H3AsO4] [H2AsO4 –] [HAsO4 2–] [AsO4 3–]
–2 [H3AsO3] [H2AsO3–]
–2
–3 –3
–4 –4
log[C]

log[C]

–5 + –5
[H ] [H+]
–6 [OH–] [OH–]
–6 [HAsO32–]
–7
–7
–8 pKA2 = 14.22
–8 pKA3 = 19.22
–9
–9
–10 [AsO33–]
0 2 4 6 8 10 12 14 –10
0 2 4 6 8 10 12 14
pH
pH

FIGURE 7.56  Logarithmic transformation of arsenate (AsO43−) FIGURE 7.57  Logarithmic transformation of arsenite (AsO33−)
concentration versus pH. concentration versus pH.

The  most common companions of arsenic in natural sedi-
ments are iron (Fe), manganese (Mn), and sulfur (S). Of these,
iron plays the most significant role, and since iron concentra-
tions in most sediments typically range from 0.5% to 5% by
weight (5,000–50,000 mg/kg), the role of iron in controlling
geogenic arsenic mobility is significant. Naturally occurring
HFO particles have an adsorption affinity for both arsenate
(As5+) and nonionic arsenite (As3+). Nonionic arsenite (As3+)
can sorb to HFO particles through Lewis acid–base interac-
tions, with anionic arsenate (As5+) sorption occurring through
coulombic (electrostatic) and Lewis acid–base (electron pair)
interactions (Figure 7.59).
The biogeochemistry of arsenic in sediments is complicated
by the strong binding of arsenate (As5+) to minerals like iron
oxide (FeOOH). Hence, bacterial reduction of ferric iron (Fe3+)
to ferrous iron (Fe2+) typically releases any bound arsenate
(As5+) and makes it available for further chemical or biological
reduction. The thermodynamic reduction of arsenate (As5+) to
arsenite (As3+) in the absence of oxygen could be chemically
slow and may require bacterial mediation. The investigation
into the number of species of microorganisms capable of dis-
similatory (using inorganic compounds as electron acceptors
in energy metabolisms153) arsenate (As5+) reduction reveals a
great diversity. The realization that arsenate (As5+) is indeed a
suitable electron acceptor and is readily available in both natu-
ral and contaminated environments suggests that even more
unrelated species will be discovered.154 Thus, arsenic mobility
related to engineering aquifer geochemistry is an important
consideration of an in situ remediation design and is discussed
in terms of secondary water quality in Chapter 3.
400 Remediation Engineering

20

15 H3AsO40

10 H2AsO4–

5 HAsO42–
pE

AsO43–
0 H3AsO30

–5

H2AsO3–
–10

–15
0 2 4 6 8 10 12 14
pH

FIGURE 7.58  pE–pH stability diagram of aqueous arsenic (As) species (As–O2–H2O). Species shown include arsenic acid (H3AsO40),
dihydrogen arsenate (H2AsO4−), hydrogen arsenate (HAsO42−), arsenate (AsO43−), arsenous acid (H3AsO30), and dihydrogen arsenite
(H2AsO3−). Recall arsenate (AsO43−) is arsenic in the plus-five valence state (As5+) and represents the more oxidized version of arsenic, and
arsenite (AsO33−) is arsenic in the plus-three valence state (As3+) and represents the more reduced version of arsenic. It is fitting then, based
on the scale of pE shown in this figure, that fully deprotonated (“dehydrogened”) arsenite (AsO33−) would not be visible. This pE–pH stabil-
ity diagram was calculated assuming a temperature of 25°C and an arsenic concentration of 1.3 × 10 −6 M. This figure was made using PH
Redox Equilibrium EQuation in C language with the wateq database.

Geogenic arsenic MeOH2+ O– O

Natural arsenic control: As
Arsenate:
Lewis acid–base (electron) interactions and MeOH2+ O– OH
Columbic (electrostatic) interactions
Arsenite:
Lewis acid–base (electron) interactions only

FIGURE 7.59  Geogenic characteristics of arsenic.

There is evidence in the literature that some control of sol-
uble arsenic can be realized through interaction of the arsenic
with dissolved iron (assumed to be ferrous iron [Fe2+]) and
reactive sulfide (S2−). In the presence of sulfides, precipita-
tion may remove soluble arsenite (As3+) and exert some con-
trol over trace arsenic concentrations. These processes are
complex, and an example of this complexity is the undesir-
able observation that arsenic also can form stable aqueous
complexes with hydrogen sulfide (H2S). Arsenic solubility
decreases at low oxidation–reduction potential and acidic pH,
potentially due to the formation of arsenic sulfides (realgar
[AsS] and arsenic trisulfide or orpiment [As2S3]) and arseno-
pyrite (FeAsS). The arsenic sulfide species are readily oxi-
dized and solubilized if the oxidation–reduction potential or
pH increase.53,155 It is expected that the greatest measure of
control will be provided through adsorption, incorporation,
and coprecipitation with HFO floc once the ambient aerobic
and oxidizing poise is restored. Solid–solution partitioning
coefficients (Kd; Section 7.4.2.4.2) describing the retardation
of dissolved arsenate (As5+) and arsenite (As3+) to advective
transport range from 2 L/mg for clean quartz (SiO2) to greater
than 500,000 L/mg for HFO96. Despite the fact that the actual
sorption capacity of natural soils is likely to be many times
less than that reported for laboratory-grade HFO particles, the
results confirm the extent to which naturally occurring metal
oxides and clays can control geogenic arsenic mobility under
aerobic conditions. In fact, the research indicates that the total
sorption capacity of the soil is unlikely to be a limiting factor.
Based on the discussion earlier, the migration of soluble
arsenic beyond the boundary of a reducing zone appears
unlikely, and the restoration of aerobic/oxidizing conditions
beyond an engineered or naturally reducing zone appears
likely to sufficiently restore background arsenic concentra-
tions in groundwater (Figure 7.14). Geochemical data from
two wells are presented in Figure 7.14, which provides an
example of arsenic mobilization under established reducing
conditions. After injection, the well identified as influenced
with carbon shows increased concentrations of methane,
In Situ Treatment of Metals
TOC, manganous manganese (Mn2+), and arsenic with a
decrease in sulfate (SO42−). The well identified as downgra-
dient of the injection demonstrates almost 5  years of data
postinjection. Most notably the arsenic concentration remains
below laboratory detection limits, even though TOC from the
upgradient injection appears to have reached this downgradi-
ent well. This implies that arsenic that was mobilized as a
result of the carbon injection was attenuated as groundwater
moved downgradient.
Based on available empirical data and published research,
it is reasonable to expect that the dissolution of arsenic within
an engineered or naturally reducing zone is a transient phe-
nomenon that will be limited to the boundaries influenced by
treatment reagent and that will reverse once the original aero-
bic and oxidizing poise of the aquifer is restored. Site-specific
areas of focus from a regulatory or stakeholder perspective
may include the following:
• The size of the in  situ engineered or naturally
reducing zone: The size of these zones is typically
established by equilibrium between the amount of
carbon substrate present, the availability/recharge
of electron acceptors, microbial consumption of the
carbon, advective equilibrium between the mobile
and immobile fractions of the aquifer, and dilution.
As the carbon moves through an aquifer, its con-
centrations diminish due to microbial consumption,
dual-domain equilibrium, and dilution, eventually
allowing microbial activity to return to pretreat-
ment levels. It is at or just beyond this point that the
geochemical environment will recover its aerobic/
oxidizing poise because the utilization of electron
acceptors falls short of the natural recharge.
• The time required for an in  situ engineered reduc-
ing zone to dissipate: Upon completion of remedial
efforts, the reducing conditions within an IRZ will
dissipate. Without a continuing source of degradable
organic carbon, the influx of electron acceptors will
eventually allow the natural aerobic/oxidizing poise
to be reestablished and should result in the immobi-
lization of any dissolved arsenic solubilized within
the IRZ. The length of time for this to occur may
also consider the stored carbon in biomass, which
has been shown to contribute to anaerobic reduc-
ing conditions after the supplied carbon source is
exhausted.156
• Competitive sorption: Certain anions can out com-
pete with arsenic for sorption sites on HFO particles
(i.e., phosphate [PO43−], bicarbonate [HCO3−], and
silicate [SiO42−]).
Contaminated groundwater normally contains arsenite (As3+)
and arsenate (As5+), the ratio being dependent on the biogeo-
chemical conditions of the groundwater system. Between
them, arsenate (As5+) is more amenable to removal by a major-
ity of reaction mechanisms. Natural biogeochemical cycles
of ferrous and ferric iron (Fe2+ and Fe3+, respectively) and
401
arsenite and arsenate (As3+ and As5+, respectively) are linked,
and iron chemistry controls arsenic contamination in shal-
low groundwater systems. Under aerobic conditions, ferric
iron (Fe3+) and manganic manganese (Mn4+) oxides remove
arsenic from the dissolved phase likely through coprecipita-
tion and adsorption. Preoxidation of arsenite (As3+) to arse-
nate (As5+) followed by selective sorption onto the surfaces
of microparticles of HFO is the underlying mechanism for
excellent arsenate (As5+) removal. However, the effectiveness
of HFO particles varies markedly for arsenite (As3+) removal.
Combined reactions of arsenite (As3+) oxidation to arsenate
(As5+) and the introduction of ferric iron (Fe3+) can be accom-
plished by implementing the Fenton’s reaction (Chapter 6)
within an IRZ. Preoxidation followed by injection of ferric
chloride (FeCl3) can also achieve the same objective.
7.4.4.3 Radionuclides
Some atomic nuclei are unstable (that is, radioactive), and
during the spontaneous changes that take place within the
nucleus, various forms of radiation are emitted. While all
elements that have more than 83 protons are naturally radio-
active, it is possible artificially to produce unstable isotopes,
or radionuclides, of virtually every element in the periodic
table.157 Here, focus is given only to uranium (U), technetium
(Tc), and plutonium (Pu).
7.4.4.3.1 Uranium
Uranium is a naturally occurring radionuclide that occurs
as the 238U (most abundant) and 235U isotopes, with minor
quantities of the 234U isotope present as a decay product of
the 238U isotope. Natural uranium contains only 0.7% of fis-
sile (able to undergo nuclear fission) 235U, and enrichment to
3% 235U is required for use in power generation. Uranium is
transported through groundwater in the oxidized U6+ valence
state, typically as uranyl (UO22+) under acidic to slightly alka-
line conditions. Under strongly alkaline conditions, the mixed
oxidation state complex triuranium octoxide (U3O8) exists.
In the presence of carbonate (CO32−), stable uranium carbon-
ate complexes (UO2(CO3)34− or UO2(CO3)22−) predominant,
and when groundwater becomes sufficiently, reducing urani-
nite (UO2) precipitation occurs with uranium in the reduced
insoluble U4+ valence state. Above a pH of about 5.0, carbon-
ates prevail. At elevated uranium concentrations in ground-
water, solid uranyl carbonate (UO2CO3) exists over a fairly
narrow pH range of 5.0–6.0, with dissolved uranyl carbon-
ate (UO2CO3) anions existing from near neutral to strongly
alkaline conditions. Throughout this range, uranium remains
in the uranyl (UO22+) oxidation state. An oxidation–reduction
potential versus pH diagram (pE–pH stability diagram) for
uranium is provided as Figure 7.60.
In situ groundwater remediation of uranium using an anaer-
obic biological process is well established.140–142,158–165 These
studies report that the addition of an organic carbon source
to a typical uranium plume will result in uranium precipita-
tion as insoluble uraninite (UO2) and that sulfides (S2−) can
be coprecipitated with the uranium to provide long-term ura-
ninite (UO2) stability. Others have shown that uranyl (UO22+)
402
20
15
UO2(CO3)22–
UO2CO30
UO22+
10
5 UO2(CO3)34–
pE
U4+
0 0.40
Uraninite (UO2)
–5
–10
–15
0 2 4 6 8 10
pH
FIGURE 7.60  pE–pH diagram of aqueous U species (U–C–O–H).
Notice the numerous compounds of uranium carbonate (UO2CO30
(rutherfordine), UO2(CO3)22−, and UO2(CO3)34−) over a broad range
of pH at mildly oxidizing conditions, typical of an uninfluenced
aquifer. These soluble compounds promote uranium transport
throughout the aquifer. Uraninite (UO2), which is relatively insol-
uble under reducing conditions, shows stability over a broad range
of pH indicating that uranium under reducing conditions will likely
precipitate out of groundwater as uraninite (UO2). This pE–pH sta-
bility diagram was calculated assuming a temperature of 25°C and
the following uranium and carbon (as bicarbonate [HCO3−]) concen-
trations, respectively: 4.2 × 10 −7 M, and 4.9 × 10 −3 M. This figure
was made using PH Redox Equilibrium EQuation in C language
with the wateq database.
reduction can be rapidly achieved in an aquifer contain-
ing excess organic carbon where acetate (C2H3O2−), lactate
(C3H6O3−), and formate (CHO2−) is supplied. An example of
a successful in  situ uranium treatment strategy is presented
in Figure 7.61.
SRBs have been shown to be capable of uranium (UO22+)
reduction as well.164,165 The process summarized in the litera-
ture primarily relies on SRBs to take soluble sulfate (SO42−)
and reduce the sulfate (SO42−) to sulfide (S2−). Sulfide (S2−)
then chemically reacts with ferrous iron (Fe2+) to make iron
sulfides (FeS). The sulfate (SO42−) reduction/iron sulfide
(FeS) formation process is a process that occurs in soils
and sediments of lakes, rivers, swamps, and estuaries; it is a
nearly universal process wherever oxygen and other electron
acceptors can be excluded or minimized. SRBs are nearly
ubiquitous bacteria. SRBs are often active in clay lenses in
otherwise aerobic aquifers, and they are also abundant in root
zones where photosynthetic exudates are produced or plant
biomass is degraded.
It has been shown that SRBs are abundant in groundwater
containing high concentrations of uranium (UO22+) at a site
in Shiprock, New Mexico, and that these bacteria are capable
of both uranium (UO22+) and sulfate (SO42−) reduction result-
ing in iron sulfide (FeS) and uraninite (UO2) precipitation.
Microbial reduction of uranium (UO22+) was shown to result
in soluble uranium (UO22+) concentrations as low as 1 pCi/L
(1.48 µg/L).164 A curie is a U.S. unit of measure of the intensity
Remediation Engineering
1.00
0.90
Uranium concentration (mg/L)
0.80
Total uranium
UO2(OH)3– 0.70
Dissolved uranium
0.60 MCL
UO2(OH)42–
0.50
0.30
0.20
0.10
MCL = 0.030 mg/L
0.00
Mar‐00
Sept‐00
Mar‐01
Sept‐01
Mar‐02
Sept‐02
Feb‐03
Aug‐03
12 14
Date
FIGURE 7.61  Successful treatment of uranium. The total ura-
nium (representing all forms of soluble uranium) and the dissolved
uranium (representing the uranyl [UO22+] form in the U6+ oxidation
state) both decrease simultaneously. This is expected as the more
reduced form of uranium (uraninite [UO2]) is comparatively insol-
uble and would precipitate out and not be detected in an aqueous
sample.
of radioactivity, and 1 curie is equal to 3.7 × 1010 disintegra-
tions per second (dps). The SI unit of measure of the intensity
of radioactivity is the becquerel (Bq), which is equal to 1 dps.
Pico is the metric prefix for one trillionth, so a “picocurie” is
one trillionth of a curie. Picocuries are often used for conve-
nience when describing the intensity of the radioactivity of
radionuclides. The conversion of picocuries per liter (pCi/L)
to a mass concentration (µg/L) is element specific and for ura-
nium is 1 pCi/L = 1.48 µg/L.166
In the absence of iron (and other oxidized minerals), sul-
fate (SO42−) reduction in aquifers will lead to accumulation
of aqueous sulfide species (H2S and HS−; Section 7.3.1.1.3).
Where oxidized iron minerals (such as hematite [Fe2O3]) are
abundant (range 1%–3%), sulfide (S2−) will react with the iron,
reducing the ferric iron (Fe3+) to ferrous iron (Fe2+). Ferrous
iron (Fe2+) formed in this way is relatively soluble; however,
additional sulfide (S2−) formed will quickly react with the fer-
rous iron (Fe2+), and at pH greater than 6.5, iron sulfide (FeS)
minerals will rapidly precipitate. The temporary increase in
iron concentrations will last for a period of a few months. The
pH will have to be monitored to ensure that the iron sulfide
(FeS) precipitates from solution. The presence of the IRZ at
the forward edge of the plume will prevent iron migration
beyond the treatment area.
7.4.4.3.2 Technetium-99
The isotope 99Tc is a product of nuclear fission reactions and
is formed in kilogram quantities during nuclear reactions. It
has been released into the environment during weapons test-
ing and the disposal of low and intermediate level radioac-
tive wastes. 99Tc has been found in groundwater at sites where
nuclear wastes have been reprocessed or stored. The stable
In Situ Treatment of Metals
20
2+
15 TcO
TcOOH+
10
TcO(OH)20
5 TcO4–
pE
0 escaping technetium (Tc) from breached radioactive waste
Tc3O4(s)
–5
–10
–15
0 2 4 6 8 10 12 14
pH
FIGURE 7.62  pE–pH stability diagram for the technetium–water
system. The two primary compounds driving technetium geochem-
istry are the pertechnetate anion (TcO4−) and the polymeric techne-
tium species (TcnOp(4n–2p)), in this instance shown as Tc3O4. Various
technetium oxides are shown under oxidizing and strongly acidic
conditions. Noteworthy is that if sulfide (S2−) is present (as in an
engineering reducing environment), Tc3O4 is likely to speciate into
technetium disulfide (TcS2), another solid precipitate of technetium.
This pE–pH stability diagram was calculated assuming a tempera-
ture of 25°C and a technetium concentration of 1.0 × 10 −10 M. This
figure was made using the Lawrence Livermore National Laboratory
database combined with the wateq database.
pertechnate (TcO4−) anion is mobile in the environment and
is taken up into the food chain as an analog of sulfate (SO42−).
Due to the low solubility of reduced technetium (Tc), the
oxidation–reduction chemistry of technetium (Tc) is crucial
in governing its mobility (Figure 7.62). Several recent studies
have shown that 99Tc can be removed from aqueous solution
via the reduction of pertechnetate (TcO4−) to insoluble, low
valence forms. Technetium (Tc7+) can act as respiratory elec-
tron acceptor, and direct enzymatic reduction of technetium
(Tc7+) has been reported. On the basis of broad-metal reduc-
tase activity against high valence metals (hexavalent chro-
mium [Cr6+], ferric iron [Fe3+], manganic manganese [Mn4+],
and uranyl [U6+]), SRBs may be able to reduce technetium
(Tc7+) enzymatically. This hypothesis is also supported by the
fact that the pertechnate anion (TcO4−) is bioavailable as a sul-
fate (SO42−) analog and may therefore be a surrogate electron
acceptor for anoxic growth. Hence, microbial reduction of the
pertechnate anion (TcO4−), likely as a sulfide (S2−) precipitate,
should be a preferred method for remediating 99Tc contami-
nated groundwater systems.167,168
99Tc has a half-life of 2.13 × 105 years. Reference to the
oxidation–reduction pH diagram (Figure 7.62) for the sys-
tem Tc–S–O–H shows that the pertechnate anion (TcO4−) is
the stable species under ordinary aerobic conditions. As the
reductive precipitation technology is implemented and the
system moves toward anaerobic, reductive conditions, this ion
is reduced first to technetium dioxide (TcO2) and then to one
of two mixed oxidation state hydrous oxides, Tc3O4 or Tc4O7.
Finally, as reductive conditions stabilize and sulfides (S2−) are
403
generated, the stable compound technetium disulfide (TcS2)
becomes the predominant species. In the absence of sulfide
(S2−), Tc3O4 is reduced to the hydroxide, Tc(OH)2. Technetium
disulfide (TcS2) is known to be stable in the presence of sul-
fide (S2−). The stability of the technetium disulfide (TcS2) spe-
cies is well documented under sulfur-present conditions in
laboratory experiments and may further retard and retain any
containers.
An even more emphatic conclusion regarding a slightly
different technetium sulfide stoichiometry, technetium hepta-
sulfide (Tc2S7), has been presented. The pertechnetate oxy-
anion (99TcO4−), a potentially mobile species in leachate from
a breached radioactive waste repository, was removed from a
brine solution by precipitation with sulfide (S2−), ferric iron
(Fe3+), and ferrous sulfide (FeS) at normal environmental pH.
Hematite (Fe2O3) and goethite (FeOOH) were the predomi-
nant minerals in the precipitate obtained from the pertech-
netate oxyanion (99TcO4−) and ferric iron (Fe3+) reaction. The
observation of small particle size and poor crystallinity of the
minerals formed in the presence of pertechnetate (99TcO4−)
suggested that the technetium (Tc) was incorporated into the
mineral structure after reduction to a lower valence state.
Amorphous ferrous sulfide (FeS), an initial phase precipitat-
ing in the pertechnetate oxyanion (99TcO4−) and ferrous iron
sulfide (FeS) reaction, was transformed to goethite (FeOOH)
and hematite (Fe2O3) on aging. The black precipitate obtained
from the pertechnetate (99TcO4−) sulfide (S2−) reaction was
poorly crystallized technetium heptasulfide (Tc2S7), which
was insoluble in both acid and alkaline solution in the absence
of strong oxidants. The results suggested that ferrous- and/
or sulfide-bearing groundwater and minerals in host rocks or
backfill barriers could reduce the mobility of technetium (Tc)
through the formation of less soluble technetium-bearing fer-
ric iron (Fe3+) and/or sulfide (S2−) minerals.
7.4.4.3.3 Plutonium
As a result of activities ranging from nuclear weapons test-
ing, plutonium production, and nuclear accidents, significant
quantities of soils and groundwater systems have been con-
taminated with plutonium (Pu) and other actinides (elements
89–103 on the periodic table of elements). Migration of plu-
tonium from waste disposal basins had been thought to be
insignificant, given that plutonium was believed to be particle
reactive, and hence would be transported in groundwater at a
much slower rate than in cases of more mobile radionuclides
(uranyl [UO22+] and pertechnetate [TcO4−]). Recently, how-
ever, concerns have increased due to speculation that pluto-
nium migration might be enhanced through colloid-facilitated
transport.
A detailed oxidation–reduction versus pH diagram for plu-
tonium (Pu) is presented in Figure 7.63. Here, the solid com-
pound plutonium dioxide (PuO2) occupies the largest area of
stability. It is estimated that the solubility of undissociated
plutonium hydroxide (Pu(OH)4) is at 1 × 10 −17 M in this larg-
est stability region. For comparison, a maximum permissible
concentration in drinking water is 0.08 µg/L (1 × 10 −9.5 M).
404 Remediation Engineering

20 PuO22+

PuO2+
15
Pu(OH)22+
10 PuOH3+

5 PuO2(s)
pE Pu3+

–5

–10

–15
0 2 4 6 8 10 12 14
pH

FIGURE 7.63  pE–pH stability diagram for the plutonium–water system. Over a broad range of oxidation–reduction and pH conditions,
plutonium is stable as plutonium oxide (PuO2), with plutonium in the +4 oxidation state. Based purely on this speciation, plutonium mobility
in situ may be minimal—though colloidal transport should be considered as discussed in the text. This pE–pH stability diagram was calcu-
lated assuming a temperature of 25°C and a plutonium concentration of 4.1 × 10 −11 M. This figure was made using the Lawrence Livermore
National Laboratory and Nuclear Energy Agency database combined with the wateq database.

Thus, the conventional view until recently was that only under
extreme oxidation–reduction conditions and in the presence
of acidic pH do the soluble plutonium species become pos-
sible. Recently, however, two routes of mobilization, colloidal
transport and oxidation of plutonium dioxide (PuO2) by water,
have been discovered. The oxidized fraction of the plutonium
is in the more mobile Pu6+ valence state.
Reductive metal precipitation technology may be able
to counteract the routes of mobilization for plutonium. The
reducing environment provided by reagent injection may be
sufficient to reverse the slow oxidation suspected. While this
reduction is unlikely to be fully irreversible, the slow rate of
the oxidative reaction may allow this reduction to be a feasible
treatment technology if applied on a periodic “maintenance”
basis. It is also theoretically possible that the reductive process
could remove colloidal metals as well in a variety of ways: (1)
mechanical entrapment by the increased quantity of biomass,
(2) direct electrostatic attraction to the new biomass surfaces,
and (3) altering the overall charge balance of the system. If the
reductive technology was applied to plutonium, the pH would
need to be carefully controlled because the soluble Pu3+ ion is
predominant at acidic pH, especially under reducing conditions.
7.5 PERMANENCE ON IN SITU
METALS TREATMENT
IRZ strategies to address elevated metal concentrations in
groundwater rely on the formation of durable precipitates.
A reliable metal precipitation strategy is one that evaluates
the ambient geochemistry and contrasts precipitate stability
under ambient, contaminant, and engineered conditions. This
means that metals will remain present in the aquifer matrix,
but their solubilities will be low enough to sustain acceptable
dissolved-phase concentrations, as long as the aquifer chem-
istry remains at an acceptable pH and oxidation–reduction
potential. It will always be possible to resolubilize precipi-
tated metals through extreme geochemical shifts, and the
in situ treatment strategy must create metal precipitates that
are durable under reasonably foreseeable aquifer chemistry
composition (pH, ionic strength/ionic composition, creation
of oxidizing or reducing conditions, etc.).
One factor that influences long-term stability is the possi-
bility for competing precipitation/coprecipitation endpoints
depending on the chemistry used during treatment and the
kinetics of formation. An example would be the intended
precipitation of nickel sulfide (NiS). If conducted at alkaline
pH, some of the nickel could precipitate as nickel hydroxide
(Ni(OH)2) and be more susceptible to remobilization upon
establishing circumneutral pH (i.e., approximately 7.0) (Figure
7.13). Therefore, although acidity neutralization or secondary
coprecipitation mechanisms may result in a decrease of dis-
solved metal concentrations under engineered conditions, the
permanence of in situ metal precipitation that rely significantly
on hydroxide or oxide coprecipitation may be susceptible to dis-
solution upon reestablishing ambient geochemical conditions.
It has been discussed at length in Chapter 4 and elsewhere36
that stored contamination (in this case acidity/alkalinity) in
the immobile fraction of the aquifer may be viewed as a con-
tinued source of contamination to the mobile fraction of the
aquifer. If, as the stored acidity/alkalinity in the immobile
fraction equilibrates with the mobile fraction through slow
advection and (minimally) diffusion, there is a potential for
In Situ Treatment of Metals
acidic/alkaline pH conditions, then previously coprecipitated
metal hydroxides and metal oxides may be subjected to dis-
solution. Not all coprecipitation reactions will be susceptible
to dissolution under ambient geochemical conditions, but if
an existing source of acidity/alkalinity remains in situ, unpre-
dictable dissolution of coprecipitates may impede site closure.
This is a demonstration of two key design parameters devel-
oped throughout this chapter:
1. The expected in situ solubility of the achieved metal
precipitate should result in a dissolved phase equilib-
rium solubility of the targeted metal that is less than
the regulatory standard under a range of expected
geochemical conditions.
2. The effectiveness of in  situ metal precipitation
is chiefly associated with distributing treatment
reagents throughout the impacted aquifer to achieve
sufficient contact with stored acidity/alkalinity and
dissolved metals to protect the freshly precipitated
solids and ensure permanence of the remedy.
In cases where there may be an anticipated incompatibility
between the precipitated form of the metal and the natural envi-
ronment, the rate of dissolution compared with the groundwater
flux can still keep dissolved concentrations in compliance with
the applicable numeric cleanup goals. This must be properly
confirmed both superficially and mechanistically. And while
we only have a limited capacity to anticipate the future, there
are other controls both geochemical and institutional that can
be drawn on as appropriate to increase the level of certainty.
7.5.1  Sulfides
A recurring theme in in  situ metal precipitation is that the
resultant form of the “contaminant” (i.e., the metal) is a spar-
ingly soluble precipitate, and the metal is not destroyed or
converted to another compound. Therefore, when a metal is
precipitated out of groundwater, it is important to consider
typical fluctuations in groundwater geochemistry (oxidation–
reduction potential, pH, ionic strength) and how they may
influence the resultant solubility. This section explores the
stability of metal sulfides (MeS) as well as the susceptibil-
ity of metal sulfides (MeS) to “reoxidize” with reversion of
an IRZ to ambient geochemistry. Additionally, the naturally
occurring geology is considered with respect to a capacity to
resist solubility increases postremediation.
The solubility of metal sulfides (MeS) is suppressed during
treatment under anaerobic conditions when reactive sulfide
(S2−) is present. Posttreatment, metal sulfides (MeS) tend to
be slightly more soluble due to the reactivity with dissolved
oxygen. However, the rate of dissolution will be limited by the
following factors:
1. The natural rate of oxygen influx, which for most
sites will be minimal due to the low solubility of oxy-
gen (i.e., 8–30 mg/L at ambient groundwater temper-
atures and pressures) and slow groundwater velocity.
405
2. The scavenging of oxygen by reduced iron sulfides
(FeS) and other reduced phases formed within the
reactive zone, which can be hundreds of times more
prevalent than the sulfide precipitates formed by the
target metal.
3. The generally low solubility products (Ksp) for most
metal sulfides (MeS) (Tables 7.6 through 7.8).
4. In situations where the targeted metal sulfides
(MeS) are incorporated within a much greater
matrix of reduced iron minerals, oxidation of the
iron minerals creates a protective coating that to
some degree passivates the rest of the underlying
solid mass.169 Fresh iron hydroxides that form will
have some capacity to sequester a number of target
metals through sorption. How effective these pro-
cesses might be will vary from site to site and must
be carefully considered.
These factors discourage resolubilization of metal sulfides
(MeS), keeping dissolved concentrations of targeted metals
below applicable cleanup standards over the long term.
7.5.2 Element Re-oxidation
The value and positive remedial benefit of in situ metal pre-
cipitation has been discussed at length in this chapter. Specific
focus has been placed on engineered in  situ metal precipi-
tation, which generally requires mildly to strongly reduc-
ing conditions and manipulates coprecipitation and electron
transfer with primarily iron and sulfur species. The reduced
conditions under which the metal precipitates form encour-
age the stability of these insoluble minerals. However, as the
influence of the established IRZ diminishes due to ambient
flux of mildly acidic and oxidizing groundwater through the
treatment zone, the potential for dissolution via reoxidation
of oxidation–reduction potential sensitive metals (i.e., chro-
mium, uranium) increases. The potential and likelihood for
reoxidation of some oxidation–reduction potential sensitive
metals is discussed in this section.
Reduced selenium (Se0 or Se2−) and molybdenum (Mo4+)
that may end up sequestered within an IRZ are susceptible
to reoxidation to soluble forms (i.e., selenate [SeO42−] or
selenite [SeO32−] and molybdate [MoO42−]) under aerobic
conditions, but there are a number of factors that will limit
their rebound. Some portion of the reduced selenium (Se0
or Se2−) and molybdenum (Mo 4+) minerals will likely be
incorporated within and occluded by other reduced mineral
precipitates, such as iron sulfides (FeS). During the resto-
ration of aerobic conditions, the surfaces of these minerals
can develop a protective coating that would passivate the rest
of the underlying mineral mass, offering long-term protec-
tion of incorporated selenium (Se0 or Se2−) and molybdenum
(Mo4+), preventing it from reacting completely.169 Further,
freshly formed iron oxyhydroxide minerals formed during
this process will have some capacity to sequester (through
sorption) remobilized selenium and molybdenum (i.e., sel-
enate [SeO42−] or selenite [SeO32−] and molybdate [MoO42−])
406
and suppress the formation of dissolved metals at concentra-
tions requiring additional remediation.
7.5.2.1 Chromium
The primary end product of the hexavalent chromium (Cr6+)
to trivalent chromium (Cr3+) reduction process is chromium
hydroxide (Cr(OH)3), which readily precipitates out of solution
under alkaline to moderately acidic and alkaline ­conditions
(Section 7.3.1.1.3.2; Equations 7.7 through 7.10). To ensure that
this process will provide both short- and long-term effective-
ness in meeting groundwater cleanup objectives, the chro-
mium precipitates must remain immobilized within the soil
matrix of the aquifer. The trivalent chromium (Cr3+) precipi-
tates cannot be subject to dissolution or oxidation of trivalent
chromium (Cr3+) back to hexavalent chromium (Cr6+) once
groundwater conditions revert back to natural conditions.
Based on the results of significant research conducted on the
in situ chromium reduction process, it is readily apparent that
the chromium hydroxide (Cr(OH)3) precipitate is essentially
an insoluble, stable precipitate, immobilized in the soil matrix
of the aquifer. The solubilities of trivalent chromium (Cr3+)
and chromium hydroxide (Cr(OH)3(s)) are influenced more
significantly by acidic conditions than alkaline conditions
(Figure 7.24).
Contrary to the numerous natural mechanisms that cause
the reduction of hexavalent chromium (Cr6+) to trivalent chro-
mium (Cr3+), there appear to be only a few natural mecha-
nisms for the oxidation of trivalent chromium (Cr3+). Indeed,
only two constituents in the subsurface environment (dis-
solved oxygen and manganese dioxide [MnO2]) are known
to oxidize trivalent chromium (Cr3+) to hexavalent chromium
(Cr6+).170–174 The results of studies conducted on the potential
reaction between dissolved oxygen and trivalent chromium
(Cr3+) indicate that dissolved oxygen will not cause the oxida-
tion of trivalent chromium (Cr3+) under normal groundwater
conditions. However, studies have shown that trivalent chro-
mium (Cr3+) can be oxidized by manganese dioxides (MnO2),
which may be present in the soil matrix. However, only one
phase of manganese dioxide (MnO2) is known to oxidize
appreciable amounts of trivalent chromium (Cr3+) and this
process is inversely related to groundwater pH. Hence, the
reoxidation of trivalent chromium (Cr3+) to hexavalent chro-
mium (Cr6+) in a natural aquifer system is highly unlikely.
The chromium hydroxide (Cr(OH)3) precipitate has a low
solubility (solubility product, Ksp = 6.7 × 10 −31), and thus little
of the chromium hydroxide (Cr(OH)3) is expected to remain
in solution. It has been reported that aqueous concentration
of trivalent chromium (Cr3+), in equilibrium with chromium
hydroxide (Cr(OH)3) precipitates, is around 0.05 mg/L within
the pH range of 5.0–12.0 (Figure 7.51). The pH range of natu-
ral aquifer systems will be within 5.0–12.0, and, hence, the
potential for the chromium hydroxide (Cr(OH)3) to dissolve
is unlikely.
7.5.2.2 Uranium
In relative terms, expressed in molar ratios of uranium to all
of the other reduced compounds stored in the aquifer, the
Remediation Engineering
potential reoxidation of uraninite (UO2) will be low compared
to the potential reoxidation of ferrous iron (Fe2+), sulfide (S2−),
and other reduced species. Utilizing iron sulfide (FeS) com-
pounds alone, more than 1 × 104 mol of iron sulfide (FeS) will
be present for every mole of uraninite (UO2). Any proposed
remediation plan should anticipate the introduction of oxygen
and nitrate (NO3−) via natural pathways and provide for suffi-
cient reduced compounds to exhaust these sources of reoxida-
tion (i.e., “oxidants”). As the aquifer materials are exposed to
oxidants, iron sulfide (FeS) would oxidize at least as rapidly
as the precipitated uraninite (UO2) and consume the oxidants.
Because the ratio of iron sulfide (FeS) to uraninite (UO2) is
large, a limited amount of oxidant will be available to react
with uraninite (UO2). Because uraninite (UO2) will be precip-
itated first during treatment, the iron sulfide (FeS) precipitate
would be deposited over the top of the uraninite (UO2) as an
iron sulfide (FeS) coating. Iron sulfide (FeS) will therefore be
exposed to the oxidant in the groundwater before uranium-
containing precipitates would be exposed. A small amount of
the uraninite (UO2) in the aquifer may dissolve slowly, as the
iron sulfide (FeS) is depleted, and because there is so much
more iron sulfide (FeS) in the aquifer material, the uraninite
(UO2) will only mobilize at concentrations substantially less
than the allowable regulatory standards.
Iron sulfide (FeS) has been recognized as being critical to
maintaining uraninite (UO2) stability in groundwater during
and following bioremediation175,176 as well as in natural ura-
nium ore deposits. A strong correlation between uranium and
sulfur was found, indicating both a role for sulfur in deposit-
ing the uranium as well as in maintaining its deposition.177 It
is critical to note that the sulfide (S2−) continues to perform
a stabilizing function in many uranium deposits, which has
been measured at millions of years old. These deposits are
called “kinetically stable” where the sulfur acts to control
uranium stability.178
Column studies have shown that excess iron sulfide (FeS)
is an optimal material to provide an oxidation–reduction buf-
fer to prevent oxidative dissolution of uranium. It was also
stated that the more iron sulfide (FeS) present, the higher
the stability of uraninite (UO2), the mineral form that has to
be created to maintain uranium stability. A maximum con-
centration of 29 pCi/L (~43 µg/L166) of dissolved uranium*
(UO22+) was formed during reoxidation of freshly precipi-
tated uranium where a 1 × 104 molar excess iron sulfide (FeS)
was precipitated along with the uranium.175 Field data from a
study investigating the reactivity of naturally occurring pyrite
(FeS2) demonstrated that injected nitrate (NO3−) was rapidly
reduced (half-life of reduction of 2  days in a sandy aquifer
matrix), leading to the oxidation of pyrite (FeS2) to ferric iron
(Fe3+) and sulfate (SO42−) minerals, which deposited as jarosite
(KFe3(OH)6(SO4)2) and natroalunite (NaAl3(SO4)2(OH)6).
Others have shown that iron sulfide (FeS) effectively reduced
oxygen (O2) and nitrate (NO3−) from agricultural runoff when
infiltrated runoff reached the deeper aquifer.179 Iron sulfide
(FeS), reduced iron compounds in addition to iron sulfides
* Conversion from pCi/L to µg/L (for uranium) is pCi/L × 1.48.
In Situ Treatment of Metals
(including siderite [FeCO3]), and bulk organic matter can all
provide oxidation–reduction buffering in aquifers receiving
agricultural runoff.178 These examples are relevant for the
“resident farmer” scenario, indicating that even under agricul-
tural runoff scenarios, the uraninite (UO2) can be maintained
insoluble by iron sulfide (FeS).
An additional factor to maintain uraninite (UO2) stability
even in conditions where iron sulfide (FeS) has been exhausted
in the aquifer is the residual iron oxides that form after iron
sulfides oxidize. Ferric iron (Fe3+) oxides sorb uranium with
strong binding energy (bidentate and tridentate inner-sphere
complexes).180 It has been shown that these iron oxides could
maintain low dissolved uranium concentrations (less than
30  pCi/L; 44.4 µg/L).181 Similar sorption onto HFOs after
more than 30 pore volumes has also been demonstrated.182
This means that in many remediated uranium plumes, the
iron oxides that will form as oxygen enters the plume area
(transported by diffusion, in rainwater and in groundwater)
will minimize uranium from remobilizing.
Fresh amorphous ferric iron (Fe3+) oxide is a strong sorbent
for a variety of metals including uranium. This amorphous
ferric iron (Fe3+) oxide is a precursor of many natural forms of
crystalline ferric iron (Fe3+) oxides that adsorb or incorporate
into their crystalline structures many trace metals.180 Hence,
intrinsic oxidation of ferrous iron (Fe2+) may be an additional
means of establishing permanence of the precipitates. This
mechanism takes place as a result of the precipitation of iron
oxyhydroxides over already immobilized precipitates of ura-
nium and forming an insoluble barrier that crystallizes with
time.
The discussion earlier provides the information needed
to identify the necessary characteristics of a stable, fully
reduced zone. To remain stable over long periods of time, a
reduced IRZ must contain a variety of reduced compounds
after treatment, including some combination of the following:
• Iron sulfides (ranging from amorphous FeS to pyrite
[FeS2]). To ensure low soluble uranium concentra-
tions over long periods of time, the concentration of
iron sulfides (FeS) must be several orders of magni-
tude greater than the concentration of uranium in the
reducing zone.
• Elemental sulfur (S).
• Residual reduced organic carbon either incorporated
in cellular biomass or stored by microorganisms.
• Reduced uranium compounds (uraninite [UO2] and
potentially US2).
• Potentially a variety of other reduced sulfur, manga-
nese, iron, and trace mineral compounds.
For long-lived radionuclides such as uranium (which has a
half-life greater than 245,000 years for all common isotopes),
the nuclear regulatory commission (NRC) requires assurance
that uranium will not remobilize exceeding a certain con-
centration over a period of 1,000  years. Hence, the success
criteria for permanent immobilization by precipitation of ura-
nium within an IRZ should be defined in a way to incorporate
407
technological advances. This criteria should be developed in
such a way that the maximum groundwater concentration of
a precipitated radionuclide will not exceed the required con-
centration, established by NRC, at selected downgradient
compliance wells. The experience and laboratory and field
work published in the literature suggest that the rate of any
dissolution reactions under any foreseeable environmental
condition (i.e., pH 4–9, and ORP, −400 to +400 mV) will be
such that this requirement can be achieved. With respect to
the 1,000 year requirement, it can only be shown by properly
implemented biogeochemical modeling using models such as
MINTEQ, PHREEQ, and/or geochemist’s work bench.
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141. Burgos, W.D., McDonough, J.T., Senko, J.M., Zhang, G.,
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142. McDonough, J.T. 2006. Kinetics of biological uranium(VI)
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Hallowell, ME: Environmental Research Software.
 8 Sparging, Venting, and
Vacuum-Enhanced Recovery
8.1  SOIL VAPOR EXTRACTION
Soil vapor extraction (SVE) is an accepted, recognized, and
cost-effective technology for remediating soils contaminated
with volatile organic compounds (VOCs) and semi-VOCs.1,2
This technology is known in the industry by various other
names, such as soil venting and vacuum extraction. The
process involves inducing airflow in the subsurface with an
applied vacuum and thus enhancing the in situ volatilization
of contaminants. Depending on the depth of soil being reme-
diated, extraction of air laden with contaminant vapors can be
achieved with vertical extraction wells or horizontal extrac-
tion pipes.
The SVE process takes advantage of the volatility of the
contaminants to allow mass transfer from adsorbed, dis-
solved, and free phases in the soil to the vapor phase, where it
is removed under vacuum and treated aboveground. In order
for this process to be effective, the contaminants of concern
must be volatile enough and have a low enough water solubil-
ity to be drawn into the soil gas for removal. These properties
are usually expressed by the vapor pressure and the Henry’s
law constant of the compounds.
Bioventing is a process that uses a similar approach to SVE
in terms of system configuration but has a different objective.
The intent of bioventing is to induce airflow to provide oxygen
to maximize the aerobic biodegradation of the compounds,
in contrast to volatilization. This difference in approach
renders less volatile compounds to be treated by enhanced
biodegradation.
A typical in  situ SVE system couples vapor extraction
wells with blowers or vacuum pumps to remove contaminant
vapors from zones permeable to airflow. The components of
an in situ SVE system are shown in Figure 8.1 and are usually
readily available as off-the-shelf products. The choices avail-
able to treat the contaminants present in the effluent air are
many and will primarily depend on the type of contaminants
and the mass loading rate.
SVE has many advantages that make this technology
applicable to a broad spectrum of sites:
• SVE is an in situ technology that can be implemented
with a minimum disturbance to site operations.
• SVE is very effective in removing the volatile con-
taminant mass present in the vadose zone.
• SVE has the potential for treating large volumes of
soil at acceptable costs.
• The system can be mobilized and installed very
quickly.
• SVE as a technology can be easily integrated with
other technologies required for site cleanup.
8.1.1  Governing Phenomena
The basic phenomena that govern the performance of SVE
technology are very simple and easily described. The mecha-
nisms that influence the success of SVE can be grouped into
the following categories3,4:
• Mass transfer considerations that influence and limit
the partitioning of the contaminants into the vapor
phase and eventually into the soil gas
• Airflow characteristics in the vadose zone
8.1.1.1  Contaminant Partitioning
Contaminant partitioning characteristics govern the perfor-
mance and thus the eventual shutdown of the system at the
end of a successful site cleanup. Organic contaminants can
be present in the soil matrix in four basic ways (Figure 8.2):
1. As an adsorbed film on soil particles and colloids
2. As a residual immiscible liquid in the soil pore
spaces known as non-aqueous phase liquid (NAPL)
3. As vapor in soil air present in the pore space
4. As dissolved compounds in soil pore water and
groundwater
In addition, as a floating product above the water table in the
case of light non-aqueous phase liquids (LNAPLs) and as a
pooled or sinking liquid in the case of dense non-aqueous
phase liquids (DNAPLs).
When soil air remains undisturbed after contaminant
spillage and infiltration, it becomes saturated by contaminant
vapors volatilized from the liquid phase. This highly satu-
rated vapor will be removed initially when SVE is initiated.5
As this soil vapor is purged from soil pores, the concentration
of contaminants in the extracted soil air begins to decrease
as unimpacted soil gas moves in to the area, replacing the
saturated soil pore gas. As clean air enters, the equilibrium
between the formerly saturated soil pore vapor and the sorbed,
dissolved, and NAPL phase mass is disrupted (Figure  8.3).
At this stage, the interfacial mass transfer between the con-
taminant and flowing air controls the removal of contami-
nants from soil. Soil gas, due to SVE, moves much faster than
413
414 Remediation Engineering

Treated air
discharge
Vacuum Air/water
gauge Flow SVE separator
blower
Sampling meter
port

Vacuum
monitoring
well

Separate phase product (NAPL)

FIGURE 8.1  Schematic of typical components of an in situ soil vapor extraction system.

Product vapors
1 2 NAPL
in pore spaces

Sorbed to
Sand particles 3
soil particle

Silt

Clay

Product dissolved
Organic matter 4
in soil moisture

Clean soil Soil contaminated by

contaminant release

FIGURE 8.2  Phases of contaminants present in soil matrix.

the phase transfer taking place from the immiscible liquids,
soil pore water, and the adsorbed film into the soil gas. Mass
recovery rates generally drop off quickly in an SVE system
due to this equilibrium shift. It is this disruption of equi-
librium between the various phases of contaminant storage
(sorbed, dissolved, vapor, and free phase) that drives reme-
dial cleanup. In context of SVE systems, the equilibrium dis-
ruption is driven by continuous replacement of the soil gas;
the pace of which the replacement happens is directly related
to flow rate of the system. This concept is known as pore
volume exchange. At any point in the system, it should be
possible to determine the number of pore volumes replaced
on a daily or weekly basis.
Optimization of the performance of an SVE system, at a
given site, requires a fundamental understanding of the mech-
anisms controlling contaminant removal from that particular
soil matrix. Under actual field conditions, several mecha-
nisms will occur simultaneously, and the contribution of each
will shift along with the progress of remediation. Early in the
treatment, direct volatilization from immiscible liquids and
adsorbed film will dominate. Extraction of dissolved contam-
inants from the pore water and desorption from the mineral
and organic fraction of the soil will take place only when the
liquid mass of the contamination is gone. For a water-miscible
VOC such as acetone, extraction from the pore water will
occur during the early phase of treatment.
Sparging, Venting, and Vacuum-Enhanced Recovery 415

Diffusion controlled and this parameter can be conceptualized as the solubility

of the compound in air at a given temperature. More pre-

# Removed
Air flow
cisely, the vapor pressure is defined as the pressure exerted
Vapors
by the vapor at equilibrium with the liquid phase (NAPL)
of the compound at a given temperature. Vapor pressure is
Contaminated soil typically expressed in pressure units such as millimeters of
Time
mercury (mm Hg). Chemicals with vapor pressures greater
than 0.5–1.0 mm Hg (e.g., benzene, trichloroethylene [TCE])
are expected to volatilize to a significant degree when
Flow controlled released in the subsurface and will respond favorably to SVE

# Removed
technology.
Air flow For mixtures of compounds such as gasoline, the composi-
Contaminated soil
tion of the mixture also has a bearing on the vapor pressure
according to the following relationship:
Time

FIGURE 8.3  Decline in vapor concentrations under diffusion and
flow-controlled regimes.
8.1.1.2  Contaminant Properties
The physical and chemical properties of a spilled compound
control, to a great extent, the partitioning and thus the distri-
bution into the various phases described earlier (vapor, dis-
solved in pore water, adsorbed to soil particles, and NAPLs).
The distribution of a compound among the four phases
can be described by several parameters (Figure 8.4). The
degree to which a compound partitions into the vapor phase
is described by that compound’s vapor pressure and Henry’s
law constant. The soil adsorption coefficient, kd, describes
the tendency of a compound to become adsorbed to soil. The
solubility describes the degree to which a compound will dis-
solve into water.
8.1.1.2.1  Vapor Pressure
Vapor pressure is the parameter that can be used to estimate a
compound’s tendency to volatilize and partition into the gas-
eous phase. All solids and liquids possess a vapor pressure,
Pi = Xi Ai Pi o (8.1)
where
Pi is the equilibrium partial pressure of component i in the
organic mixture
Xi is the mole fraction of component i in the organic
mixture
Ai is the activity coefficient of component i in the organic
mixture as a correction factor for compensating noni-
deal behavior6,7
o
Pi is the vapor pressure of component i as a pure compound
This relationship, for example, states that the vapor pres-
sure of benzene is related to the percentage (mole fraction) of
benzene in gasoline.
Temperature also has a strong influence on the vapor
pressure of a compound. It is stated that for most interme-
diate molecular weight organic compounds, vapor pressure
increases three to four times for each 10°C increase in tem-
perature.6 In general, vapor pressure may be approximated by
P(T ) = Aexp(- B /T ) (8.2)

where
Removal Removal T is the temperature in degrees Kelvin
A, B are the constants characteristic of the substance

Air Air Based on the effects of temperature, expressed by this equa-

Vp tion, SVE effectiveness in the subsurface can be influenced
Vp

Vp
h

h
K

Contaminant by increase in temperature. However, seasonal fluctuations

liquid (NAPL)
in soil temperature are dampened with depth of the vadose
Kp
Water Soil Water S Soil zone. Steam injection, soil heating, and radio-frequency heat-
Kp, S Kp, S ing are some techniques that may enhance the volatilization
of the compounds. However, the energy cost associated with
Vp – Vapor pressure Vp – Vapor pressure many of these enhancements is notable, resulting in very little
Kh – Henry’s law constant Kh – Henry’s law constant market demand for such enhancements. In some cases, such
Kp – Partition coefficient Kp – Partition coefficient as diffusion-limited conditions or when volatile compounds
S – Solubility S – Solubility are mixed with some sparingly volatile compounds, increase
(a) (b) in temperature may result in beneficial effects in increasing
mass removal.
FIGURE 8.4  Distribution of contaminants into various phases. If the contamination present is not in the form of sepa-
(a) Three phase diagram and (b) four phase diagram. rate phase liquids (NAPLs), vapor pressure becomes a less
416
accurate predictor of SVE effectiveness. Contaminant adsorp-
tion to soil and solubility in soil moisture will determine the
relative volatility.
8.1.1.2.2  Water Solubility
The solubility of a compound controls the degree to which
the compound dissolves into pore water present in the vadose
zone. Solubility also has an important impact on the partition-
ing fate and transport of the compound. Soluble compounds
are likely to dissolve and move into the saturated zone due
to infiltration. A fluctuating water table is another means of
impacting contaminant concentration in the vadose zone and
specifically in the capillary fringe.
Solubility of a compound can be defined as the maximum
mass that can dissolve in pure water at a specific temperature
(aqueous concentrations are usually stated in terms of mass
per mass (ppm, ppb) or mass per volume (mg/L, μg/L)). For
organic mixtures, such as gasoline, solubility is additionally a
function of the mole fraction of each individual compound in
the mixture. Appendix presents the pure water solubilities for
common environmental contaminants:
Ci = Xi AiCio (8.3)
where
Ci is the equilibrium concentration of compound i in the
organic mixture
Xi is the mole fraction of compound i in the organic mixture
Ai is the activity coefficient of compound i in the organic
mixture as a correction factor for compensating noni-
deal behavior7
o
Ci is the equilibrium solubility of compound i as a pure
compound
Under typical SVE scenario, vadose zone soils are rela-
tively moist (10%–14% by weight), and contaminants are gen-
erally dissolved in pore water. Solubility is also an important
parameter for bioventing, since biodegradation of a compound
is enhanced due to the increased availability for microbial
uptake as a dissolved compound.
Cosolvation is another factor that should be taken into
account when evaluating partitioning of contaminants in the
subsurface. Cosolvation refers to a mobile phase consisting of
multiple solvents that are miscible in one another. For exam-
ple, the cosolvents can be pore water, benzene, toluene, and
TCE present in NAPL form. The solubilization of one con-
taminant into another will impact the partitioning and, thus,
the removal efficiency under SVE operation.
8.1.1.2.3  Henry’s Law Constant
The volatilization of a compound dissolved in water is gov-
erned by Henry’s law, which describes the relative tendency
for a compound in solution to exist in the vapor phase. Henry’s
law holds true for dilute solutions of solute compounds that
do not ionize or dissociate within the solvent liquid at con-
stant temperature. It is somewhat analogous to the vapor
pressure, which describes the partitioning behavior between
Remediation Engineering
a pure substance—instead of a compound in solution—and
its vapor phase. The proportionality constant that relates
concentration in solution to the partial pressure is known as
Henry’s law constant (K H) and is usually reported in units of
atm m3/mol:
Pi
KH = (8.4)
Cl
where
KH is Henry’s law constant (atm L/mol)
Pi is the partial pressure of compound in the gas phase
(atm)
Cl is the concentration in liquid at the water–vapor inter-
face (mol/L)
Henry’s law constant can also be found in a dimensionless
form using the ratio of the vapor concentration to the liquid
concentration by converting the partial pressure of the gas to
the concentration in the vapor phase using the ideal gas law:
ni P
Cv = = i (8.5)
V R ´T
where
Cv is the concentration of compound in vapor phase (mol/L)
ni is the number of moles of compound in gas phase
V is the volume of gas (L)
R is the universal gas constant (atm L/K · mol)
T is the temperature (K)
Reducing terms based on units of measure results in the
following dimensionless Henry’s law coefficient, a ratio of the
vapor concentration to the liquid concentration:
Cv
KH = (8.6)
Cl
Henry’s law constant is highly temperature dependent and
increases with increasing temperature. It is stated that Henry’s
law constant increases 1.6 times for an increase of 10°C in
temperature.7
Appendix lists the Henry’s law constants for common
environmental contaminants, and the relationship between
vapor pressure, solubility, and Henry’s law constant is graphi-
cally presented in Figure 8.5. Under moist soil conditions,
efficiency of SVE will be dependent on the Henry’s law con-
stant of the compound, similar to air stripping.8 For exam-
ple, although acetone is very volatile, efficiency of physical
removal by SVE is very low due to its high solubility. Acetone
tends to biodegrade very well and will be removed readily
under bioventing.
8.1.1.2.4  Soil Adsorption Coefficient
Adsorption, absorption, and sorption are three terms that refer
to similar phenomena.9 Adsorption is defined as the accumu-
lation occurring at an interface, absorption as the partitioning
Sparging, Venting, and Vacuum-Enhanced Recovery 417

2
1

4
10 –
10 –

10 –

10 –
10 2

10 1

10 0
100
Oxygen 2-Chloropropane
Chloroethanie
10–5
Henry’s law constant, H Iodoform
(atm m3/mol) Allyl chloride
1-Chloropropane Methylene chloride
1,2-Dichloroethylene Dibromomethane
1,1-Dichloroethane Propionaldehyde
Isobutyraldehyde
Chloroform
1,1,1-Trichloroethane
Carbon tetrachloride
1-Chloro 2-methylpropane
10–1 1-Bromobutane
1-Chlorobutane
Benzene Butyraldehyde 2-Butanone 10–6
Ethylene dichloride
Trichloroethylene
1,2-Dichloropropane
Water
Toluene
1,1,2,2-Tetrachloroethylene Ethylbutyraldehyde
2-Pentanone
Vapor pressure (atm)

n-Octane Chlorobenzene 2-Butanol

10–2 Ethylbenzene
1,2-Dibromoethane 2-Methylbutanone Isobutanol
10–7
o-Xylene Styrene Bromoform
Isopropylbenzene 1-Butanol
n-Propylbenzene Bromobenzene
1,3-Dibromopropane 2-Heptanone
3-Heptanone
1,2,4-Trimethylbenzene
n-Butylbenzene o-Dichlorobenzene 1-Pentanol
1-Heptanol n-Hexanol
10–3 2-Octanone Benzaldehyde 10–8
Hexachloroethane p-Dichlorobenzene

1-Nonanol

Benzo |o| thiophene

Nitrobenzene
o-Nitrotoluene p-Cresol Phenol
10–4 10–9
Benzyl alcohol

1,2-Benzenedial

Methyl parathion Quinoline

10–5
10–3 10–2 10–1 100 101 102 103 104 105
Solubility (mol/m3)

FIGURE 8.5  Solubility, vapor pressure, and Henry’s law constant for selected chemicals. (After Lyman, W.J. et al., Handbook of Chemical
Property Estimation Methods: Environmental Behavior of Organic Compounds, McGraw-Hill, New York, 1982.)

between two phases (e.g., accumulation from groundwa-
ter into soil organic carbon) and sorption as including both
adsorption and absorption.10,11 Often the terms adsorption
and sorption are used interchangeably, as will be the case in
this book.
In general, adsorption phenomena can be classified as
either sorbent or solvent induced.10 Sorbent-induced adsorp-
tion occurs when there is an attraction between the soil matrix
(sorbent) and the contaminants (solute), and the contaminant
accumulates at the surface due to the affinity of the surface
for the contaminant (e.g., cation exchange at the mineral sites).
Solvent-induced adsorption occurs when the contaminant is
hydrophobic (nonpolar, water disliking, and low solubility)
and finds it energetically favorable to accumulate at an inter-
face or partition into a nonpolar phase (e.g., partitioning onto
the soil organic carbon) rather than remain in the water phase.
Adsorption of contaminants to soil particles is impacted
by the two phenomena described earlier. The soil organic
content and its mineral adsorptive surfaces are both capable
of contaminant adsorption. Adsorption of contaminants at
both these locations increases the immobility of the con-
taminant and decreases the relative volatility during SVE.
Soil adsorption becomes particularly important (rate limit-
ing) under drier conditions. Soil moisture may decrease as
airflows continuously, during SVE, due to the vapor pres-
sure of water being 10 mm Hg at typical soil temperatures.
Figure 8.6 illustrates the difference in adsorption potential
under wet and drier soil conditions.
Adsorption of a contaminant to soil and organic matter is
described by the contaminant’s soil adsorption coefficient, Kd.
The total organic carbon content, foc, strongly influences the
adsorption capacity of nonionic organic compounds onto the
soil matrix. Due to the nonpolar nature of most organic con-
taminants, there is little correlation between clay content and
contaminant adsorption. While the adsorption coefficient, Kd,
of a chemical has been observed to vary significantly from
soil to soil (due to varying foc), it was observed that normal-
ization of the Kd values by the respective foc values resolved in
a parameter, koc, that was much less variable (independent of
the soil and a function only of the compound). Another way of
expressing this relationship is defining Koc as a proportional-
ity constant:
K d = foc ´ K oc (8.7)
where
Kd is the partitioning coefficient
foc is the fraction of organic carbon in soils
Koc is the organic carbon partitioning coefficient
Typical values of foc for subsurface soils have been reported
in the range of 1%–8%,9 while alluvial sandy materials have
418
Nonpolar organic
H2O
Vapor
phase
Adsorbed
layer
Solid surface
(a)
(b)
(c)
FIGURE 8.6  Illustration of volatile organic compound adsorption
under three moisture regimes. (a) Dry, (b) DAMP, and (c) wet.
been reported in the range of 0.02%–1.0%. For soils with
lower organic carbon content (  foc < 0.1%), adsorption to min-
eral grains may be dominant.
Researchers have evaluated a number of parameters for
estimating Koc values based on fundamental properties of the
contaminant. One of the easiest ways of obtaining Koc is from
the octanol–water partitioning coefficient (Kow) of the con-
taminant. The Kow of a contaminant describes the partitioning
between water (a polar phase) and octanol (a nonpolar phase).
The octanol–water partitioning is analogous to the partition-
ing in the soil matrix between the pore water and soil organic
matter. There are many equations reported in the literature to
describe the relationship between Kow and Koc.9 An example is
provided by the following equation12:
log K oc = 0.999 log K ow - 0.202 (8.8)
Most organic contaminants are more easily adsorbed to the
soil than they are desorbed. Therefore, it takes much more
time and energy for desorption than adsorption of a contami-
nant in the soil matrix. This phenomenon, known as “hystere-
sis,” tends to reduce the mass removal efficiency during SVE,
particularly during the tail end of system operation.
8.1.1.2.5  Biodegradability of Contaminant
One creative use of SVE technology is in manipulating
subsurface oxygen levels to maximize in  situ biodegrada-
tion of aerobically biodegradable compounds in comparison
Remediation Engineering
to volatilization. This modification to conventional SVE is
known as bioventing or bioenhanced soil venting. Bioventing
can reduce effluent vapor treatment costs due to a lower
required flow rate from individual wells.
Although microorganism populations in the vadose zone
are sharply reduced in number and species diversity with
depth, significant microbial degradation of some compounds
occurs throughout the vadose zone. In bioventing, the natural
biodegradation processes are enhanced by optimizing the sys-
tem to maintain a supply of oxygen as an electron acceptor for
the biodegradation process.
Most of the petroleum organic compounds such as ben-
zene, toluene, ethylbenzene, and xylenes are very easily bio-
degradable under aerobic conditions. Some of the halogenated
compounds such as methylene chloride and chlorobenzene
will also biodegrade under aerobic conditions.13,14 Most of
the alcohols, ketones, and phenolic compounds will degrade
under aerobic conditions.
In contrast to the compounds discussed earlier, microbial
degradation of volatile aliphatic chlorinated compounds, such
as TCE and PCE, occurs primarily by reductive dehalogena-
tion. Reductive dehalogenation of these compounds will take
place only under reduced, anaerobic conditions. Hence, bio-
degradation of aerobically nonbiodegradable compounds dur-
ing SVE is nonexistent or insignificant.
8.1.1.2.6 Weathering
The concept of weathering applies to SVE due to the effect
SVE has on the composition of the organic contaminant mix-
ture present in the subsurface. At a gasoline spill site, initially
at system start-up, the compounds removed will be primarily
the more lighter-end fractions that are generally both more
volatile and aerobically biodegradable. As SVE proceeds, the
extracted vapor will likely have less of the lighter-end frac-
tions and will be composed mostly of heavier compounds.
This process is commonly described as weathering. Changes
in organic contaminant mixture characteristics taking place
due to natural volatilization, solubilization, and biodegrada-
tion of the readily mobile lighter compounds are also charac-
terized as weathering. The degree of weathering will impact
the overall effectiveness of SVE operation.
8.1.1.2.7  Other Contaminant Properties
There are several other contaminant properties that may
influence the volatility and thus effectiveness of SVE opera-
tion. These properties are not as significant as the parameters
described in the last few sections and hence may be consid-
ered secondary in importance.
These properties are molecular weight, molecular struc-
ture, and polarity. Heavier and large molecules travel slowly
to and from soil micropores and tend to adsorb very strongly
to soil surfaces. During the tail end of SVE system operation,
these properties may end up as the rate-limiting mass trans-
fer properties. This may be a significant factor at petroleum
spill sites and may influence the degree of mass removal and
the residual mass left behind after a reasonable time of SVE
operation.
Sparging, Venting, and Vacuum-Enhanced Recovery
8.1.1.2.8  Contaminant Partitioning Summary
When a volatile NAPL is present in the soil matrix, the
bulk of the mass removed during SVE will be due to direct
volatilization influenced by the vapor pressures of the con-
taminants. This is analogous to a fan blowing past a pool of
gasoline or TCE. It has been reported in the literature that
more than 95% of NAPL can be removed by direct volatil-
ization after removing several hundred pore volumes of air.15
In the presence of NAPL, mass removal rates are often lin-
early related to the airflow rates. When NAPL is not present
in the subsurface, airflow requirements become very differ-
ent and are often governed by nonequilibrium rate-limiting
conditions.
Under moist soil conditions and when there is no NAPL
present, contaminant partitioning in the vadose zone can be
described by the following equation.16
CT = PbC A + wCL + aCG (8.9)
where
CT is the total quantity of contaminant per unit soil volume
CA is the adsorbed chemical concentration
CL is the dissolved chemical concentration
CG is the vapor concentration
Pb is the soil bulk density
w is the volumetric water content
a is the volumetric air content
The equilibrium relationship between vapor concentra-
tion and the associated pore water concentration is given by
Henry’s law:
CG = K H CL (8.10)
where
CG is the gas concentration
KH is Henry’s law constant
CL is the pore water concentration
The relationship between equilibrium dissolved concentra-
tion and adsorbed concentration is given by
C A = K d ´ CL (8.11)
where
CA is the adsorbed concentration
Kd is the adsorption coefficient
CL is the pore water concentration
Again, Kd = foc · Koc.
8.1.1.3  Soil Properties
The soil environment, like the contaminant characteristics,
has a significant impact on the effectiveness of SVE. Soil
properties such as porosity, air permeability, water content,
organic matter content, heterogeneity, and surface seals
impact the movement of contaminant vapors.
419
8.1.1.3.1  Soil Porosity
Vapor migration in the subsurface occurs principally through
air-filled pore spaces. Factors influencing vapor migra-
tion include the air-filled porosity (which is affected by the
water content) of a soil and the orientation of the soil pores.
Decreasing soil porosity will generally reduce the efficiency
of SVE due to the decrease in diffusive mass transport from
the soil matrix into the soil gas. Decrease in porosity also
impacts SVE effectiveness due to the decrease in available
cross-sectional area for airflow. Lower porosity soils also have
higher available surface area for contaminant binding.
8.1.1.3.2  Water Content
Soil water content has competing effects on the air perme-
ability. The primary effect of pore water is to reduce the air-
filled porosity of soil. Research information is available to
indicate that SVE would be more successful at lower water
contents, since a greater percentage of the pore space will be
air filled and thus the induced airflow will be greater for a
given vacuum.15,17
The water content also has a significant effect on the suc-
cess of SVE through its effect on adsorption characteristics
of organic compounds. Decrease in soil moisture allows for
more contaminant adsorption onto the soil matrix to play a
more prominent role in mass transfer during SVE. If the soil
adsorptive capacities are strong, the benefits of soil dewater-
ing may be partially offset due to the increased binding of
contaminants.
Soil moisture may decrease as air is circulated through soil
during SVE, since water has a vapor pressure of 10 mm Hg
at typical soil temperatures. As illustrated in Figure  8.7,
under low soil moisture conditions, contaminants will adsorb
directly on soil surfaces where fewer water molecules are
competing for adsorption sites. Contaminant adsorption is
also a function of moisture content in the soils.18 Adsorption
was the highest during ovendry conditions and decreased lin-
early with moisture content up to one monolayer. Water suffi-
cient to form 1–5 monolayers exhibited complex behavior due
to interactions between the contaminant and surface bound
water. At moisture contents greater than five monolayers,
there was a gradual increase in adsorption that was attributed
to increase in contaminant resolution.
1 2 3
1. Oven–dry to single surface
Sorption coefficient
monolayer of water
Kd 2. 1–5 surface water layers
3. >5 monolayers of surface
water
Moisture content (%)
FIGURE 8.7  Adsorption of contaminants as a function of mois-
ture content.
420
8.1.1.3.3  Soil Heterogeneity
Soil heterogeneity is caused by the structure, stratification,
type, and size of soil particles that influence both contaminant
migration and subsurface airflow pathways. An example of
heterogeneous soil conditions is a coarse silty sand formation
with interbedded clay lenses. Another example is coarse sand
formation overlain by a silty sand formation, and the preferred
extraction well configuration under this condition is shown in
Figure 8.8.
Preferred flow path due to highly permeable macropores
formed by fractures, cracks, root casts, or earthworms should
also be taken into consideration. The presence of subsurface
features, such as utility conduits, may also result in preferential
flow pathways. Preferred flow pathways have major implica-
tions with regard to SVE effectiveness due to potential short-
circuiting of induced airflow pathways. If short-circuiting
occurs, contaminants adhering to soils through which limited
airflow occurs may not be removed as rapidly as those present
in zones through which a large volume of airflows. Removal
of contaminants from soil particles in dead zones would there-
fore be more closely related to diffusion effects (Figure 8.9).
SVE blower
Zone of
contamination
Silty sands
Coarse sands
FIGURE 8.8  A cluster extraction well under varying geologic
conditions.
Air advection
Molecular diffusion
Molecular diffusion
Low permiability
Molecular diffusion
strata
Molecular diffusion
Molecular diffusion
Air advection
FIGURE 8.9  Advective/diffusive airflow schematic.
Remediation Engineering
Removal of contaminants from these dead zones may not
be enhanced by increased vacuum or flow rates but rather
removal will be limited by diffusion from these zones to the
more continuous flow paths.
8.1.1.3.4  Depth to Water Table
If the SVE well penetrates the water table, the water table
within the well will rise by an amount equal to the vacuum
applied within the screen. A 60 in. water column vacuum at
the wellhead can therefore result in a water table rise of 5 ft
(Figure 8.10). Hence, if the screen of the SVE well is less than
5 ft, the rise in the water table can block the passage of air
into the SVE well and increase the amount of water pulled
in to the system dramatically. Where required, installation of
additional SVE wells operating at lower vacuum (and there-
fore smaller radius of influence (ROI)) can reduce the amount
of water table rise and allow access to vadose zone soils.
Alternately, horizontal wells or pipes installed in trenches can
be used in shallow water table conditions, thus expanding the
available screen length for airflow and enabling operation of
the system at reduced vacuum levels. Under this condition, the
water uplift can be minimized (Figure 8.11).
However, the fluctuation of the water table can create
conditions of screen submergence during certain times of
the year. The need to induce airflows at or near the capillary
fringe will also require the bottom of the screen to be placed
very close to the water table.
SVE blower
Applied vacuum
60 in H2O
Induced air flow
5 ft
FIGURE 8.10  Water table rise during soil vapor extraction
operation.
Seal
Trench or
horizontal
pipe
Shallow
well
FIGURE 8.11  Limited radius of influence from vertical wells
under shallow water table conditions and the use of horizontal
extraction pipes.
Sparging, Venting, and Vacuum-Enhanced Recovery 421

Negative
pressure
lines
Air flow
pathways

Negative
pressure
lines
Air flow
pathways

FIGURE 8.12  Typical airflow patterns and vacuum distribution during soil vapor extraction operation.

8.1.1.4  Airflow Characteristics Open soil surface

“Short-circuiting”
The basic principle of induced airflow during SVE is very
simple. Airflow is induced in the subsurface by a pressure
gradient applied through vertical wells or horizontal trenches.
The negative pressure inside the extraction well, generated
by a vacuum blower, causes soil air to move toward the well.
Typical airflow patterns induced during SVE operation are
shown in Figure 8.12. In order to design an SVE system, the
subsurface airflow pathways and extraction flow rates must be
properly defined. Impermeable seal
The airflow field developed is dependent on many
­factors: the level of applied vacuum, available screen interval
in the vadose zone, porosity, air permeability and its spatial
variation, depth to groundwater, presence or absence of leak-
age from the ground surface, and subsurface conduits.

8.1.1.4.1  Surface Seals

The airflow pathways will be influenced by the amount of
airflow entering near the extraction well (where the pressure
gradient is the greatest). An impermeable surface seal pre-
vents air from entering near the injection well and forces air
to be drawn from a greater distance and thus contact a greater
volume of soil (Figure 8.13). Surface seals may also prevent
infiltration of rainfall and thus reduce the amount of water
removed by the extraction well.
Depending on the characteristics of the site, different
materials can be used as an impermeable seal. Existing
paved surfaces, such as asphalt or concrete layers, or a
rolled-out flexible membrane lining can be used as surface
seals.
FIGURE 8.13  Effect of surface seal on vapor flow paths.
8.1.1.4.2  Airflow in Permeable Media
Darcy’s law describes fluid flow-through porous media and
can be used to predict the pressure drop required to drive
airflow through soils in vapor extraction systems. The fol-
lowing section describes how Darcian flow is derived in a
simple 1D flow of constant area, then again derived for 2D,
radial flow where the cross-sectional area changes over the
flow path.
422 Remediation Engineering

A(cm2)

Q (g/s)

P
a b
L (cm)

FIGURE 8.14  Diagram of fluid flow through a porous volume with L

a constant cross-sectional area, A (1D flow).

FIGURE 8.15  Relationship between pressure, P, and path length,

8.1.1.4.2.1  Darcian Flow through Constant Cross L, when cross-sectional area is constant. dP/dL is the slope of the
Section  Darcy’s law states that the fluid flux per unit cross- pressure–path length relationship.
sectional area is proportional to the rate of pressure drop
along the flow path. It is expressed as follows:

Q dP
=K (8.12)
A dL
where

dP/dL
Q is the extracted flow rate
A is the cross-sectional area of airflow
K is the soil pneumatic conductivity
P is the pressure
L is the length of flow path
a
Figure 8.14 depicts the fluid flow through a porous medium b
L
volume element with a constant cross section. The flow travels
through the volume element, crossing through planes “a” and
FIGURE 8.16  Graphical representation of the integration of the
“b,” perpendicular to the flow direction. rate of pressure drop, dP/dL, over a path of length L, when the cross-
The constant of proportionality, K, is called the con- sectional area, A, is constant.
ductivity. In the case of airflow, K is termed the pneumatic
conductivity. Q is stated in mass flow units because air is a
compressible fluid. The rate of pressure drop, hence the pneu- The rate of pressure drop along a path of length L can be
matic conductivity, is related to the number of molecules or determined by integrating the rate of pressure drop. Figure 8.16
mass, passing through the porous medium per unit time—not provides a graphical representation of the integration.
the volume (which carries more or less mass as the pressure The integration is performed after rearranging Equation
rises and falls). In fact, due to the pressure drop observed as 8.13, to isolate dP, as follows:
air passes through soil, the density of air decreases along its
flow path. Q
dP = dL (8.14)
Airflow through a volume element with a constant cross KA
section yields a constant rate of pressure drop along the flow
The integration of dP over the interval from plane “a” to plane
path. This can be illustrated by rearranging Equation 8.12 to
“b” (variable distances from the vacuum source) yields the
isolate the rate of pressure drop per unit path length (dP/dL):
total pressure drop over that interval, which is designated ΔP:
dP Q
= (8.13) b
Q
ò KA dL (8.15)
dL KA
DPa ®b =
a
where
Q, K, and A are constants Because Q, K, and A are constants in 1D flow, they are moved
dP/dL is also a constant outside the integrand:
b
This can be represented graphically, as shown in Q
Figure 8.15. Pressure decreases at a constant rate along the
flow path, L.
DPa ®b =
KA ò
dL (8.16)
a
Sparging, Venting, and Vacuum-Enhanced Recovery 423

Pa Pb
Qout

dP/dr
a

b
a b
Vacuum r
trench
FIGURE 8.18  Graphical representation of the integration of the
FIGURE 8.17  One-dimensional flow characterization, showing rate of pressure drop, dP/dr, over a path from “a” to “b” when the
air withdrawal from a vacuum trench at a rate, Q(g/s). Pressure cross-sectional area, A, is a function of 1/r.
in the soil atmosphere is measured at two probes, at distances a
and b from the trench. Pressure values Pa and Pb are observed at Figure 8.18 showed the relationship between dP/dL and L, in
the probes. This information can be used to calculate pneumatic
which the rate of pressure drop, dP/dL, is constant, regard-
conductivity.
less of the position along the flow path, L. In radial flows that
are generated by vertical wells, the rate of pressure drop is
Completing the integration, we get a function of 1/r. Figure 8.19, a graphical representation of
Equation 8.20, shows the dramatic reduction of the rate of
Q pressure drop as a function of increasing radial distance, r,
DPa ®b = (b - a) (8.17)
KA from the radial flow source (or sink).
Equation 8.20 can be integrated to provide the pressure
Equation 8.17 describes pressure drop in 1D flow, like that drop exerted along a radial flow path, as determined by the
which will be observed between two parallel vapor extraction flow rate and pneumatic conductivity.
trenches. Figure 8.17 provides an example of 1D flow, show-
ing the measurements needed to calculate pneumatic conduc-
SVE
tivity, K, from field observations. likelihood Time
To calculate pneumatic conductivity from field observa- Vapor of Soil air since
tions, Equation 8.17 is rearranged to isolate K, and ΔP is cal- pressure success permeability release
culated as the difference between pressures observed at points
“a” and “b”: 104 Weeks
High
Q Butane
103 Months
K= (b - a) (8.18) Success (gravel,
( Pb - Pa ) A Pentane very coarse
102 likely sand) Years
Benzene
8.1.1.4.2.2  Darcian Equation for Radial Flow  Airflows Toluene 101
moving to or from isolated vertical wells follow radial flow Weeks
Xylene
patterns. Unlike the 1D flows discussed earlier, radial flows 1 Medium
travel through variable cross-sectional area. The cross- Phenol Success (fine sand) Months
10–1 somewhat
sectional area, A, is a function of the radial distance from the Naphthalene likely Years
well (r) and the thickness of the porous medium (h). Cross- 10–2
sectional area, A, can be described as a function of r and h as
follows: 10–3 Weeks
Success
A = 2prh (8.19) Aldicarb 10–4 less Low Months

likely (clay)
This value can be substituted into Equation 8.13. In this case, Years
the designation for distance traveled is r rather than L:
Match point
dP Q
= (8.20)
dr K × 2prh FIGURE 8.19  Soil vapor extraction applicability nomograph.
424
Rearranging,
Q Contaminants Amenable to Soil Vapor Extraction
dP = dr (8.21)
K × 2prh
Moving constants outside the integrands, we get
b b
Q 1
ò
a
dP =
K × 2ph ò r dr (8.22)
a
Integrating both sides of the equation, we get
Q phase distribution, concentrations, and contaminant type will
Pb - Pa = é ln(b) - ln(a) ùû (8.23)
K × 2ph ë
Simplifying the equation, we get
Q æbö
DPa ®b = ln ç ÷ (8.24)
K × 2ph è a ø
Equation 8.24 is the formulation of Darcy’s law for radial
(2D) flow in a porous medium. This equation can be utilized
to interpret pneumatic conductivity tests and to support SVE
design calculations that link pneumatic conductivity and soil
air exchange rates.
8.1.2 Applicability
There are many criteria that need to be evaluated before
deciding the applicability of SVE at a given site. The appli-
cability of this technology is greatly influenced by the
information obtained from contaminant and site charac-
terization activities (Figure 8.19). Contaminant character-
ization will include composition, type, age, concentration,
phase, and distribution of contaminants in the subsurface.
Site characterization will include geologic conditions, soil
moisture content, man-made site conditions, topography,
depth to water table, and horizontal and vertical extent of
contamination.
8.1.2.1  Contaminant Applicability
SVE is applicable when the contaminants present in the sub-
surface are volatile and/or aerobically biodegradable. As a
simplified guideline, a compound or mixture of compounds is
a likely candidate for SVE application by physical removal if
it has both of these characteristics:
• Vapor pressure of 1.0 mm Hg or more at 20°C
• Henry’s law constant greater than 0.001 atm m3/mol
or greater than 0.01 in the dimensionless form of
Henry’s law constant
Examples of contaminants amenable to SVE are listed in
Table 8.1.19
The impact of solubility is reflected by the Henry’s law
constant since the additive effects of solubility and vapor
Remediation Engineering
TABLE 8.1
Henry’s Law Constant Vapor Pressure
Contaminant (atm · m3/mol) (mm Hg)
Benzene 0.00548 (25°C) 76 (20°C)
Toluene 0.00674 (25°C) 22 (20°C)
Trichloroethene (TCE)
Tetrachlorethene (PCE)
0.0099 (20°C)
0.00029
57.8 (20°C)
20 (26.3°C)
pressure are nonlinear. As noted in previous sections, the
determine the mass removal efficiencies and the time required
for site cleanup.
Evaluation of bioventing should be accompanied by the
comparison of biodegradation rates to volatilization of the
contaminants. If the contaminants are biodegradable, empha-
sis should be focused on the required mass removal rates and
the time of cleanup. Presence of excessive levels of CO2 and
depletion of O2 in the soil gas is an indication of ongoing natu-
ral aerobic biodegradation of contaminants in the vadose zone.
8.1.2.2  Site Characterization
SVE is typically more applicable in cases where the contami-
nated unsaturated zone is relatively permeable and homoge-
neous. Geologic parameters such as porosity, soil structure,
and air permeability influence the extractability of induced
airflow. Site surface topography can also influence the suc-
cess of an SVE system. Ideally the site should be covered by
an impermeable surface to minimize short-circuiting of air-
flow and infiltration. The presence of utility trenches (gener-
ally constructed with high permeability fill material) will also
cause short-circuiting of airflow pathways.
Site characterization activities include
• Geologic and hydrogeologic characterization
• Contaminant distribution assessment (vertical and
horizontal)
• Soil gas surveys
• Water table elevation and fluctuations
• Barometric pressure changes
• Presence of LNAPL on top of the water table or iso-
lated globules (“ganglia”) in the soil matrix
• Groundwater concentrations
Comprehensive geologic assessment will be complete only
when information is collected on distinct geologic strata,
subsurface conduits, depth to the water table, and seasonal
fluctuation of the water table. Additionally, the estimated val-
ues of the physical properties (such as permeability, moisture
content, organic carbon fraction) of each of the geologic strata
should be collected. It is always important to develop detailed
geologic cross sections in as many directions as possible.
Most geologic cross sections are developed through analy-
sis of drilling logs and site information available on tanks,
Sparging, Venting, and Vacuum-Enhanced Recovery
Underground Underground
utilities Former UST PIT
utilities
Silty sands
Interbedded
clay layers
Medium sand
Silty sands
Coarse sand
FIGURE 8.20  Typical cross section at a candidate site for soil
vapor extraction.
pipes, etc. An example of a subsurface cross section used to
evaluate the applicability of SVE is shown in Figure 8.20.
8.1.3  System Design
SVE technology has been implemented in the past using various
design approaches that vary from an intuitive empirical approach
to using sophisticated design models. The primary goals of SVE
system design are to achieve the following objectives:
• Specification of system components such as vacuum
blower, extraction wells, effluent air treatment unit,
air/water separator, pipes, and manifolds
• Selecting operating conditions such as extraction
vacuum levels, airflow rates, contaminant vapor con-
centrations, and well spacing
• Estimation of cleanup levels, remediation time
frame, residual concentrations, etc.
• Meeting the constraints imposed by cost limitations
and permitted discharge limits, etc.
Prior to initiation of system design, a thorough evaluation of
applicability of SVE should be completed. However, due to
uncertainties and inherent limitations associated with natural
heterogeneities, site characterization data, and accurate pre-
diction of contaminant partitioning, system design objectives
have to be realistic and flexible. Hence, SVE system design
has to incorporate modification of operating conditions even
after system start-up. The additional cost required to build
in adequate flexibility is usually very small compared to the
potential benefits in the long term.
SVE system design activities can be grouped into two
basic categories:
1. System operating parameters
a. Extraction airflow rate
b. Extraction vacuum
c. Well spacing or radius of influence
d. Contaminant concentrations
2. System components and equipment
a. Number of extraction wells
b. Well locations
425
c. Well construction (depth, screened interval)
d. Extraction blower
e. Air/water separator
f. Equipment manifolding and piping
g. Instrumentation and control (measurement
devices such as flow meters, pressure gauges,
and control valves)
h. Vapor treatment unit
Table 8.2 presents the significance of some design criteria on
SVE system performance.
8.1.3.1  Pilot Testing
It is prudent to perform a field pilot test at all SVE sites to
first verify that the site is a suitable candidate for soil venting
and also to collect full-scale design parameters. Since the data
collected during a pilot test involve collecting site-specific
engineering design parameters, it is logical to call this test a
field design test. Field design test activities are focused upon
the collection of data to determine soil pneumatic conductiv-
ity of the soil, well spacing requirements (radius of influence),
extracted soil gas concentrations and composition, and the
required flow rates and vacuum levels. Regardless of the size
of the final system and site conditions, the field design test
system should consist of the following components, at a mini-
mum (Figure 8.21):
• Vapor extraction test well.
• Vacuum blower to induce airflow.
• At least three vacuum monitoring points, at varying
radial distances from the test well based on initial
estimate of the potential vacuum influence.
• Vapor treatment system (if required); vapor phase
granular activated carbon may be sufficient for a
short term pilot test.
• Calibrated flow meter(s) or pitot tube(s).
• Calibrated vacuum gauges.
• Sampling ports in the process lines.
• Sampling devices (sampling pumps, syringes).
• Soil gas analytical instruments (PID, FID, field gas
chromatograph, etc.).
A field design test usually consists of extracting contaminated
air from the extraction well, at various flow regimes, and mea-
suring the response to the applied vacuum in at least three
monitoring points. The vacuum in the monitoring points is
measured by installing vacuum seals and gauges on the sur-
rounding monitoring wells and taking readings from them
at different intervals during the various flow regimes. The
extraction airflow rate from the venting wells is periodically
measured, using flow meters or pitot tubes, at different time
intervals of the various flow regimes. Air samples are taken
from the extracted air at critical times of the test to analyze for
the concentration and composition of contaminants. Multiple
air samples (or field readings) can be collected during each
flow regime: one right after initiation of air extraction, one
right before ending air extraction (after removal of at least one
426
TABLE 8.2
Soil Vapor Extraction System Design Criteria
Design Criteria
The necessary vacuum to achieve adequate airflow
(pore volume exchange) and radius of influence
Airflow rates to achieve adequate mass removal and
closure within required time
Well screen positioning
Soil moisture content monitoring and manipulation
Passive well placement
Off-gas treatment technology
Operation and maintenance and remote monitoring
No-failure piping and well design
Closure SVE system management
Vacuum
gauge
Vacuum monitoring point
FIGURE 8.21  Soil vapor extraction pilot test schematic.
to two pore volumes), and one during the middle of the test.
Additional samples may be required if an air sparge pilot test
is being conducted concurrently; with the recommendation
that the air sparge pilot test begin after sufficient SVE pilot
test, data have been collected. Additional air samples would
be collected from the SVE pilot system after the air sparge
Remediation Engineering
Significance
The required vacuum dictates the type and size of vacuum pumps or blowers to utilize.
Airflow requirements will dictate vacuum equipment and air emission control equipment sizing.
Airflow requirements to be dictated by modeling, pilot testing, and closure levels.
Positioning of the well screens will be critical to successful design. Well screens will be placed
within the water table to accommodate water table fluctuations and screened at various intervals to
ensure adequate flow throughout the soil. Screening intervals will be particularly important in
ensuring that flow is induced throughout the contaminated zones.
Soil moisture controls air permeability and equilibrium concentrations. Its proper manipulation may
enhance system performance. High moisture in the extracted airstream requires separation before
vapor treatment.
Passive wells provide influent air and can be located to minimize “dead,” no-flow zones that may
develop in multiple extraction point configurations.
Pilot test data, cost analysis, and operation and maintenance logistics will enable the appropriate
selection of off-gas treatment technologies.
If the property is to be developed and the wells will not be accessible, remote system monitoring
needs to be considered.
Underground piping layout may consist of duplicate sections in sensitive areas to ensure nonfailure.
All underground piping should be vacuum or pressure tested prior to burial.
Management strategies should be developed for the last months prior to closure. System pulsing,
passive venting with natural wind-driven vacuum can be considered.
Air inlet
pipe Air
discharge
Air/water Valves
Flow separator
meter Air
treatment
unit
rf low
Vapo
Contaminated soil
system has been initiated to understand the contribution of
vapor phase impacts from the air sparge system.
The extraction well location for the field design test should
be selected within the area to be treated by the full-scale sys-
tem. If the geologic conditions across the contaminated zone
vary significantly, the need for more than one field testing
Sparging, Venting, and Vacuum-Enhanced Recovery
location should be evaluated. The screened interval of the
extraction well should be placed within the contaminated
zone. Since induced airflow below the screened interval is
generally not significant, the screen should be placed accord-
ingly to attain the desired air distribution within the contami-
nated zone. Caution should be exercised to avoid any short
circuit pathways (such as utility trenches) to obtain the best-
quality data.
The configuration of the typical SVE vertical well is shown
in Figure 8.22. Horizontal wells or trenches should be consid-
ered for shallow water table conditions. In practice, existing
groundwater monitoring wells have been used for SVE field
design tests as vapor extraction wells. This is usually done to
achieve cost savings, and caution must be provided to ensure
that the screened interval of the groundwater monitoring well
will provide the required air distribution.
The number of required monitoring points and the depths
of installation will increase if the site geology is heteroge-
neous (Figure 8.23). Often, one tries to locate the test in an
area where existing groundwater monitoring points can be uti-
lized as the vacuum monitoring points. Again, caution should
be exercised to avoid compromise on the quality of data col-
lected. Vacuum monitoring points can also be installed in an
inexpensive manner by using small diameter pipe installed by
direct-push methods.
The capacity of the vacuum blower to be used for the field
design test is usually picked based upon experience, geologic
2–4˝ diameter SCH. 40 PVC
header sloped to well
5΄–0˝
minimum
6΄–0˝
15΄–0˝
FIGURE 8.22  Typical soil vapor extraction well.
427
conditions, the expected flow rate, and the available power
supply. Availability of various types of vacuum pumps within
specific flow and vacuum ranges is shown in Figures 8.24 and
8.25. Depending on the site geologic conditions, a high flow,
low vacuum regime or a low flow, high vacuum regime may
be required. Two vacuum blowers operated in series or paral-
lel may be required for the field design test to attain the flow
regime under certain site-specific conditions.
The assembly and connection of the vapor extraction test
well, with the vacuum blower, flow meters, and pressure
gauges are shown in Figure 8.21. Since most vacuum blow-
ers are driven by fixed-speed motors, extraction flow rates are
often controlled by installing flow control valves and an air
inlet/dilution valve at the suction end of the vacuum blower.
Partial opening of the air inlet valve provides the means to
control the airflow rate from the extraction well and also the
potential for overheating of the vacuum blower. It is very
important to locate the flow meters and vacuum gauges before
the air inlet valve for accurately measuring the flow character-
istics of the extraction well (Figure 8.21).
During the field design test, two to three flow regimes
can be achieved by manipulating the air inlet/dilution valve.
Initially, the air inlet valve should be closed when the vac-
uum blower is activated. The vacuum distribution in the
soil should be allowed to reach steady conditions. One can
check whether the steady condition is reached by reading the
changes in induced vacuum at the vacuum monitoring wells.
To blower
Bentonite/cement
grout to surface
2–4˝ diameter SCH. 40 PVC
casing
Bentonite seal
(2΄ Minimum)
2–4˝ diameter SCH. 40 PVC
screen
Silica sand
Undisturbed soil
End cap
428 Remediation Engineering

Road box

Fittings for purging

and sampling

Teflon tubing
Geological
unit 1

3΄–5΄ (typ.) Bore hole

Bentonite
seal (typ.)
Contaminated zone

Vapor probe

Undisturbed earth
Geological
unit 2

Washed sand
pack (typ.)
Geological
unit 3

2˝ PVC cap

FIGURE 8.23  Nested probe monitoring well.

Usually stabilization takes place within the first 15–30 min of the extraction wellhead. Similarly, the inlet valve can be opened
pumping. Once stable, the field data collected can be used to further to get a 40%–50% higher vacuum at the wellhead.
directly determine the pneumatic conductivity of the soil by As noted earlier, the screening of the applicability of SVE
rearranging Equation 8.24: should be performed before and during the field design test.
As a summary of the discussion in previous sections, Table 8.3
Q æbö presents the variables that will impact the applicability, selec-
K= ln (8.25)
DPa ®b × 2ph çè a ÷ø tion, and design of an SVE system.

where 8.1.3.2  Design Approaches

Q is the extracted flow rate
h is the thickness of vadose zone where soil vapor flow
is induced, often equal to the height of exposed well
screen
a is the distance from extraction well to nearest vacuum
monitoring point
b is the distance from extraction well to next vacuum moni-
toring point
ΔP is the pressure differential between point a and b
The next step is to repeat the steps mentioned earlier by
opening the air inlet valve to get 20%–25% higher vacuum at
Several design approaches are available for design of SVE
systems. While not all methods are described, the methods
presented in the following sections (empirical, radius of influ-
ence, pore volume exchange) constitute a good, better, best
approach to practical SVE design that can be done using data
collected during the pilot test. Other methods, such as the use
of computer simulation models that may or may not rely on
site-specific pilot test data can also be used.
8.1.3.2.1  Empirical Approach
This is the most simplistic of all the design approaches and
is based upon previous experience, a good understanding
Sparging, Venting, and Vacuum-Enhanced Recovery 429

100 K 100 K

Turbine vacuum pumps

Regenerative vacuum pumps

10 K 10 K (direct drive)

1000 1000
Gas flow (SCFM)

Gas flow (SCFM)

Turbotron
(belt drive)

100 100

10 10

1 1
0 2 4 6 8 10 12 14 16 18 20 22 24 26 28 0 2 4 6 8 10 12 14 16 18 20 22 24 26 28
Vacuum (inches of mercury) Vacuum (inches of mercury)

FIGURE 8.24  Operational ranges based on available turbine vac- FIGURE 8.25  Operational ranges based on available regenerative
uum pump models. vacuum pump models.

of the site conditions, site constraints, general guidelines,

and (mostly) intuition. No site-specific data are collected to
determine design parameters such as well spacing, vacuum
requirement, achievable flow rate, or discharge treatment TABLE 8.3
requirement. The design is based on the basic geologic infor- Soil Vapor Extraction System Variables
mation and the selection of system components to meet the Site Conditions Soil Properties
predicted operating conditions. Unfortunately, performance of
Distribution of volatile organic Pneumatic conductivity
the resulting system may not meet the remediation objectives.
compounds
In some cases, the use of existing system or a skid-mounted
Depth to groundwater table Porosity
system bought from a vendor could be made to match the
Location of heterogeneities and Organic carbon content
design objectives. However, this approach also will be inef- structures
ficient in meeting the remediation objectives. The initial cost Atmospheric pressure Soil moisture content
savings may be offset by poor system performance, extended Barometric changes Particle size distribution
operational time frame, and potential redesign of the whole Temperature Soil structure
system.
Contaminant Properties Process Control Variables

8.1.3.2.2  Radius of Influence Approach Vapor pressure Air extraction rate

Henry’s law constant Extraction vacuums
This approach is perhaps still the most widely used approach
Solubility Extraction well locations
in industry.20 The extraction flow rate, vacuum, number of
Adsorption coefficient Radius of influence
wells, and their locations are selected based on the informa- Density Ground surface seals
tion obtained from a field pilot test. The pilot test is conducted Contaminant levels and composition
to obtain steady-state vacuum vs. distance relationships for a in the extracted air
given site. Extracted air temperature
The steady-state vacuum levels measured at monitoring Extracted air moisture content
wells located at varying radial directions are plotted on a Power usage
semilog graph paper, as shown in Figure 8.26. Vacuum levels
430 Remediation Engineering

70 VEW 1–5
Vapor extraction
60 well locations
50
Measured vacuum (in H2O)

40
VEW 1
VEW 2
30
VEW 5
20 VEW 4

10

VEW 3
5
Zone of contamination

0
0.1 1 10 100 1000 R – Radius of influence
Distance from extraction well (ft)
FIGURE 8.28  Determination of the required number of wells
FIGURE 8.26  Vacuum vs. distance plot on a semilog paper. from the radius of influence.

are measured in various radial directions to compensate for
the possible geologic variations in the subsurface. A best-fit
line is then drawn through the points, as shown in Figure 8.26.
The radius of influence of the extraction well is then deter-
mined as the distance at which a sufficient level of vacuum
will be present to induce airflow. This “cutoff” vacuum level
has been variously defined as 0.1 in. H2O, 1.0 in. H2O, or 10%
of the applied vacuum at the extraction well. This arbitrary
cutoff vacuum level is an empirical value based on prior expe-
rience and geologic conditions.
The tailing effect of vacuum with distance is shown in
Figure 8.27.
Once the radius of influence has been determined, overlap-
ping circles with this radius are drawn on a site map over the
zone of contamination (Figure 8.28). The number of wells and
Vacuum
the locations of wells to cover the contaminated zone can be
obtained this way. It must be noted that the vacuum vs. dis-
tance relationship may vary across the site and that the radius
of influence may not be constant for all the extraction wells.
In this approach, the required screen lengths are estimated
according to the depth of contamination as shown in a geo-
logic cross section. Once the number of wells and the screen
interval in each well has been selected, the total extraction
airflow rate can be summed to determine the total flow of the
system, and selection of the appropriate vacuum blower can
be done by matching the required airflow rate and the vacuum
levels (plus piping losses) to the appropriate operating curve
of various off-the-shelf blowers.
The limitation of this method lies in the arbitrary nature of
the cutoff vacuum level described earlier. Cleanup of vadose
zone soils relies on disruption of the equilibrium between
phases (sorbed, vapor, and dissolved), which is directly related
to the pore volume exchange and/or velocity of the soil gas
at the radius of influence. An arbitrarily chosen vacuum that
defines the radius of influence does not guarantee flow. As an
example, a sealed jar could be under measurable vacuum but
does not have associated flow and therefore no equilibrium
disruption to drive remediation. Additionally, the chosen vac-
uum requirement is often so low that the effect of barometric

surging can overwhelm the vacuum at the design radius of

influence. Barometric surging is described as the exchange of
atmospheric air in to the vadose zone at high barometric pres-
sure and the reverse at low barometric pressure. Figure 8.29
shows an example dataset of barometric pressure fluctuation
over a 3-day period. The rate of change fluctuates between
−0.5 and +0.5 in. of water per hour, which is potentially more
significant in terms of pore volume exchange than an arbi-
trarily chosen radius of influence of 0.1 in. of water column.
Distance from well
8.1.3.2.3  Pore Volume Exchange Approach
FIGURE 8.27  Tailing effect of vacuum away from an extraction The pore volume exchange approach applies the same site-
well. specific data collected in pilot tests but gives the designer
Sparging, Venting, and Vacuum-Enhanced Recovery
410
409
Barometric pressure (in. H2O)
408
407
406
405
0 1000
FIGURE 8.29  Barometric pressure data and rate of pressure change over a 3-day period.
a more reliable, predictable effectiveness at the chosen
radius. The designer chooses the pore volume exchange
rate (PVER) based on experience, time frame required for
cleanup, rules of thumb, or published guidance. As indi-
cated earlier, more than 95% of NAPLs can be removed by
direct volatilization after removing several hundred pore
volumes of air.15 This doesn’t account for the sorbed phase
mass or relatively inaccessible mass that may be limited by
diffusive processes. Typically, designs based on pore vol-
ume exchange target 1 pore volume per day for purposes of
removal by volatilization and up to 10 pore volumes per day
for aggressive systems. Higher PVERs can result in poorer
efficiency due to the time it takes for contaminant mass to
migrate from the source (sorbed sites, soil pore water, etc.)
to primary flow paths.
Pore volume exchange can be converted to flow, shown in
the following equation and depicted in Figure 8.30:
Q = PVER × p × (r 2) × h × ne (8.26)
Q
r and a 40 ft target treatment radius. The second graph then
h
ne
FIGURE 8.30  Diagram of soil vapor extraction well and radial
volume defined by a pore volume.
431
1.0
Barometric pressure
Rate of pressure change (in. H2O per hour)
Rate of change
0.5
0.0
–0.5
–1.0
2000 3000 4000 5000
Elapsed time (min)
where
Q is the extracted flow rate
PVER is the pore volume exchange rate
r is the radial distance where minimum pore volume
exchange is desired
h is the thickness of soil where soil gas is expected to flow
(may be the well screen length)
ne is the effective soil porosity
Once the PVER is chosen, the flow rate for each well can be
determined, and the required vacuum at the wellhead is cal-
culated based on the pneumatic conductivity determined by
the pilot testing procedures described earlier (Equation 8.26).
The advantage of the pore volume exchange method is
that the designer is able to choose between multiple options
for well spacing and corresponding flow rates and required
vacuum based on a chosen pore volume exchange. Figure 8.31
shows a graph of individual well flow rate as a function of tar-
get treatment radius and varying PVERs. A similar graph can
be built for any site using known (or estimated) values for ne
(effective porosity) and h (thickness of vadose zone where soil
gas is expected to flow). Using this figure, the designer could
determine that 15 SCFM is required for a PVER of 3 per day
shows the required pressure drop, which is based on the site-
specific pneumatic conductivity. In this example, for the same
target treatment radius and PVER, a pressure drop of 4 in. of
water is required at the wellhead (indicating a highly perme-
able vadose zone). Once these parameters are established, the
number of wells and positioning are overlaid on the impacted
interval, the total flow rate are determined by summing the
individual flow rates for each of the wells, and selection of
the appropriate vacuum blower can be done by matching
the required airflow rate and the vacuum levels (plus piping
losses) to the appropriate operating curve of various off-the-
shelf blowers.
432 Remediation Engineering

Required well flow as a function of outer radius Required ∆P as a function of outer radius
(0.5–10 pore volumes per day) (0.5–10 pore volumes per day)
40 40
0.5 0.5
35 1 35 1
2 2
30 3 30 3
5
Required well flow (SCFM)

5
10 10

Required ∆P (w.c)
25 25

20 20

15 15

10 10

5 5

0 0
10 20 30 40 50 60 10 20 30 40 50 60
Target treatment radius (ft) Target treatment radius (ft)

FIGURE 8.31  Required flow rate and pressure drop as a function of target treatment radius for various pore volume exchange rates.

As noted earlier, there are factors other than soil pneumatic
conductivity that govern the airflow field during SVE. Soils
with higher porosities will allow a higher flow for the same
induced vacuum. Porosity influences the intrinsic air perme-
ability and is related to the particle size distribution of soil.
Coarse textured soil will generally have higher porosities and
thus higher permeabilities.
The presence of subsurface features that are less restrictive
to flow may result in preferential flow in directions different
than expected based on site geologic conditions. Subsurface
utility conduits (electric, telephone, sewer, and water) may be
bedded in materials much more permeable than surrounding
soils. Preferential flow paths will be formed if these conduits
intersect the zone of vacuum influence.
perturbation caused by the SVE system to the contaminant
partitioning and predict contaminant concentrations within
the various media at different time frames.
8.1.3.3  Operational Considerations
Where traditional SVE is employed, the vacuum applied at the
well screen dissipates as a function of the radial distance from
the well. At a point equidistant between any two SVE wells, a
vacuum can be measured, but a gradient no longer exists to drive
soil gas movement in either direction. In other words, the two
SVE wells are exerting a force exactly equal and in two oppos-
ing directions, resulting in zero movement of the soil gas at
that point. Figure 8.32 illustrates this point by depicting a graph
of the vacuum vs. distance between two SVE wells applying

8.1.3.2.4  Modeling Approach Air out Air out

Computer simulation modeling can also be used to design
SVE systems. This allows the model user to vary operating
parameters and observe a simulation of the result. The type of
models available for SVE system design can be classified into
airflow models and multiphase transport models.
Flow type models, available in the public domain, such
as HYPERVENTILATE and AIR 3D, simulate only air-
flow under varying operating conditions. Airflow models
therefore allow for selection and optimization of well place-
ment and well screening within the contaminated zone. This
selection is based on a predetermined, minimal acceptable P 0
airflow.
Multiphase transport modeling allows for simulating the
SVE process over time based upon the selected well layout.
The multiphase transport models are therefore often pre-
ceded by simple airflow models that locate extraction wells. FIGURE 8.32  Profile of vacuum versus distance between two
The multiphase transport models simulate the subsurface identical soil vapor extraction wells.
Sparging, Venting, and Vacuum-Enhanced Recovery 433

equal vacuum. At the inflection point, the vacuum gradient is In  this case, the injection well is under pressure and the
zero, resulting in a point of stagnation at that location. extraction under vacuum. The gradient of the line is consis-
One way to overcome the challenge is to install injection tent between the two points, even though the vacuum directly
or air inlet wells located at numerous places at an SVE site between the two is zero. Flow is induced from left to right,
depending on the needs. The function of air inlet wells is sweeping across the former point where the vacuum vector
to control the subsurface airflow and overcome preferential was equal but opposite due to the two extraction wells in
pathways and dead zones (Figure 8.33). Air injection wells are Figure 8.32.
passive and can be installed at the edge of a site, so as not to Remediation using an injection and extraction network can
induce flow of contamination from an adjacent site. Typically, be designed with flexibility to change the polarity (injection/
injection and inlet wells are similar in construction and can be extraction) as required to eliminate points of stagnation.
interchanged during SVE operation. Figure 8.35 shows a network of injection wells (open circles)
In systems where both injection and extraction are and extraction wells (closed circles) with arrows indicating
employed, the vacuum profile between two wells of opposite major and minor flow paths between injection and extraction
polarity is dramatically different, as shown in Figure  8.34. wells. The lowest performing areas are depicted by the dia-
mond shapes in between. With relative ease, a second phase
Air in Air out of operation could be completed by changing select injection
Site boundary wells to withdrawal mode, and vice versa. Figure 8.36 shows
the same network of wells in such a second phase, with simi-
lar arrows drawn to show primary and secondary pathways
and low performing areas. Note that the prior low-performing
Dead zone areas are now under primary pathways, specifically targeting
the mass that was difficult to access during the first phase of
operation.
Other methods for addressing nodes of poor treatment
are available. For instance, periodic adjustment of the flow
and vacuum in a standard SVE (withdrawal only) can also
vary the point of no flow between any two wells. Referring
Air
to Figure 8.32, if the SVE wells were changed such that the
extraction
Air vacuum in the well to the left was twice that of the vacuum
well
extraction in the well to the right, the point at which the vacuum was
well
Air equal and from opposing directions would shift to the left,
Air flow injection inducing some amount of flow directly between the two wells.
stagnation well
zone
Periodic adjustments to the vacuum field designed to address
Vapor flow points of stagnation can be beneficial to removal efficiency
after the initial setup of the system has been operated to a
FIGURE 8.33  Use of air injection wells during soil vapor extrac- point of diminishing returns.
tion operation.

Air in
P 0
FIGURE 8.34  Profile of vacuum versus distance between an air
injection and extraction well.
8.1.4  Bioventing
Air out
In most cases, SVE has been primarily applied for the
removal of VOCs from the vadose zone utilizing volatil-
ization as the primary mass transfer mechanism. However,
introduction of atmospheric air into vadose zone soils can be
utilized to enhance the degradation of VOCs that are aero-
bically biodegradable (Figure 8.40). Bioventing can reduce
vapor treatment costs and can also result in the remediation
of semi-VOCs that cannot be removed by direct volatiliza-
tion alone.15,25
In bioventing, the aerobic biodegradation processes are
optimized to become the dominant process by modifying
the venting system. Bioventing systems use the same blowers
used in SVE systems to provide specific distribution and flux
of air through the contaminated vadose zone. An SVE system
attempts to maximize airflow through the soil to maximize
the rate of volatilization of contaminants into the airstream.
A biovent system attempts to sufficiently manage the airflow
434
FIGURE 8.35  Injection and extraction network layout (first phase).
FIGURE 8.36  Injection and extraction network layout (second
phase).
rate to achieve maximum oxygen usage by the vadose zone
microbial populations. Consequently, the biovent airflow rates
are commonly an order of magnitude lower than SVE air-
flow rates. In terms of pore volume exchange, where a system
designed for volatilization might range from 1.0 (standard) to
10 (aggressive) pore volumes per day, a bioventing system can
operate successfully using a PVER of 0.1 pore volumes per
day (1 pore volume every 10  days). The oxygen introduced
Remediation Engineering
stimulates the indigenous microorganisms to degrade the con-
taminants to more benign compounds such as carbon diox-
ide, water, and biomass. For example, degradation of benzene
takes place according to the equation
C6H 6 + 7.5O2 ® 6CO2 6H 2O + Biomass (8.27)
Based on this equation, about 3.5 g of O2 are required per
gram of benzene degraded. This method is relatively power-
ful, because atmospheric air contains 21% oxygen. During
implementation of bioventing, soil gases present in the sub-
surface are generally monitored to ensure the presence of
aerobic conditions. The gases monitored are O2, CO2, and
CH4. Increased levels of CO2 (atmospheric level is 0.03%) and
depletion of O2 indicates a higher level of microbial activity
that are using the oxygen in the subsurface. However, at sev-
eral sites,26 oxygen utilization has proven to be a more useful
measure of biodegradation rates than carbon dioxide produc-
tion. Abiotic factors such as soil pH and alkalinity may influ-
ence the soil gas O2 concentrations. Higher pH and higher
alkalinity soils will exhibit little CO2 in the soil gas due to
the formation of carbonates. The soil water content will also
impact the measurable CO2 in the soil gas due to the solubil-
ity of CO2. During bioventing, oxygen concentrations in the
vadose zone should be periodically measured to ensure that
the system is delivering adequate oxygen that the demand of
oxygen is being met.
8.1.4.1  Laboratory Testing
A series of analyses can be performed on-site soil samples
to evaluate the potential for microbial degradation of the
contaminants. The evaluations are conducted to determine
whether the site soil samples have (1) a generally healthy
microbial population without being stressed by the contami-
nant concentrations and (2) specific microbial species capable
Sparging, Venting, and Vacuum-Enhanced Recovery
of degrading the contaminants present. In addition, an analy-
sis should be performed to determine the availability of solu-
ble N- and P-containing nutrients such as ammonium, nitrate,
and phosphates. Environmental parameters such as pH and
moisture content should also be evaluated.
Total heterotrophic microorganisms and specific degrader
microorganisms population is enumerated using the plate
count procedure. At least 105 colony-forming units (CFU) per
gram of soil should be present in the soil samples for bio-
venting to be feasible. Microbial population in the range of
107–108 CFU/g of soil is considered very healthy for biovent-
ing. Measurement of respiration rates can also be performed
in the laboratory, using site soil samples, to evaluate the
microbial activity.
In the past, biodegradability of specific contaminants was
also evaluated in the laboratory. Currently, there is an abun-
dance of data on biodegradability of common environmental
contaminants (Appendix).
8.1.4.2  Design of Bioventing Systems
The design of a bioventing system has three basic require-
ments. The following are the basic requirements in order of
importance15,20:
1. Maintain an oxygen flux through the contaminated
soils matching the rates of active, aerobic biodegra-
dation in those soils.
2. Maintain soil moisture within an optimal range for
microbial activity.
3. Supply growth-limiting nutrients as needed to bol-
ster microbial populations.
In order for these requirements to be satisfied, several oper-
ating parameters of a bioventing system need to be properly
designed. These are discussed in the following.
8.1.4.2.1  Oxygen Flux
As described earlier, there are different objectives for SVE
and biovent systems. A biovent system can operate at a
much lower flow rate, which is intended to maintain oxygen
20
O2 concentration as a percentage
15
10
5 4
0 2
Intiation of
bioventing
FIGURE 8.37  Typical O2 and CO2 percentages in the soil gas during bioventing.
435
concentrations that support aerobic bioactivity. Viable aerobic
bioactivity is typically found in contaminated sites where the
oxygen levels in the soil are above 2%. When the oxygen con-
tent of the soil air falls below 2%, aerobic bioactivity becomes
dormant or absent. At this point, the soil air is dominated
instead by carbon dioxide and methane. In examining field
data on vadose zone air quality, keep in mind that the soil air
is made up of a large number of small-scale zones or micro-
zones, arrayed like a 3D jigsaw puzzle determined by the geol-
ogy and contaminant distribution. Within each microzone,
the air can either be (1) replenished relatively frequently and is
thus aerobically active, (2) replenished relatively infrequently
and is thus aerobically dormant with high carbon dioxide lev-
els, or (3) largely stagnant and active only anaerobically with
accumulating products such as methane and carbon dioxide.
Most monitoring or extraction wells intersect several of these
microzones. If it intersects only the first type or only the third
type of microzones described earlier, the results will seem
clear-cut. If the well intersects a mixture of microzone types,
the results can be ambiguous and confusing. Typical O2 and
CO2 percentages in the soil gas during bioventing are shown
in Figure 8.37.
8.1.4.2.2  Soil Moisture
For a bioventing system, it is very important to maintain a
moderate soil moisture, usually in the range of 40%–60% of
field capacity to maintain viable, aerobic bioactivity within
the manipulated zone. If soil moisture increases appreciably
above this range, the resultant pore sizes for air movement
shrinks, decreasing the air permeability and flow rates. For
these reasons, it may be important to include in the design
some means of adding moisture to the contaminated zone
such as in arid climates or under buildings where little infil-
tration is expected. It should be noted that impact of soil mois-
ture on biodegradability is also influenced by the solubility of
the contaminant.
Availability of O2 is the rate-limiting step for bioventing
in most cases. Optimum moisture content plays a signifi-
cant role, but not as dominant as the availability of oxygen.
Macronutrients such as N and P and the micronutrients are
O2 levels in the soil gas
CO2 levels in the soil gas
10
CO2 concentration as a percentage
8
6
Significant
Steady state biodegradation mass removed
Time
436 Remediation Engineering

generally available in the site soils. In rare cases, N and 8.1.4.3  In Situ Respiration Test
P-containing soluble salts may have to be added to the site An in situ respiration test is perhaps the best method currently
soils. Nitrogen and phosphorus initially consumed by the available to assess the rates of biodegradation that can be
microbial mass are constantly recycled due to the lysis of dead sustained by a bioventing system. This section describes the
microbial cells. Hence, the need and availability of N and P steps that are generally necessary for successfully carrying
are critical only during the early stages of microbial growth. out an in situ respiration test.
8.1.4.2.3 Temperature
8.1.4.3.1 Equipment
Temperature dependency of biodegradation rates has been
The equipment needed for carrying out an in situ respiration
reported to follow the van’t Hoff–Arrhenius equation,20,26,27
test can be fairly simple. If an SVE pilot test is also to be
as well as the Phelps equation.20,27 The van’t Hoff–Arrhenius
carried out at the site, the test can make use of that pilot test
equation is as follows:
equipment that is comparable to those listed in the following.
Also, should a more rigorous test be required, some or all of
Y = Ae - Ea / RT (8.28)
the optional equipment can also be used. The basic equipment
where needed is listed in the following:
Y is the temperature-corrected biodegradation rate
A is the baseline degradation rate • Small air compressor or blower (a minimum of
Ea is the activation energy 1–2  cfm capacity). Examples of easily available
R is the gas constant equipment include car tire inflation pumps or air
T is the absolute temperature mattress inflation pumps. These can be plugged into
a car cigarette lighter or other electric outlet.
The Phelps equation, which describes the relationship • Oxygen (O2) field monitoring device for air, with
between respiration rate and temperature, is as follows: ±0.5% accuracy or less. Examples include ferrite
meter, explosimeter, and Gastech meter.
Rt = R7q( ) (8.29) • Carbon dioxide (CO2) field monitoring device for air
t -7

with ±0.5% accuracy or less.
where • In-line sampling and field monitoring devices.
Rt is the rate at temperature t°C
R7 is the rate at 7°C 8.1.4.3.2  Test Procedures
θ is the thermal coefficient 1. Monitor the candidate wells for O2, CO2, CH4, and
total volatile organics concentrations in the adja-
The design criteria of a bioventing system are summarized cent vadose zone. Use the wells with at least a por-
in Table 8.4. tion of their screen extending above the water table.
Throughout these test procedures, remove several
well casing volumes prior to collecting and analyz-
ing samples.
TABLE 8.4 2. Select a well for the test in a moderately contami-
nated area with predominantly aerobic bioactivity.
Design Criteria for a Bioventing System
Soil contaminant concentrations should be greater
Parameter Impact than 50 mg/kg. It is important to remember that,
1 Lateral and vertical extent of Contaminant mass estimate regardless of the conditions currently prevailing at
contamination the site, whether anaerobic, aerobic, or both, biovent-
2 Geology of the contaminated Manipulation of airflow in various ing will ultimately convert the site to active, aerobic
zone zones and thus required airflow biodegradation. We must select those contaminated
rates and vacuum levels subareas of the site that can quickly and easily be
3 Air residence time and pore Biodegradation rates, required converted to active, aerobic bioactivity during the
volume exchange airflow rates, and thus extraction test. Failure to select a proper test site will likely
blower capacities
result in negative results.
4 Location of air extraction wells Design of the bioventing system
3. Prior to beginning the test, measure the O2, CO2,
and air recharge conditions and
CH4, and total volatile organics concentrations in the
the need for air injection wells
5 Soil moisture content and Design of moisture and nutrient
test well.
background nutrient levels addition systems 4. Inject at least 1000 ft3 of air into the test well. Air
6 Continuous monitoring of O2, Focused monitoring and can be injected in up to five wells. It is generally
CO2, and other soil gas optimization of bioventing advisable to mix 1%–2% He with the injected air as
concentrations performance a tracer gas. Detection of He implies that the air sam-
pled is the same that was injected and the changes
Sparging, Venting, and Vacuum-Enhanced Recovery
in its makeup can be attributed to microbial activ-
ity. A volume of 1000 ft3 is deemed necessary to
avoid boundary effects from interfering with the test
results. Regardless of the capacity of the air pump
used, this volume of air should be injected within
24 h. It usually takes about 24 h for the soil micro-
bial populations to convert from their dormancy to
active respiration. If a higher capacity pump is used,
monitoring may optionally be carried out during the
remainder of the 24  h period. However, the respi-
ration rates monitored are typically distinctly lower
than the respiration rates subsequently measured. At
the least, it provides a testing period for assessing the
accuracy of the monitoring devices.
5. Begin periodic monitoring of O2 and CO2 concentra-
tions in the test well 24 h following the start of air
injection. Samples should be analyzed at least sev-
eral times per day and, at most, hourly. The actual
frequency should be selected in the field so that the
data collected show a definite trend in O2 and CO2
concentrations in spite of the scatter caused by meter
error.
6. Continue the monitoring of the test well until O2
and CO2 concentrations have changed at least 5%.
Preferably, the test would be conducted until the O2
and CO2 concentrations have changed over 10%.
This duration is necessary to define a definite trend
through much of the range in O2 concentration that
active, aerobic biodegradation occurs. This will
likely require a test duration of at least 1 day and
possibly 2 days.
7. The data should be analyzed for both zero-order and
first-order relationships. For zero-order analysis,
compare the O2 and CO2 concentrations with respect
to time (e.g., [O2] vs. time). For first-order analysis,
compare the ratio of the test O2 and CO2 concentra-
tions to the initial concentrations with respect of
time. Determine the linear regression equation for
each analysis as well as the coefficient of determi-
nation (R2). Select the order of analysis that has the
higher R2 values. Previous studies have empirically
found both approaches to be appropriate. Usually
(but not always), the O2 depletion trends have been
found to be more reliable than CO2 production trends.
However, this is partly a function of the monitoring
devices used and the geochemistry of the given site.
8.1.5  Monitoring Requirements
As noted earlier, the performance of an SVE system has to be
optimized and fine-tuned continuously as the system opera-
tion proceeds. Monitoring data are used to assess system per-
formance and calibration of models and to guide necessary
operational changes and equipment modifications.
The most important performance monitoring parameter
is soil concentration. If the concentrations of contaminants
in soil are dropping at a satisfactory rate, then the system
437
is obviously performing well. The operational monitoring
parameters described in the following are secondary in terms
of performance but necessary to guide operational decision-
making and ensure proper operation and longevity of the sys-
tem. The simplest way of assessing SVE process performance
is to monitor the flow, vacuum responses and the concentra-
tion, and composition of the contaminants in the extracted air.
This is the minimum monitoring required to identify mass
removal rates and any changes in the subsurface conditions
impacting the flow characteristics. Table 8.5 presents an
expanded list of monitoring requirements and the impacts on
system performance.
8.1.6  Vapor Treatment Technologies
The most common technologies for abatement of airstreams
laden with VOCs and semi-VOCs, hereafter collectively
referred to as VOCs, are described briefly in the following.
The types of common VOCs that require abatement when
present in an airstream are as follows:
• Aliphatic hydrocarbons
• Aromatic hydrocarbons
• Chlorinated hydrocarbons
• Alcohols, ethers, and phenols
• Ketones and aldehydes
Applicability of the most common vapor abatement technolo-
gies to these contaminant types is shown in Table 8.6.
8.1.6.1  Thermal Oxidation
An industry proven technology for VOC abatement is oxida-
tion, either catalytic or thermal. Oxidation units can destroy
nearly 75% of the VOC and toxic emissions targeted by the
Clean Air Act Amendments of 1990 and greater than 97% of
the VOCs in a VOC-laden airstream. Thermal oxidation, also
known as thermal incineration, operates on a simple premise:
sufficiently heating a VOC in the presence of oxygen will con-
vert the VOC to carbon dioxide and water.
A thermal oxidation unit typically consists of a blower to
move VOC-laden air, a filter–mixer to mix the VOC-laden
air, a fan to supply combustion air (if additional oxygen is
required), a combustion unit consisting of a refractory-lined
combustion chamber and one or more burners or electric heat-
ing elements, heat-recovery equipment, and a stack for atmo-
spheric release of the abated air.
The operating temperature of the combustion chamber
is one of the primary parameters that influence the VOC
destruction efficiency of a thermal oxidation system. The
temperature must be sufficiently elevated to meet efficiency
goals and prevent the emission of products of incomplete
combustion. VOC-laden air with low concentrations of VOCs
may not possess the oxidation energy required to maintain
the necessary temperature to promote complete combus-
tion (1200°F–2000°F); therefore, oxidation of these streams
would require supplemental fuel (e.g., natural gas or pro-
pane) or electrical energy to supply the additional energy
438 Remediation Engineering

TABLE 8.5
Soil Vapor Extraction System Performance Monitoring Requirements
Data Required
Flow rate with time
Applied vacuum with time
Extracted air concentration with time
Extracted air composition with time
Monitoring well vacuum measurements
Impact(s)
Pore volumes removed per day
Subsurface changes with respect to air permeability
Subsurface air distribution
Subsurface changes in air permeability, moisture content
Induced air distribution and zone of influence
Rate of mass removal
Typically declines with time
Cumulative mass removed
Decline to low mass removal rates can occur well before soil cleanup standards are reached.
Volatilization phase shifting to diffusive phase
Vapor treatment technologies
Weathering of contaminants
Rate of mass removal
Microscopic scale phenomena of contaminant partitioning
Volatilization phase shifting to diffusive phase
Ability to reach soil cleanup standards
Aerobic vs. anaerobic conditions
O2/CO2 concentration ratios will be an indicator of biodegradation activity in the subsurface.
Vapor treatment technologies
Areal extent of vacuum coverage
Induced airflow distribution pattern

TABLE 8.6
Applicability of the Most Common Vapor Treatment Technologies to Different Types of Volatile
Organic Compounds
VOC Type
Treatment Technology Aliphatic HC Aromatic HC Chlorinated HC Alcohols, Ethers, Phenols Ketones, Aldehydes
Thermal oxidation × × × × ×
Catalytic oxidation × × a × ×
Adsorption × × × ×
Condensation × × × × ×

a Sometimes applicable.

required to maintain the necessary combustion temperature.
Conversely, VOC-laden air with very high concentrations of
VOCs (between the upper and lower explosive limits) may
require dilution air to prevent explosion.
Heat recovery equipment may be installed with a thermal
oxidation system to preheat the VOC-laden airstream prior to
combustion by utilizing the heat content of the postcombus-
tion airstream. Preheating the incoming stream reduces the
amount of supplemental fuel that would be required to main-
tain the necessary combustion temperature.
In addition to combustion temperature, two other param-
eters that influence the VOC destruction efficiency of a ther-
mal oxidation system are residence time and degree of mixing.
Residence time is the amount of time required for complete
oxidation of VOCs. Generally, residence time varies from
0.5 to 1 s.30 Longer residence times may be required if cer-
tain VOCs such as chlorinated organic compounds are pres-
ent. The residence time is affected by the degree of mixing
of the VOC-laden stream prior to combustion. More thor-
oughly mixed VOCs require less residence time for complete
oxidation.
There are three types of thermal oxidation systems:
straight-through, recuperative, and regenerative. They are dif-
ferentiated by the equipment used for heat recovery.
There are two common types of straight-through thermal
oxidation systems. An afterburner or direct flame oxidizer uti-
lizes a direct-fired burner in an insulated combustion chamber
to promote combustion. A flameless thermal oxidizer utilizes
a ceramic media packed combustion chamber that is main-
tained above the autoignition temperature of the VOCs by
Sparging, Venting, and Vacuum-Enhanced Recovery
Combustion air* Thermal
Supplementary fuel oxidizer
* Required under specific conditions.
FIGURE 8.38  Schematic diagram of a recuperative thermal oxidizer.
utilizing the heat of combustion and thus requires no flame
except for during initial heating. Neither has heat-recovery
equipment. The combustion chamber is sized to allow for
the necessary residence time at a certain airflow velocity to
achieve a desired destruction efficiency. These systems have
the lowest capital cost but are typically the most expensive to
operate. High VOC concentrations will help minimize auxil-
iary fuel consumption.
Recuperative systems (Figure 8.38) use a heat exchanger,
typically crossflow, counterflow, or concurrent flow, for heat
recovery. The VOC-laden airstream is preheated by the trans-
fer of heat from the postcombustion airstream. This system is
sized based on the flow rate, and the cost generally increases
in proportion to the heat exchanger’s efficiency that is dictated
by its design and materials of construction. The recupera-
tive system is typically best suited for moderately high VOC
concentrations where heat generation can significantly offset
supplemental fuel requirements.
Regenerative systems use ceramic material for heat recov-
ery. The ceramic material is stored in separate beds located on
both ends of a central combustion chamber. As hot air leaves
the combustion chamber, it heats the ceramic material located
in the postcombustion ceramic bed. Periodically, the direction
of airflow is reversed such that VOC-laden air is heated by
what was previously the postcombustion ceramic bed. This
heated air then enters the combustion chamber, oxidizes, and
then heats what is currently the postcombustion ceramic bed.
They generally use less supplemental fuel than the other sys-
tems because of the superior heat transfer capability of the
ceramic material. As a result, these systems may be attractive
for abatement air with low VOC concentrations.
During thermal oxidation of chlorinated hydrocarbons,
hydrochloric acid (HCl) fumes are formed in addition to CO2
and H2O. As a result, removal of the HCl formed is neces-
sary before the treated air is discharged to the atmosphere.
Consideration must be given to materials of construction
for postcombustion equipment that may be subject to con-
tact with hydrochloric acid. A scrubber installed before the
exhaust stack will facilitate the removal of the acid present
in the effluent airstream prior to discharge. Caustic soda or
potash can be used as the absorbent solution in the scrubber.
439
Emission source
Scrubber*
Dilution air*
Stack
Heat
exchanger
(optional)
Incomplete combustion of VOCs may lead to solubilization of
the residual VOCs in the scrubbing solution. Care should be
taken to dispose the neutralized scrubbing solution properly
under these circumstances.
In summary, the design criteria for thermal oxidation are
governed by
• Influent airflow rate
• Influent VOC concentrations
• Influent VOC composition
• Combustion temperature
• Residence time
• Degree of mixing
• Oxygen present in the combustion chamber
8.1.6.1.1  Internal Combustion Engines
The use of internal combustion (IC) engines for VOC abate-
ment represents a unique application of thermal oxidation and
deserves a brief mention. IC engines have been adapted such
that they can be connected directly to a VOC-laden air steam,
draw the vacuum necessary to promote flow of the VOC-
laden airstream in to the engine, and ultimately combust the
VOCs emitting only water and carbon dioxide. This technol-
ogy is appropriate for abatement of airstreams with very high
VOC concentrations and is not recommended for long-term
VOC abatement. IC engines are typically appropriate for spill
responses and new releases.
8.1.6.2  Catalytic Oxidation
Catalytic oxidation is very similar to thermal oxidation and
combines a conventional-type heat exchanger with a cata-
lyst. A catalyst inside the combustion unit lowers the acti-
vation energy for combustion; thus, combustion occurs at a
lower temperature than for thermal oxidation. The catalyst,
either precious or base metal, will allow oxidation to occur at
a fairly low temperature of about 500°F–700°F. As a result,
supplemental fuel costs for catalytic oxidation are usually
much lower than for an equally applicable thermal oxidation
system. In the absence of a supplemental fuel supply or under
safety restrictions for flame combustion, electric power may
be a convenient means to heat the influent airstream.
440
Catalytic incinerator
Combustion air*
Supplementary fuel Preheater
* Required under specific conditions.
FIGURE 8.39  Schematic diagram of a catalytic oxidizer.
Typical catalyst materials include platinum, palladium, and
metal oxides such as chrome alumina, cobalt oxide, and cop-
per oxide–manganese oxide.30 The average catalyst lifetime is
2–5 years, after which deactivation by inhibitors, blinding by
particle entrainment, and thermal aging can render the cata-
lyst ineffective thus requiring regeneration or replacement.
Catalytic materials may be inserted into the combustion unit
in either a monolithic or beaded configuration.
Because of its sensitivity to VOC-laden airstreams and
process operating characteristics, the catalyst dictates the
optimum operating conditions for a catalytic oxidation sys-
tem (Figure 8.39). There is an inverse relationship between
destruction efficiency and process flow rates. The higher the
destruction efficiency desired, the lower the flow rate that can
be processed. Higher flow rates require the installation of
multiple catalysts.
Catalytic oxidation systems are not effective in streams
containing lead, arsenic, sulfur, silicone, phosphorus, bis-
muth, antimony, mercury, iron oxide, tin, zinc, and other cata-
lyst deactivators. These compounds have a tendency to mask
or poison the catalyst’s cell structure. When this occurs, the
catalyst’s ability to drive the combustion reaction decreases,
thus requiring more energy (supplemental fuel or electricity)
to promote complete combustion. Masking of the catalyst
may also cause airflow restrictions whereby more horsepower
could be needed to push the air through the system. In order
to prolong the lifetime of the catalyst, it has to be cleaned
periodically to remove deactivators and particulates.
Catalytic oxidation systems are typically applied to low-
VOC-concentration streams (<2000 parts per million by vol-
ume), since high VOC concentrations and associated high heat
contents can generate enough heat of combustion to thermally
decompose the catalyst. Dilution air may be required when
the influent VOC concentrations are high. The temperature
and pressure across the catalyst bed should be monitored to
ensure catalyst viability. The temperature rise across the cata-
lyst indicates the extent of VOC oxidation; a decrease in the
temperature rise across the catalyst may indicate that VOC
oxidation is incomplete. Since excessive heat can deactivate
most catalysts, the inlet temperature to the catalyst bed must
be kept sufficiently low to preserve catalyst activity. Similarly,
Remediation Engineering
Emission source
Dilution air*
Stack
Heat exchanger
Catalyst bed (optional)
the pressure drop across the catalyst is also an indication of
the catalyst bed viability. The substantial amount of process
control required to operate a catalytic oxidizer is illustrated
in Figure 8.40.
Design criteria for catalytic oxidation systems can be sum-
marized as follows:
• Influent airflow rate
• Influent VOC concentrations
• Influent VOC composition
• Operating temperature
• Catalyst properties
• Space velocity and retention time
• Oxygen present in the combustion chamber
• Presence of impurities and poisoning compounds
• Type of heat exchanger
• Availability of energy source (electricity vs. supple-
mental fuel)
8.1.6.3 Adsorption
Adsorption refers to the process where gaseous VOC mol-
ecules contact a solid adsorbent and bond via weak intermo-
lecular forces. Granular activated carbon is the most common
adsorbent in use today for VOC removal mostly owing to the
relatively large available surface area of the granules. Other
adsorbents include silica gel, alumina, synthetic media, and
specialized resins. Activated carbon is derived from wood,
coal, or other carbonaceous raw materials such as coconut
shells. Granular activated carbon prepared from coconut
shells can be prepared in large particle sizes necessary to help
minimize pressure drop and is extremely hard, which leads to
low attrition even under rough handling and high gas velocity
conditions.
The adsorption of VOCs on the micropore surfaces of
carbon is mainly a physical process involving van der Waals
type forces. Since these interactions are weak, the VOC is
in dynamic equilibrium with the carbon surface and is being
constantly adsorbed and desorbed. This adsorption/desorption
process causes the VOC to be retained in the carbon pore
structure. The more the VOC is “like” the carbon surface,
the stronger it will interact with the surface. For example,
Sparging, Venting, and Vacuum-Enhanced Recovery 441

Vapor source

Dilution inlet valve Fresh air

Purge/block
valve
Purge air E

115 VAC

P S

115 VAC

Soil vent system Combustible gas

blower sensors
E
Blocking Alarm
valve controller
Nonhazardous
Flame area
arrestor
MP
Effluent air

Bypass damper Heat exchanger

MP

Post cat.
Hi limit sensor MT
T T

Catalyst Heater controls

Heater
T

Hi limit sensor

MT MP
T T
Process/Lo limit sensor

Power
230 VAC, 1φ or 3φ

T Thermocouple

S P Airflow monitored by P pressure sensor

MT Monitoring thermocouple Process stream

Catalytic scavenger
system Power
MP Monitoring port
Control signal
E ASVA automated safety
Electrically actuated valve valve assembly Connection to
process
Manually actuated valve

FIGURE 8.40  Catalytic oxidizer piping and instrumentation diagram.

molecules consisting mainly of aromatic or aliphatic moieties
will adsorb more strongly than oxygenated molecules.
Vapor-phase granular activated carbon is generally used
in a fixed bed, and the contaminated air is passed through the
adsorbent bed. The adsorption of VOCs from air by a carbon
bed is a continuous process but for convenience of presenta-
tion can be envisioned as taking place in layers. Thus, one can
envision that when a contaminant stream passes through the
bed, some contaminant is removed by layer “a” at the entrance
of the bed, leaving a lower contaminant level in the stream
442
to contact the next layer “b.” Layer “b” then in turn removes
more of the contaminant. The reduction of contaminant level
as the stream contacts further layers of unused carbon con-
tinues until finally layer “z” is reached. The layers of “a” to
“z” are known as the adsorption zone or the mass transfer
zone (MTZ). As the flow continues, the MTZ progressively
advances and propagates until breakthrough occurs. The fol-
lowing factors play important roles in adsorption dynamics
and the length and shape of MTZ:
• Type, size, and macro- and micropore surface area
of the carbon
• Depth of the adsorbent bed and empty bed contact
time
• Gas velocity
• Temperature of the influent airstream
• Concentration of contaminants to be removed
• Moisture content and relative humidity
• Pressure of the system
• Vapor pressure of the contaminants to be adsorbed
• Possible decomposition or polymerization on the
carbon surface
Adsorption decreases with increasing temperature. Because
the equilibrium capacity of adsorbents is lower at higher tem-
peratures, the dynamic or breakthrough capacity will also be
lower, and the MTZ proportionately changes with tempera-
ture. It should be also noted that the adsorption process is
exothermic and involves the liberation of from 2 to 5 kcal/mol
of heat. As the adsorption front moves through the bed, a tem-
perature front also proceeds in the same direction, and some
of the heat is imparted to the gas stream. When the gas leaves
the adsorption front, the heat exchange will reverse and the
gas will impart heat to the bed. This increase in temperature
in downgradient zones in the bed decreases the capacity in
that zone. As a result, the maximum inlet concentration to a
carbon bed should be limited to less than 10,000 ppmv.
The relative humidity and the moisture content of the influ-
ent stream also have a significant impact on the adsorption
Influent stream
Adsorbers
Low-pressure
stream
FIGURE 8.41  Schematic diagram of a fixed regenerative bed carbon adsorber.
Remediation Engineering
capacity of the bed. Small quantities of moisture actually
enhance the adsorption process, as the heat of adsorption
is carried with the moisture. However, relative humidi-
ties in excess of 50% tend to lessen the effectiveness of the
bed. Moisture knockout systems or in-line heaters installed
upstream of the bed will help to alleviate this problem.
Moisture content plays an important role when treating efflu-
ent airstreams of an air stripper. Polymeric adsorbent resins
that are significantly more hydrophobic than carbon have
shown to be able to adsorb at least 10 times more VOC mass
than activated carbon.
When using activated carbon for air treatment, the spent
carbon must be replaced or regenerated. If the replacement
option is chosen, as soon as the carbon is spent, it is removed
and sent to an off-site reprocessing facility to be regenerated.
This option is preferred when the total mass of VOCs to be
removed during the life of the project is not high.
When the contaminant mass to be removed is high, fixed
regenerative beds should be considered. On-site regenera-
tive beds consist of two or more beds of activated carbon.
Continuous operation of the system is maintained by the con-
current adsorption in at least one bed and desorption by the
other beds. A schematic diagram of a fixed regenerative car-
bon bed is shown in Figure 8.41.
Desorption of the carbon bed refers to the process or regen-
erating the carbon to restore its adsorbing capabilities and
preserve its useful life (usually 2–5 years). The desorption pro-
cess normally lasts 1–2 h and consists of the following three
steps: regeneration of the carbon, bed drying, and returning
the bed to its operating temperature. Carbon regeneration is
accomplished by volatilizing the adsorbed compounds either
by raising the temperature of the carbon bed via steam (steam
desorption) or lowering the temperature in the bed to vacuum
conditions to increase the vapor pressure of the adsorbed
VOCs (vacuum desorption). The adsorption time of each bed
is dependent on the influent mass flux rate and is usually final-
ized during the installation and start-up period. The automatic
cycling of beds between adsorption and desorption modes is
controlled by an onboard programmable logic controller.
Condenser
Decanter
Exhaust to atmosphere
Sparging, Venting, and Vacuum-Enhanced Recovery
When chlorinated organic compounds are present, HCl
may be produced during steam regeneration of the carbon
beds. Accumulation of HCl in the beds may corrode the
container and require periodic replacement. Under such cir-
cumstances, use of a container that has a corrosion-resistive
internal surface such as Teflon or Haztalloy should be used.
Another method of overcoming the same concern is to use
heated nitrogen as a carrier gas under vacuum desorption con-
ditions. Nitrogen also helps in maintaining an inert environ-
ment in the bed. The nitrogen containing all the purged VOCs
is condensed, and the VOCs are separated as a liquid before
reusing the nitrogen gas.
When the influent airstream flow rates are small and the
total VOC mass is less, smaller-sized carbon canisters that are
usually of 55 gal in volume and contain approximately 200 lb
of carbon can be used. Once the carbon becomes saturated,
these canisters are disposed and replaced with a new canister.
Carbon adsorption is not effective for controlling highly
volatile VOCs (such as vinyl chloride), which do not adsorb
well. Similarly, highly nonvolatile VOCs (compounds with
very high molecular weight) that do not desorb well are also
not good candidates for removal by carbon adsorption.
Design criteria for carbon adsorption systems can be sum-
marized as follows:
• Influent airflow rate
• Influent VOC concentrations
• Influent VOC composition
• Adsorption capacity
• Influent air temperature
• Influent air moisture content and relative humidity
• Adsorption equilibria related to waste mix
8.1.6.4 Condensation
Condensation is the process of removing VOCs from a non-
condensable gas stream. Condensation can occur by lowering
the gas stream temperature at constant pressure or increasing
the gas stream pressure at constant temperature (or a combi-
nation of both).31
There are two popular types of condensers: surface and
direct contact. Surface condensers are generally shell and
tube heat exchangers where coolant flows inside the tubes
to condense the VOCs in the gas stream flowing outside the
tubes. Contact condensers operate by spraying a cool liquid
directly into a gas stream to cool it and condense the VOCs.
In both types of condensers, the VOCs may be reused or dis-
posed. Excessive influent moisture content will impact the
process by ice formation. Removal of moisture prior to con-
densation may be required under those circumstances.
Coolants used to condense VOCs include chilled water,
brine solutions, chlorofluorocarbons (CFCs), and cryogenic
fluids.31 Chilled water is an effective coolant down to approxi-
mately 45°F. Brine solutions are effective coolants down to
approximately −30°F. CFCs are effective coolants down
to approximately −90°F. However, the production and use of
most CFCs are expected to be eliminated by the year 2000.
Cryogenic fluids, mainly liquid nitrogen or carbon dioxide,
443
Treated effuent air stream
Influent air stream Condenser Condensed VOCs
Coolant
Refrigeration unit
FIGURE 8.42  Schematic diagram of a refrigerated condenser.
can be effective down to temperatures as low as −320°F.
Figure 8.42 is a schematic diagram of a typical condensation
system.
This technology is energy intensive and may be cost pro-
hibitive under most situations. This technology should be
considered for compounds not amenable to other abatement
technologies or where chemical condensate can be sold to
recover operating costs.
Design criteria for condensation systems are as follows:
• Influent airflow rate
• Stream composition
• Required condensation temperature
• Mixture dew point
• Moisture content in influent stream
8.1.6.5  Cost Considerations
Capital and annualized costs of vapor treatment technolo-
gies are fundamental to the selection of a specific technology.
Clearly, a treatment technology that proves to be overwhelm-
ingly expensive for the amount of VOCs to be treated will be
eliminated early in an equipment selection process.
As fundamental as costs are to equipment selection, they
are also very unit specific, because of their dependence on
unique stream characteristics such as flow rate, VOCs com-
position and concentration, and operating temperature. It is
presumptuous to conclude that a cost estimate for a particular
treatment technology based on a specific set of operating con-
ditions can be applied universally to every other possible set
of operating conditions.
Another important aspect to consider during design of
a subsurface remediation system is the expected decline of
VOC concentration in the airstream during the life of the proj-
ect. A particular technology that may be very cost-effective
during the initial, high-concentrations phase may not be cost-
effective as the concentrations decline. A break-even analysis
should be performed by including the capital costs, operating
costs, and the impact on operating costs due to the decline of
VOCs concentration in the airstream to be treated. An exam-
ple of such an analysis performed for three technologies for a
specific stream is shown in Figure 8.51. The other technolo-
gies were eliminated during the initial screening process.
Energy required to operate the systems is the major
component contributing toward the annual operating costs.
Availability of a specific energy source may have a significant
444 Remediation Engineering

impact on the operating cost. For example, propane may be
1.5 times more expensive than natural gas, and electricity may
be 3.5 times more expensive than natural gas.
8.2  IN SITU AIR SPARGING
In situ air sparging is a remediation technique that has been
used successfully since about 1985, most commonly for the
remediation of VOCs dissolved in the groundwater, sorbed
to the saturated zone soils, and trapped in soil pores of the
saturated zone. This technology is often used in conjunction
with vacuum extraction systems (Figure 8.43) to remove the
stripped contaminants and has broad appeal due to its pro-
jected low costs relative to conventional approaches.
A typical air sparging system has one or more subsurface
points through which air is injected into the saturated zone. At
the technology’s inception, it was commonly perceived that
the injected air travels up through the saturated zone in the
form of air bubbles34–36; however, it is more realistic that the
air travels in the form of continuous air channels.37–39 Air bub-
bles may form in highly conductive aquifers characterized by
gravel and cobbles, but most applications are in sandy aquifers
with hydraulic conductivities much less than 10 −1 cm/s, where
formation of air channels is expected. The airflow paths will
be influenced by pressure and flow rate of the injected air and
depth of injection; however, structuring and stratification of
the saturated zone soils appear to be the predominant fac-
tors.37–39 Significant channeling may result from relatively
subtle permeability changes, and the degree of channeling
will increase as the size of the soil pore throats get smaller.
Research shows that even minor differences in permeability
due to stratification can impact sparging effectiveness.38
In addition to conventional air sparging, which is injec-
tion of air, as shown in Figure 8.43, many modifications of
the technique to overcome the geologic/hydrogeologic limita-
tions to the technology’s success will also be discussed in this
chapter.
8.2.1  Governing Phenomena
In  situ air sparging is potentially applicable when volatile
and/or aerobically biodegradable organic contaminants are
present in water-saturated zones, under relatively permeable
conditions. The in  situ air sparging process can be defined
as injection of compressed air at controlled pressures and
volumes into water-saturated soils. The contaminant mass
removal processes that occur during the operation of air
sparging systems include (1) in situ air stripping of dissolved
VOCs, (2) volatilization of trapped and adsorbed phase con-
tamination present below the water table and in the capillary
fringe, and (3) aerobic biodegradation of both dissolved and
adsorbed phase contaminants.
It was found that during in situ air sparging of petroleum
hydrocarbon sites, in the short term (weeks/months), stripping
and volatilization account for much more removal of hydro-
carbons than does biodegradation.40 Biodegradation only
becomes more significant for mass removal with long-term
system operations. This phenomenon makes sense since the
lower molecular weight compounds in a petroleum mixture
are often the most volatile and would be removed early in

Pressure Ambient air inlet Discharge

gauge Pressure
Qi
Oil-free gauge
air Vapor
compressor Pressure
gauge treat-
Pressure Blower ment
regulator Pi
Land surface
Saturated zone Vapor
monitoring probes extraction Mounded water table
well/trench during operation
Unsaturated zone
monitoring probe
Static water level

Air channels
or
bubbles
Explanation
Hi Depth of injection
Hi Pi Injection pressure
Qi Injection flow rate
Zone of
contamination

Air
sparging
point

FIGURE 8.43  Air sparging process schematic.

Sparging, Venting, and Vacuum-Enhanced Recovery
the lifecycle of the system, whereas the longer chain, higher
molecular weight compounds are less likely to volatilize
and therefore rely on biodegradation mechanisms during air
sparging.
8.2.1.1  In Situ Air Stripping
Among the three contaminant removal mechanisms discussed
earlier, in situ air stripping may be the dominant process for
some dissolved contaminants. Henry’s law constant provides
a qualitative assessment of the potential removal efficiencies
of dissolved VOCs during air sparging. Compounds such as
benzene, toluene, xylenes, ethylbenzene, TCE, and tetrachlo-
roethylene (PCE) have been considered to be very easily strip-
pable. However, a basic assumption made in analyzing the air
stripping potential during air sparging is that Henry’s law
applies to the volatile contaminants and that all the contami-
nated water is in close communication with the injected air.
In-depth evaluation of these assumptions exposes the short-
comings and complexities of interphase mass transfer during
air sparging.
First of all, Henry’s law is valid only when partition-
ing of the dissolved contaminant mass has reached equi-
librium at the air–water interface. However, the residence
time of air traveling in discrete channels may be too short
to achieve the equilibrium due to the high air velocities
and short travel paths. Another issue is the validity of the
assumption that the contaminant concentration at the air–
water interface is the same as in the bulk water mass. Due
to the removal of contaminants in the immediate vicinity
of the air channels, it is safe to assume that the contami-
nant concentration is going to be lower around and near air
channels than outside the channels. To replenish the mass
lost from the water around the air channel, mass transfer by
diffusion and convection must occur from water away from
the air channel.
180
160
140
Molecular weight (g/mol)
120
100
1,4-Dioxane
80
TBA
60
Acetone
40
1e–6 1e–5
FIGURE 8.44  Two rate-limit model showing lines of equal spargeability based on both the molecular weight and Henry’s Law Coefficient.
445
Practitioners relying solely on the Henry’s law constant as
an indicator of the relative ease of contaminant removal may
be disappointed by lack of results. Removal of COCs through
stripping is best described by a two-rate-limit model. The first
rate limit describes the rate of VOC migration across the stag-
nant water zone toward the air channel; determined by com-
pounds specific aqueous phase diffusion constants and the
distance from the air channel. The second rate limit describes
the rate of VOC transfer across the aquifer/air channel inter-
face, determined by the concentration difference between the
aqueous phase and air channel, and the Henry’s law coeffi-
cient. The two most influential chemical characteristics are
the molecular weight and Henry’s law coefficient. Lower
molecular weight favors migration toward the air channel and
higher Henry’s Law coefficients favor transfer from aqueous
phase to gaseous phase, as shown in Figure 8.44. Early stud-
ies indicate a high likelihood of success when the Henry’s law
constant is higher than 10 −5 atm m3/mol.41 As shown in Figure
8.44, the Henry’s law constant for compounds like acetone
and methyl ethyl ketone is higher than 10 −5, but air sparg-
ing has not been successful applied to these compounds. Case
studies for PCE and TCE removal via air sparging are well
documented; however, MTBE has been a challenge to remove
from groundwater via stripping.42 This concept can also be
applied to SVE as contaminants move from soil pore water to
the gas/water interface and change state.
It is likely that the density of air channels plays a sig-
nificant role in mass transfer efficiencies by minimizing the
distances required for a contaminant molecule to migrate
to the air channel. In addition, the density of air channels
will also influence the interfacial surface area available for
mass transfer. The literature suggests that the air channels
formed during air sparging mimic a “viscous fingering”
effect, and that two types of air channels are formed: large-
scale channels and pore-scale channels.43 The formation of
Lines of equal spargeability
PCE
Inc
rea
si ng CCl4
effe
ctiv Freon
ene
ss
TCE 1,1,1-TCA
O-Xylene
Ethylbenzene
1,2-DCA
1,1-DCA
cis-1,2-DCE 1,1-DCE
Toluene
MTBE
THF Benzene
MEK
Vinyl chloride
Chloroethane
1e–4 1e–3 1e–2 1e–1 1e+0
Henry’s law coefficient (atm m3/mol)
446
both types of channels enhances the channel density and the
available interfacial surface area.
It has been proposed that in situ air sparging also helps to
increase the rate of dissolution of the sorbed phase contami-
nation, and eventual stripping below the water table. This is
due to the enhanced dissolution caused by increased mixing
and the higher concentration gradient between the sorbed and
dissolved phases under sparging conditions.
8.2.1.2  Direct Volatilization
The primary mass removal mechanism for VOCs present in
the saturated zone during pump and treat operations is resolu-
bilization into the aqueous phase and the eventual removal
with the extracted groundwater. During in situ air sparging,
direct volatilization of the sorbed and trapped contaminants
is enhanced in the zones where airflow takes place. Direct
volatilization of any compound is governed by its vapor
pressure, and most VOCs are easily removed through vola-
tilization. Figure 8.43 is a schematic of an air channel mov-
ing through an aquifer containing sorbed or trapped (NAPL)
contamination. In the regions where the soil is predominantly
air-saturated or the air channel is next to the zone of trapped
contaminants, the process is similar to SVE or bioventing,
albeit in a microscopic scale.
Where significant levels of residual contamination of
VOCs or NAPLs are present in the saturated zone, direct
volatilization into the vapor phase may become the dominant
mechanism for mass removal in areas where air is flowing.
This may explain the significant increase in VOC concentra-
tions typically observed in the SVE effluents at many sites.40
8.2.1.3 Biodegradation
In most natural situations, aerobic biodegradation of biode-
gradable compounds in the saturated zone is rate limited by
the availability of oxygen. Biodegradability of any compound
under aerobic conditions is dependent on its chemical struc-
ture and environmental parameters such as pH and tempera-
ture. Some VOCs are considered to be easily biodegradable
TABLE 8.7
Examples of Contaminant Applicability for In Situ Air Sparging
Contaminant Molecular Weight
Benzene Low (MW = 78.11)
Toluene Low (MW = 92.14)
Xylenes Low (MW = 106.17)
Ethylbenzene Low (MW = 106.17)
TCE Moderate (MW = 131.4)
PCE Moderate (MW = 165.82)
Gasoline constituents Low
Fuel oil constituents Moderate/high
Note: MW, molecular weight (g/mol); H, Henry’s law constant (atm · m3/mol); VP, vapor pressure (mm Hg) at 20°C; t1/2, half-life
during aerobic biodegradation, hours.
a It should be noted that the half-lives can be very dependent on the site-specific subsurface environmental conditions.
Remediation Engineering
under aerobic conditions (e.g., benzene, toluene, acetone,
vinyl chloride) and some are not (e.g., TCE and PCE).
Typical dissolved oxygen (DO) concentrations in uncon-
taminated groundwater are less than 4.0 mg/L. Under anaer-
obic conditions induced by the natural degradation of the
contaminants, DO concentrations in groundwater are often
less than 0.5 mg/L. DO levels can be raised by air sparging
up to 6–10 mg/L under equilibrium conditions.34,40,44 This
increase in the DO levels will contribute to enhanced rates of
aerobic biodegradation in the saturated zone. This method of
introducing oxygen for enhanced biodegradation rates is one
of the inherent advantages of in  situ air sparging. However,
the oxygen transfer into the bulk water is a diffusion-limited
process. The diffusion path lengths for transport of oxygen
through groundwater are defined by the distances between air
channels. Where channel spacing is large, diffusion alone is
not sufficient to transport adequate oxygen into all areas of the
aquifer for enhanced aerobic biodegradation. The pore-scale
channels formed and the induced mixing during air sparging
enhances the rate of oxygen transfer.43
8.2.2  Applicability
8.2.2.1  Examples of Contaminant Applicability
Contaminant type is a major variable affecting air sparging
design and contaminant mass removal rate. Based on the
discussion in the previous section, Table 8.7 describes the
applicability of air sparging for a few selected contaminants
based on the properties of strippability, volatility, and aerobic
biodegradability. In order for air sparging to be effective, the
VOCs must transfer from the groundwater into the injected
air, and oxygen present in the injected air must transfer into
the groundwater to stimulate biodegradation.
The criterion for defining contaminant strippability
is based on the Henry’s law constant being greater than
1  ×  10 −4  atm m3/mol, with consideration of the molecular
weight (Figure  8.45). In general, compounds with a vapor
pressure greater than 0.5–1.0 mm Hg can be volatilized easily;
Strippability Volatility Aerobic Biodegradabilitya
High (H = 5.5 × 10−3) High (VP = 95.2) High (t1/2 = 240)
High (H = 6.6 × 10−3) High (VP = 28.4) High (t1/2 = 168)
High (H = 5.1 × 10−3) High (VP = 6.6) High (t1/2 = 336)
High (H = 8.7 × 10−3) High (VP = 9.5) High (t1/2 = 144)
High (H = 10.0 × 10−3) High (VP = 60) Very low (t1/2 = 7704)
High (H = 8.3 × 10−3) High (VP = 14.3) Very low (t1/2 = 8640)
High High High
Low Very low Moderate
Sparging, Venting, and Vacuum-Enhanced Recovery
100
80 Stripping and volatilization
Percent removal
60
40
Biodegradation
20
0
Gasoline Mineral JP-4 Diesel
spriits
Contaminant (increasing density)
FIGURE 8.45  Qualitative presentation of potential air sparging
mass removal for petroleum compounds.
however, the degree of volatilization is also limited by the
flow rate of air. The half-lives presented in Table 8.7 are esti-
mates in groundwater under natural conditions without any
enhancements to improve the rate of degradation.
Many of the constituents present in heavier petroleum
products such as no. 6 fuel oil will not be amenable to either
stripping or volatilization (Figure 8.45). Hence, the primary
mode of remediation, if successful, will be due to aerobic bio-
degradation. Required air injection rates under such condi-
tions will be lower and influenced only by the requirement to
introduce sufficient oxygen into the saturated zone.
Figure 8.45 qualitatively describes different mass removal
phenomena in a simplified version under optimum field con-
ditions. The amount of mass removed by stripping and vola-
tilization have been grouped together, due to the difficulty
in separating them in a meaningful manner. However, the
emphasis should be placed on total mass removal, particularly
of mobile volatile constituents, and closure of the site regard-
less of the mass transfer mechanisms.
8.2.2.2  Geologic Considerations
Successful implementation of in  situ air sparging is greatly
influenced by the ability to achieve significant air distribution
within the target zone. Good vertical pneumatic conductiv-
ity is essential to avoid bypassing or channeling of injected
air horizontally, away from the sparge point. It is not an easy
task to evaluate the pneumatic conductivities in the horizontal
and vertical direction for every site considered for in situ air
sparging.
Geologic characteristics of a site are very important when
considering the applicability of in situ air sparging. The most
important geologic characteristic is stratigraphic homogeneity
or heterogeneity. Presence of low-permeability layers under
stratified geologic conditions will impede the vertical pas-
sage of injected air. Laboratory-scale studies38 illustrate the
impact of geologic characteristics on air channel distribution.
447
Grade Grade
Impervious Highly permeable
layer layer
Contaminants Contaminants
No. 6
FIGURE 8.46  Potential situations for the enlargement of a con-
fuel oil
taminant plume during air sparging.
Under  laboratory conditions, injected air may accumulate
below the low-permeability layers and travel in a horizontal
direction, thus potentially causing fugitive migration of con-
taminant-impacted vapors to uncontaminated areas (Figure
8.45). High permeability layers may also cause the air to
preferentially travel laterally, again potentially causing an
enlargement of the plume (Figure 8.46). Horizontal migration
of injected air limits the volume of soils that can be treated
by direct volatilization due to the inability to capture the
stripped contaminants. Horizontal migration can also cause
safety hazards if hydrocarbon vapors migrate into confined
spaces such as basements and utilities. Hence, homogeneous
geologic conditions are important for the success and safety
of in situ air sparging.
Both vertical permeability and the ratio of vertical to
horizontal permeability decrease with decreasing average
particle size of the sediments in the saturated zone. The
reduction of vertical permeability is directly proportional
to the effective porosity and average grain size of the sedi-
ments.45 Hence, based on the empirical information available,
it is recommended that the application of conventional in situ
air sparging be limited to saturated zone conditions where the
hydraulic conductivities are greater than 10 −3 cm/s.37,46
8.2.3  Description of the Process
8.2.3.1  Air Injection into Water-Saturated Soils
The ability to predict the performance of air sparging systems
is limited by the current understanding of airflow in the water-
saturated zone and limited performance data. There were two
schools of thought in the literature describing this phenom-
enon. The first and the widely accepted one describes that
the injected air travels in the vertical direction in the form of
discreet air channels. The second school of thought describes
injected air travels in the form of air bubbles. Airflow mecha-
nisms cannot be directly observed in the field. However, con-
clusions can be reached by circumstantial evidence collected
at various sites and laboratory-scale visualization studies.
Sandbox model studies performed38,39 tend to favor the
“air channels” concept over the “air bubbles” concept.
448
In  laboratory studies simulating sandy aquifers (grain sizes
of 0.075–2 mm), stable air channels were established in the
medium at low injection rates. Under laboratory conditions
simulating coarse gravels (grain sizes of 2 mm or larger), the
injected air rose in the form of bubbles. At high air injection
rates in sandy, shallow, water-table aquifers, the possibility for
fluidization (loss of soil cohesion) around the point of injec-
tion exists37,39 and thus the loss of control of the injected air
may occur.
8.2.3.2  Mounding of Water Table
When air is injected into the saturated zone, groundwater
must necessarily be displaced. The displacement of ground-
water is a pressure response that has both a vertical and lat-
eral component. The vertical component will cause a local
rise in the water table, sometimes called water table mound-
ing. Mounding has been used by some as an indicator of
the “radius-of-influence” of the sparge well during the early
stages of development of this technology.34,35,44,47,48 The mag-
nitude of mounding depends on site conditions (e.g., aquifer
hydraulic conductivity, depth of sparge well below the water
table, air injection rate) and the location of the observation
wells relative to the sparge well. Mounding can vary from a
negligible amount to several feet in magnitude.
Simulations of the flow of air and water around an air
sparging well were performed with a multiphase, multi-
component simulator (TETRAD) originally developed for
the study of problems encountered during exploitation of
petroleum and geothermal resources.49,50 The simulations
were performed by defining two primary phases of transient
behavior that lead to a steady-state flow pattern (Figures 8.47
and 8.48). The first phase is characterized by an expansion
in the region of airflow (Figure 8.48). During this phase, the
rate of air injection into the saturated zone exceeds the rate
of airflow out of the saturated zone into the vadose zone. It
is during this transient expansion phase that groundwater
mounding first develops and reaches its highest level, where
it extends from near the injection well to beyond the region
of airflow in the saturated zone. When injected air breaks
Air sparging well
Ground level
Early stages Later stages
of the mound of the mound
Water level
Later stages of the
expansion phase
Early stages of the
expansion phase
Air channel
FIGURE 8.47  The first transient behavior after initiation of air
injection into the saturated zone.
Remediation Engineering
Air sparging well
Ground level
Mound disappears The mound at the beginning
at steady state of the collapse phase
Water level
Beginning of
collapse phase
Extent of
steady state phase
Air channel
FIGURE 8.48  The second transient behavior before reaching
steady state during air sparging.
through to the vadose zone, the region of airflow in the satu-
rated zone begins to collapse or shrink. During this second
transient phase of behavior, the preferred pathways of higher
air permeability from the point of injection to the vadose
zone are established. The air distribution zone shrinks until
the rate of air leakage to the vadose zone equals the rate of
air injection. During this collapse phase, mounding near
the sparge well dissipates. When steady-state conditions are
reached, little or no mounding exists. This behavioral pattern
has also been observed in the field37,48,50 (Figure 8.49). This
behavior reflects the building and decay of the groundwater
mound at a sparging location.
The transience of groundwater mounding at most sites has
important implications for the risk of lateral movement of the
contaminant plume. Because the water table returns close to
its presparging position during continuous air injection, the
driving force for lateral movement of groundwater caused by
air injection becomes very small. Once the well is at a steady-
state condition (water table comes to equilibrium), there is no
additional, outward radial movement of water. From a math-
ematical perspective, consider a single air sparge well with
a 10 ft radius of influence in a sand aquifer and assume 10%
Height of the mound (in.)
Time of sparging (h)
FIGURE 8.49  Appearance and disappearance of groundwater
mound during in situ air sparging.
Sparging, Venting, and Vacuum-Enhanced Recovery
of the aquifer pore space is displaced by air channels. The
actual radial distance groundwater is required to move can be
calculated by
V = pr 2hn (8.30)
where
V is the volume of water in the aquifer
r is the air sparge well radius of influence
h is the hydrostatic head above air sparge well screen =
hydro
n is the soil porosity
1.10V
rnew = (8.31)
phn
where rnew is the radius required to accommodate new volume
of air/water.
Substituting Equation 8.30 and reducing terms, we get
rnew = 1.10r 2 (8.32)
The final radius (rnew) is 10.5 ft, meaning that the radial move-
ment of groundwater attributable to the air sparge well is only
6 in., giving an idea of the scale of the risk of “spreading” of
the plume during air sparging.
An important aspect of groundwater mounding is that it
is not a direct indicator of the physical presence of air in the
saturated zone. Water table mounding at a given place and
time may or may not be associated with the movement of air
in the saturated zone at the same location. Some mounding
will occur beyond the region of airflow in the saturated zone.
Additionally, a transient pressure increase without water table
mounding commonly occurs beyond the limits of airflow,
especially where airflow is partially confined. Because of its
transient nature and the fact that the water table is displaced
ahead of injected air, water table mounding can be a mislead-
ing and overly optimistic indicator of the distribution of air-
flow within the saturated zone.
8.2.3.3  Distribution of Airflow Pathways
It is often envisioned that airflow pathways developed during
air sparging form an inverted cone with the point of injec-
tion being the apex. This would be true only if soils were
perfectly homogeneous or comprised of coarse-grained sedi-
ments, and the injected airflow rate was low. During labo-
ratory experiments using homogeneous media with uniform
grain sizes, symmetrical airflow patterns about the vertical
axis were observed.38 However, media simulating mesoscale
heterogeneities yielded nonsymmetrical airflow patterns.38
The asymmetry apparently resulted from minor variations
in the permeability and capillary air entry resistance, which
resulted from pore-scale heterogeneity. Hence, under natural
conditions, it is realistic to expect that symmetric air distribu-
tion will never occur.
These same experiments also indicated that the channel
density and thus the interfacial surface area increased with
449
increased airflow rates, since higher volumes of air occupy
an increased number of air channels. Assuming that the air
channels are cylindrical in shape and that the number of
channels and air velocity in the channel remains the same
even for a change in airflow rate, the interfacial surface area
will be increased by a ratio (Q final/Qinitial)0.5, where Q is the
airflow rate.
Air distribution near the air sparge well is based on the
pressure gradient from the injection of air, driving air move-
ment laterally. As the pressure gradient dissipates, buoyancy
effects take over driving the air upward only. Further lat-
eral movement is driven solely by the geology and the path
of least resistance to the vadose zone. At some height above
the air sparge well screen, additional increase in ROI as the
air moves upward should not be expected. It is reported in
some literature that, at low sparge pressures, air travels 1–2 ft
horizontally for every foot of vertical travel.34 However, it
should be noted that this correlation was not widely observed.
It was also reported that as the sparge pressure is increased,
the degree of horizontal travel increases.35,41,49 Field observa-
tions have indicated that airflow channels extend 10–40 ft
away from the air injection point, independent of flow rate
and depth of sparge point.40,45,49
8.2.3.4  Groundwater Mixing
Mixing of groundwater during air sparing is an important
mechanism to overcome the diffusional limitation for con-
taminant mass transfer and provide adequate oxygen transport
into the aquifer. Groundwater mixing during air sparging may
significantly reduce the diffusion limitation for mass transfer
without generating any changes in the bulk groundwater flow.
It has been shown that non-steady-state mixing mechanisms
induced in opposite directions at different times as a result
of pulsed sparging operations will enhance the mass removal
efficiencies.41,48
There are many possible mechanisms for groundwater
mixing during air sparging.41 Several possible mechanisms
are as follows:
• Physical displacement by injected air
• Capillary interaction of air and water
• Frictional drag by flowing air
• Water flow in response to evaporative loss
• Thermal convection
• Migration of fines
Groundwater is physically displaced by air as it moves
through the saturated zone soil during sparging. This pro-
cess occurs during nonsteady-state airflow conditions, where
the percentage of air saturation changes with time until
the formation of spatially fixed air channels. The amount
of mixing due to this physical displacement is dependent
upon the amount of groundwater displaced and the duration
of nonsteady-state flow conditions. The rate of water dis-
placement is permeability limited and, therefore, the dura-
tion of these effects is generally greater in low-permeability
soils. The process will take place over both microscopic
450
distances  (inches) and site-scale distances. Pulsed sparg-
ing will frequently create nonsteady-state conditions and
enhance groundwater mixing.41
8.2.4  System Design Parameters
In the absence of readily available and reliable models for the
in situ air sparging process, empirical approaches are used in
the system design process. The parameters that are of signifi-
cant importance in designing an in situ air sparging system
are listed:
• Air distribution (zone of influence)
• Depth of air injection
• Air injection pressure and flow rate
• Injection mode (pulsing or continuous)
• Injection well construction
• Contaminant type and distribution
8.2.4.1  Air Distribution (Zone of Influence)
During the design of air sparging systems, it may be very dif-
ficult to define a radius of influence in the same manner it
is used in pump and treat and/or soil venting systems. Due
to the asymmetric nature of the air channel distribution and
the variability in the density of channels, it is safer to assume
a “zone of influence” rather than a radius of influence37,39,51
(Figure 8.50).
It becomes necessary to estimate the “zone of influence”
of an air sparging point, similar to any other subsurface
(a)
Subtle geologic
changes
(c)
FIGURE 8.50  Zones of influence under various operating conditions. (a) Homogeneous geology, low airflow, (b) homogeneous geology,
moderate to high airflow, (c) heterogeneous geology, low airflow, and (d) heterogeneous geology, moderate airflow.
Remediation Engineering
remediation technique, to design a full-scale air sparging sys-
tem consisting of multiple points. This estimation becomes
an important parameter for the design engineer to determine
the number of required sparge points. The zone of influence
should be limited to describing an approximate indication of
the average distance traveled by air channels from the sparge
point in the radial directions, under controlled conditions.
As noted earlier during a numerical simulation study on air
sparging,49 three phases of behavior were predicted following
initiation of air injection (Figures 8.47 and 8.48). These are
(1) an expansion phase in which the vertical and lateral limits
of airflow grow in a transient manner, (2) a second transient
period of reduction in the lateral limits (collapse phase), and
(3) a steady-state phase, during which the system remains
static as long as injection parameters do not change. The zone
of influence of air sparging was found to reach a roughly coni-
cal shape during the steady-state phase.
Based on the inverted cone airflow distribution model,
many air sparging system designs are performed based on the
zone of influence measured during a field design test. When
a hot spot or source area is under consideration for cleanup, it
is prudent to design the air sparging system in a grid fashion
(Figure 8.51). The grid should be designed with overlapping
zones of influence that provide complete coverage of the area
under consideration for remediation. If an air sparging curtain
is designed to contain the migration of dissolved contami-
nants, the curtain should be designed with overlapping zones
of influence in a direction perpendicular to the direction of
groundwater flow.
(b)
Subtle geologic
changes
(d)
Sparging, Venting, and Vacuum-Enhanced Recovery 451

Direction of These parameters should be measured in the moni-

groundwater flow
Source area
Contaminant
plume
Air sparging points
with overlapping zones
of influence
FIGURE 8.51  Air sparging point locations in a source area and in
a curtain configuration.
A properly designed pilot test can provide valuable infor-
mation. The limitations of time and money often restrict field
evaluations to short-duration single-well tests. Potential mea-
suring techniques (Figure 8.52) of the zone of influence have
evolved with this technology:
• Measurement of the lateral extent of groundwater
mounding in monitoring wells34,35,46,48
This was the earliest technique used during the very
early days of implementation of this technology.
However, it did not take long to realize that the lat-
eral extent of the mound is only a reflection of the
amount of water displaced and does not necessarily
correspond to the zone of air distribution.
• Measurement of the increase in DO levels and
redox potentials in comparison to presparging
conditions35,36,47,52–55
toring well itself by using field probes. Oxygen
transfer could take place during sample collection
and handling and may bias the results of the analy-
sis. This concept lost its value when it was realized
that the injected air travels in the form of channels
rather than bubbles. Increases in DO levels in the
bulk water due to diffusion-limited transport of
oxygen will be noticeable only during a long-term
pilot study. In most cases, the increased DO levels
observed during short-duration pilot tests were due
to the air channels directly entering the monitoring
wells and not due to overall changes in DO levels
in the aquifer and therefore may also depend on the
density of both air channels in the subsurface and the
monitoring well network.
• Measurement of soil gas pressures
This technique involves the measurement of any
increase in the soil gas pressure above the water table
due to the escape of the injected air into the vadose
zone. The escaped air will quickly equilibrate in the
vadose zone and may spread over a larger area than
the zone of air distribution in the vadose zone. As a
result, during the combined operation of soil vent-
ing and air sparging, measurement of this parameter
may be totally misleading.
• Increase in head space pressure within sealed satu-
rated zone monitoring probes (piezometers) that are
perforated below the water table only
This technique is widely used and currently con-
sidered to be the most reliable in terms of detecting
the presence of air pathways at a specific distance
in the saturated zone. When an air channel enters a
monitoring probe via the submerged screen, the head

Monitoring well points

MW-C MW-F
MW-A MW-B MW-D MW-E Land surface

∆h2
∆h3 ∆h4 Static water level
∆h1
∆p3 ∆p4
∆p1 ∆h = 0 ∆h = 0
∆DO4
∆DO1 ∆p = 0 ∆p = 0
∆DO3
∆DO = 0 ∆DO = 0
Air channels
∆p2
∆DO2
Explanation
∆h Change in water-level
elevation
∆p Change in pressure
Air
sparging point ∆DO Change in DO levels

FIGURE 8.52  Air sparging test measurements.

452
space pressure could increase up to the hydrostatic
pressure at the point of entry. However, the tech-
nique depends on the density of air channels being
enough to ensure intersection with a monitoring well
and actual distribution of air channels may extend
beyond the furthest monitoring probe.
• The use and detection of insoluble tracer gases,
such as helium and sulfur hexafluoride37,51,55
Initial monitoring of the tracer gas in the vadose
zone is typically performed while the SVE system is
off. The potential to balance the mass of the injected
tracer and the amount of recovered tracer raises the
level of confidence in the estimation of the capture
rate of injected air. The use of sulfur hexafluoride
as a tracer gas has the advantage due to its solubility
being similar to that of oxygen. Hence, the detection
of sulfur hexafluoride in bulk water will be an indi-
cator for the diffusional transport of oxygen. This
technique will also provide information on vapor
flow paths and vapor recovery efficiencies during air
sparging.
• Measurement of the electrical resistivity changes in
the target zone of influence as a result of the changes
in water saturation due to the injection of air (elec-
trical resistivity tomography [ERT] method)56
Tomography is a method of compiling large amounts
of 1D information in such a way as to produce a 3D
image (CAT scans, MRIs, and holograms make use
of tomography). ERT is a process in which a 3D
depiction of air saturation within the saturated zone
is generated by measuring the electrical resistance of
the soil between electrodes placed at various loca-
tions on wells during installation. Other tomographic
methods include vertical induction profiling (VIP)
and geophysical diffraction tomography (GDT).
VIP is similar to ERT, except that ERT uses
a direct current (DC) potential while VIP uses a
500  Hz alternating current (AC). The use of AC
makes it possible to detect electrical field strength by
induction, so existing PVC wells can be used without
the requirement for subsurface electrode installation.
GDT is another 3D subsurface imaging technology
that could be used to characterize air movement
through the subsurface during air sparging. GDT is
a high-resolution acoustic technique that provides
quantitative subsurface imaging by measuring varia-
tions in acoustic velocity between various locations
on the ground surface and depths in monitoring
wells.
ERT may be the most reliable method among all
the techniques discussed in this section. The high
drilling costs, associated with installing large num-
bers of electrodes in the subsurface, preclude it from
being used widely.
• Measurement of moisture content changes within
the target zone of influence using time-domain
reflectometry (TDR) technique
Remediation Engineering
TDR is a well-established and accurate means to
measure the moisture content of soils and has been
widely used in the agricultural industry. When
injected air travels within the zone of influence, mois-
ture content will decrease due to the displacement of
water. TDR data, collected from probes placed in the
aquifer, can accurately reflect the changes in mois-
ture content.
• Neutron probe technique to measure the changes in
water saturation57
This technique utilizes a neutron probe to measure
changes in water saturation (thus air saturation)
below the water table during air sparging. The neu-
tron probe detects the hydrogen in water and thus
translates into a “water” saturation value. The water
saturation values can be converted to air saturation
values. The neutron probe can also detect the hydro-
gen in petroleum hydrocarbons and hence can bias
the “fluid” saturation values.
• The actual reduction in contaminant levels due to
sparging
This evaluation gives an indication of the extent of
the zone of influence in terms of contaminant mass
removal, but the test has to be run long enough to
collect reliable data.
Since cost and budgetary limitations influence how a field
design test is performed, availability of resources will deter-
mine the type of method used. The most reliable method is
the one that measures the changes in electrical resistivity due
to changes in air/water saturation. The most cost-effective
method is the one that determines the head space pressure
within the saturated zone probes.
8.2.4.2  Depth of Air Injection
Among all the design parameters, the depth of air injection
may be the easiest to determine, since the choice is very much
influenced by the contaminant distribution. It is prudent to
choose the depth of injection at least a few feet deeper than the
“deepest known point” of contamination. However, in real-
ity, the depth of injection is often influenced by soil struc-
turing and extent of stratigraphic layering, since injection
below low-permeability zones should be avoided. The major-
ity of industry experience is based on injection depths of less
than 30–60 ft below the water table, although the author has
knowledge of applications at depths of 90 ft.34,40,55 The depth
of injection will influence the injection pressure, flow rate, and
materials of construction where deep air sparging is required.
8.2.4.3  Air Injection Pressure and Flow Rate
Injected air will penetrate the aquifer only when the air pres-
sure exceeds the sum of the water column’s hydrostatic pres-
sure and the threshold capillary pressure, or the air entry
pressure. The air entry pressure is equal to the minimum
capillary entry resistance for the air to flow into the porous
medium. Capillary entry resistance is inversely proportional
to the average diameter of the grains and porosity.45,49
Sparging, Venting, and Vacuum-Enhanced Recovery
The injection pressure necessary to initiate in  situ air
sparging must be able to overcome the following:
1. The hydrostatic pressure of the overlying water col-
umn at the point of injection.
2. The capillary entry resistance to displace the pore
water; this depends on the type of sediments in the
subsurface.
The capillary pressure can be quantitatively described,49
under idealized conditions, by the following equation:
2s
Pc = (8.33)
r ence than under the steady-state conditions; therefore, pulsing
where
Pc is the capillary pressure
s is the surface tension between air and water
r is the mean radius of curvature of the interface between
fluids
This equation reveals that as r decreases, the capillary
pressure increases. Generally, r will decrease as grain size
decreases. Therefore, the required pressure to overcome cap-
illary resistance increases with decreasing sediment size.
The pressure of injection (Pi) in feet of water could be
defined as
Pi = Hi + Pa + Pd (8.34)
where
Hi is the saturated zone thickness above the sparge point
(feet of water)
Pa is the air entry pressure of formation (feet of water)
Pd is the air entry pressure for the screen and packing
The air entry pressure for a formation is heavily dependent
on the type of geology. In reality, the air entry pressure will
be higher for fine-grained (1–10 ft of water column pressure)
than coarse-grained media (1–10 in. of water column pres-
sure). When Hi is significantly greater than Pa and Pd com-
bined, it is likely that air will enter the formation primarily
near the top of the injection screen.
The typical values of injected airflow rates reported in
the literature range from 1 to 15 cfm per injection well.37,46
Injection airflow determinations are also influenced by the
ability to recover the stripped contaminant vapors through
a vapor extraction system, thus containing the injected air
within a controlled air distribution zone.
8.2.4.4  Injection Mode (Pulsing and Continuous)
Direct and speculative information available in the literature
indicates that the presence of air channels can impede but does
not stop the flow of water across the sparging zone of influ-
ence. The natural groundwater flow through a sparged zone
of an aquifer will be slowed and diverted by the air channels
due to changes in water saturation and thus relative hydraulic
453
permeability. Whether this effect is measurable at most field
sites is questionable. This potentially negative factor could be
overcome by pulsing the air injection and thus minimizing
the decrease in relative permeability due to changes in water
saturation.
An additional benefit of pulsing is increased mixing of
groundwater resulting from air channels formation and col-
lapse during each pulse cycle. This should also help to reduce
the diffusional rate limitation for the transport of contami-
nants in the bulk water phase toward the air channels, due
to the cyclical displacement of water during pulsed air injec-
tion. As noted earlier, the expansion phase during air sparging
(Figures 4.5 and 4.6) appears to have a greater zone of influ-
may improve the efficiency of air sparging by creating cycli-
cal expansion and collapse of the zone of influence.
Pulsing has also been shown to benefit the removal of
LNAPL, such as would be encountered at hydrocarbon-
impacted sites.58 Pulse cycles for any given well are typically
on the order of an hour on and a few hours off, depending on
the number of zones included in the operational cycle. This
means that the water table mounding and dissipation could
occur multiple times a day. Where LNAPL or highly satu-
rated soil is present, the movement of the water table through
that zone brings oxygen in to the zone encouraging biodegra-
dation. Potential vertical “spreading” of NAPL upward may
also be a benefit, as the mass becomes more accessible to SVE
processes in the vadose zone.
While these are described as benefits, air sparging is not
advised for heavily impacted sites, where multiple feet of
LNAPL can be measured. Generally speaking, multiphase
extraction or SVE can be used to remove the majority of
volatile compounds from the vadose zone and minimize the
thickness of LNAPL at a site prior to the air sparging sys-
tem is initiated and used to enhance removal of the remaining
inches or feet of measurable NAPL, the residual saturation,
and dissolved-phase groundwater impacts.
Pulsing of air sparge wells is also more cost-effective than
a continuous operational mode. Consider a site where 20 air
sparge wells are required to cover the area of impacts. The
well spacing is set based on a flow rate required to achieve the
radius of influence, and the design well pressure set based on
the requirement to achieve that flow rate. If all wells are oper-
ated continuously at 5 cfm, the total system must be designed
to achieve 100 cfm. If the site is split in to 5 zones and only 4
wells are operated at a given time, requiring only 20 cfm. This
results in not only a reduction in capital cost for the purchase
of the compressor, but a larger cost reduction is achieved
through the energy savings due to the reduction in horse-
power. Other reductions can be realized, such as a smaller
SVE system required to collect and treat the contaminated
vapor stream, and a smaller building (or container) footprint
required for the treatment system.
8.2.4.5  Injection Well Construction
Injection wells must be designed to accomplish the desired
distribution of airflow in the formation. Conventional design
454 Remediation Engineering

Casing Grade
Cement

Grout

Grout

Bentonite

Bentonite plug Sand Sparge screen (1–2 ft)

Grout

Bentonite
Filter Sand
pack
(a) (b)

Grade

(c)

FIGURE 8.53  (a–c) Schematic showing conventional design of an air sparging point for shallower applications.

of an air sparging well is shown in Figure 8.53. Schedule 40
or 80 PVC (polyvinyl chloride) piping and screens in various
diameters can be used for the well construction. In both con-
figurations, the sparge point should be installed by drilling a
well to ensure an adequate seal to prevent short-circuiting of
the injected air up the well bore.
Injection well diameters are relatively small diameter due
to the relative ease of injecting air (as opposed to water) and
are usually 1–2 in. However, as the diameter of the well is
reduced, the pressure drop due to the flow-through piping
increases and may become significant, especially at deeper
depths.
The well screen location and length should be chosen
to maximize the flow of injected air through the zone of
contamination. At typical injection flow rates, most of the
air will escape through the top few inches of the screen.
A 10-slot PVC screen is normally used for air sparging
applications.
8.2.4.6  Contaminant Type and Distribution
Volatile and strippable compounds will be most amenable
to air sparging, though it is anticipated that nonvolatile, but
aerobically biodegradable compounds can also be addressed
by this technique. There is no limit on the dissolved concen-
trations of contaminants treatable by air sparging. For air
sparging to be effective, the air saturation percentage and the
radius and density of air channels are important factors for
mass transfer efficiencies of both contaminants and oxygen.
The rates of stripping and biodegradation are both limited by
diffusion through water. It is not possible to optimize them
separately.55
8.2.5  Pilot Testing
At times, small full-scale air sparging systems are installed
without site-specific pilot study data, relying prior experience
or rules of thumb to design the well spacing and placement
Sparging, Venting, and Vacuum-Enhanced Recovery 455

(such as an assumed vertical to horizontal ratio for develop-

ment of a radius of influence). A pilot test is always recom- TABLE 8.8
mended for sites with questionable geology or contaminants Evaluation of Site-Specific Parameters as a Preliminary
to reduce the risk of poor full-scale performance. The pilot Screening Tool
study could be most appropriately defined as a field design
Favorable
study, since the primary objective is to obtain site-specific Condition Conditions Impact
design information. Also, because vapor extraction is usu-
Saturated zone soil 10 cm/s
−3 Applicability, flow rate
ally a complimentary technology to in  situ air sparging,
permeability vs. pressure mass
simultaneous pilot testing of the integrated system is highly
(horizontal) removal efficiencies vs.
recommended. transport rate
Short-term pilot tests play a key role in the selection and Geologic stratification Sandy, gravelly Applicability, air
design of in situ air sparging systems. Most conventional pilot and anisotropy soils, homogenous distribution
tests are less than 24–48 h in duration and consist of monitor- Aquifer type Unconfined Recovery of injected air
ing changes in several of the following parameters: Depth of contamination Less than 40–50 ft Sparging depth (injection
below the water table pressure)
• Pressure buildup in sealed piezometers screened Type of contaminant High volatility, high Applicability—volatility/
below the water table strippability, high strippability/
• DO levels aerobic biodegradability
• Water levels in wells biodegradability
• Soil gas pressures Extent of Zero to minimal Applicability and mass
contamination separate phase removal efficiency
• Contaminant concentrations in soil gas
contamination (multiple sparge points)
• The presence and capture of tracer gases
Soil conditions above More than 5 ft of Ability to capture the
the water table vadose zone, stripped contamination
These parameters are assumed to be indicators of air sparging permeable soils by vapor extraction
feasibility and performance and are also used in the design Vapor flow paths
of full-scale systems. It is suggested that collection and com-
parison of as many parameters as possible will provide valu-
able insight on site-specific applicability of air sparging as a
remediation technique. soils. Care should be exercised not to apply overly
It is very important to perform a preliminary evaluation of high pressure that could fracture the formation.
the geologic and hydrogeologic conditions for the applicabil- • Injection flow rate: The injection flow rate should
ity of in situ air sparging prior to the pilot study. In addition, a be evaluated to achieve a targeted radius of influ-
thorough examination of the degree and extent of contamina- ence. The higher the conductivity of the formation,
tion should be performed. the higher the required flow rate to achieve a similar
Evaluating the site-specific parameters listed in Table 8.8 radius of influence. Typical injection flow rates are in
prior to designing a pilot test will enhance the quality of data the range of 1–15 cfm per injection point, depending
that would be collected. A typical equipment setup used for on the type of geology.
an air sparging pilot test is shown in Figure 8.43. The data that • Mass removal efficiency: Another key objective dur-
should be collected during the pilot study, to be used for the ing the field study should be to demonstrate the mass
design of a full-scale system, include the following engineer- removal efficiency of the in  situ air sparging pro-
ing parameters: cess. This can be accomplished by measuring the net
increase in contaminant levels in the effluent of the
• Zone of air distribution: For any subsurface reme- vapor extraction system after the initiation of the air
diation system, the zone of air distribution is the key sparging system. To evaluate the net increase in con-
design parameter, since it would determine the num- taminant levels in the effluent, the field test should
ber of injection points required. The zone of influ- be conducted as a sequential test in two phases. In
ence under various pressure and flow combinations the first phase, perform the vapor extraction test until
should be measured. Methods to measure the zone of 1.5–2 pore volumes are removed from the unsatu-
influence were described earlier. rated zone and the concentrations in the extracted air
• Injection air pressure: Injection air pressure is sig- reach pseudo-“steady-”state conditions, whereby an
nificantly influenced by the depth of injection and increase in concentrations due to air sparging can be
the subsurface geology. The required baseline pres- detected. Then initiate the air sparging during the
sure during the pilot test should be equal to or just second phase and monitor the contaminant levels in
above the value necessary to overcome the sparging the vapor extraction system airstream. An increase
depth (the hydrostatic head). The additional pressure in the contaminant level along with the duration
required to push air in to the formation (the air entry of this spike would indicate the short-term mass
pressure) is generally within 1–4 psi for spargeable removal efficiency due to air sparging (Figure 8.54).
456 Remediation Engineering

Dissolved, adsorbed,
and D-NAPL phase TABLE 8.9
In Situ Air Sparging System Monitoring Parameters
Contaminant concentration

Dissolved and In Situ Parameters Measurement

in the ves air stream

adsorbed phase Groundwater quality improvement Obtaining periodic groundwater

Dissolved
phase only Dissolved oxygen levels/
temperature
Redox potential/pH
Biodegradation by-products such
Time
as CO2
Soil gas concentrations
FIGURE 8.54  Contaminant removal efficiencies during a pilot
test.
Soil gas pressure/vacuum
The  second phase of the test should be continued Groundwater level
until a decline in contaminant concentrations in System Operating Parameters
the effluent airstream is observed. If the dissolved
Injection well pressure
contaminant concentrations within the zone of air Soil vapor extraction well vacuum
distribution are low, the vapor phase contaminant Injection well flow rate
spike may go unnoticed, especially without frequent Soil vapor extraction flow rate
sampling. Extraction vapor concentrations
8.2.6  Monitoring Considerations O2, CO2, N2, CH4
samples from monitoring wells after
shutting down air injection—primary
measure of success
Field probes in the monitoring wells
after shutting down air injection
Field probes in the monitoring wells
after shutting down air injection
Groundwater samples obtained with a
flow-through cell
FID, PID, explosimeter or field gas
chromatograph or laboratory air
samples
Pressure/vacuum gauge or manometer
Water level meter
Measurement
Pressure gauge or manometer
Vacuum gauge or manometer
Airflow meters
Airflow meters
FID, PID, explosimeter, field GC, or
laboratory air samples
Laboratory analysis

In  situ and aboveground monitoring data should be used to

assess the performance of operating conditions to determine
whether system adjustments or expansions are necessary.
Table 8.9 lists the various parameters that can be utilized to
monitor the system performance. The amount of data col-
lected depends on complexity and success of the system. The
primary measurement of performance of course is groundwa-
ter concentrations. The remaining parameters listed are sec-
ondary, used to show compliance with permit conditions and/
or troubleshoot lack of performance of the system.
8.2.7  Process Equipment
Successful implementation of an air sparging system is
dependent on the proper selection of the process equipment.
Primary components of an in situ air sparging system are
• Air compressor or blower
• Vacuum blower
• Fittings and tubing to connect the compressor to the
well(s)
• Air filters
• Pressure regulator
• Flow meters
• Pressure gauges
• Air drying unit
8.2.7.1  Air Compressor or Air Blower
Selection of an air compressor or air blower will depend on
the required pressure rating at which air has to be injected
(obtained from the pilot test). Air blowers (positive displace-
ment) can be used only when the required pressure rating is
less than 12–15 psi. There are various types of air compres-
sors available, such as
• Positive displacement compressors
• Reciprocating piston
• Diaphragm
• Rocking piston
• Rotary vane
• Rotary screw and lobed rotor
• Nonpositive displacement compressors
• Centrifugal
• Axial flow
• Regenerative
Positive displacement compressors generally provide the
most economic solution for systems that require relatively
high pressures. Disadvantages include low flow rates,
oil removal in some cases, and the heat generated during
operation.
Unlike the positive displacement compressor, a nonpositive
displacement compressor does not provide a constant volu-
metric flow rate over a range of discharge pressures. The most
important advantage of nonpositive displacement compres-
sors is their ability to provide high flow rates. Table 8.10 and
Figure 8.55 provide a summary of air compressor characteris-
tics. It should be noted that the size and capacity requirements
Sparging, Venting, and Vacuum-Enhanced Recovery 457

TABLE 8.10
Summary of Compressor Characteristics
Power Pressure
Class Category Type Range (hp) Range (psi) Advantages
Positive displacement Reciprocating Piston air cooled 1/2–500 10–250 Efficient, lightweight
compressors Piston water cooled 10–500 10–250 Efficient, heavy duty
Diaphragm 10–200 10–250 No seal, contamination-free
Rotary Sliding vane 10–500 10–150 Compact, high speed
Screw (helix) 10–500 10–150 Pulseless delivery
Lobe, low pressure 15–200 5–40 Compact, oil-free
Lobe, high pressure 71/2–200 20–250 Compact, high speed
Nonpositive displacement Rotary Centrifugal 50–500 40–250 Compact, oil-free, high speed
compressors Axial flow 1,000–10,000 400–500 High volume, high speed
Regenerative peripheral blower 1/4–20 1–5 Compact, oil-free, high volume

100,000 Reciprocating
from the air, it is not very effective for removing water and
(6,900 bars) oil vapors. The moisture may later condense and freeze in the
pipes downstream when very low temperatures are encoun-
tered. An air dryer prevents condensation by reducing the
Centrifugal humidity of the airstream. A practical type of dryer is the
10,000 desiccant unit, which uses a moisture-absorbing chemical,
usually in pelletized form. Water vapor also can be removed
by condensation by passing the air through a chilling unit.
Discharge pressure (psig)

Coalescing filters are also effective in removing mists of tiny

1,000 water droplets. Less costly options include heat tracing of the
Axial piping/manifold or the use of a receiver tank with a manual or
(500) automatic drain to remove the condensation.

Rotary screw 8.2.7.2  Other Equipment

100
(60) Selection of the vacuum blower will depend on the required
Sliding vane airflow rate and vacuum levels necessary for efficient subsur-
face vapor recovery. Depending on the geologic conditions
encountered, combinations such as high vacuum, low flow;
10 and low vacuum, high flow have to be evaluated. For further
Lobe
(200,000)

description of vacuum blowers, see Section 8.1.3.1.

(200)

Valves and control devices in compressed-air systems

fall into three general categories: those that control pressure,
those that control direction of airflow, and those that control
10 100 1,000 10,000 100,000 1,000,000
28,300 m3
flow rate. Information on flow control appurtenances such as
Inlet capacity (ACFM)
flow meters, valves, and pressure gauges are easily available
in the literature.
FIGURE 8.55  Air compressor characteristics.

of an air compressor required for an air sparging site will be
typically below 100 hp and 150 psi.
Oil contamination in the injected air can affect the in situ
air sparging system performance. A variety of filters have
been developed to filter out the contained oil. An alternative is
to use an oil-less compressor. Higher capital and maintenance
costs are typical of oil-less equipment as compared to their
oil-lubricated counterparts.
Some pneumatic systems cannot tolerate moisture formed
by the cooling of air caused by compression. While a mechan-
ical filter removes most of the solid and liquid particulates
8.2.8  Biosparging
As discussed in previous sections, injection of air into water-
saturated formations has a significant benefit in terms of
delivery of oxygen to the microorganisms for in situ bioreme-
diation. Biosparging is defined as the use of injected oxygen
in the saturated zone such that contaminant mass degrades in
the saturated zone or the vadose zone prior to the vapor leav-
ing the soil surface. If delivery of oxygen for the biota is the
primary objective for air injection, the volume of airflow does
not have to be at the same level required to achieve aggressive
stripping and volatilization. Historically, practitioners used
458
low flow rates to meet the oxygen demand of the formation
(0.5 cfm to less than 2 cfm per injection point). More recently,
pulsing has been used to control the mass of oxygen injected
in to the formation on a daily basis rather than controlling the
flow rate. Higher flow rates ensure development of more air
channels and achieving a larger radius of influence, keeping
the well installation more cost-effective.
Control of air channel formation and distribution and
capturing of the stripped contaminants also become less sig-
nificant under these circumstances. Application of this tech-
nique to remediate a dissolved plume of acetone, for example,
which is a nonstrippable but extremely biodegradable com-
pound, will be appropriate. Limitations caused by geological
formations also become less significant, since the path of air
channels can be allowed to follow the path of least resistance.
However, it has to be noted that the time required to increase
the DO levels in the bulk water depends on the time required
for the diffusion of O2 from the air channels into the water
surrounding the channels. It is estimated that only 0.6% of the
oxygen present in the injected air will be transferred into the
dissolved phase during air sparging.39,40,48,59 Therefore, cau-
tion must be exercised in terms of evaluating the changes in
DO levels after the initiation of biosparging. It is common
practice to assume that the observed increase in DO levels
in monitoring wells is due to the changes in the bulk water.
Direct introduction of air into the monitoring wells due to
an air channel being intercepted could also be a reason for
increased DO levels in monitoring wells.
REFERENCES
1. U.S. Environmental Protection Agency, Forced air ventilation
for remediation of unsaturated soils contaminated by VOC,
Robert S. Kerr Environmental Research Laboratory, Ada,
OK, EPA/600/52-91/016, July 1991.
2. U.S. Environmental Protection Agency, Remedial action,
treatment, and disposal of hazardous waste, Proceedings of the
17th Annual RREL Hazardous Waste Research Symposium,
EPA/600/9-91/002, 1991.
3. Bear, J., Hydraulics of Groundwater, McGraw-Hill,
New York, 1979.
4. DiGiulio, D. C. et al., Conducting field tests for evaluation of
soil vacuum extraction application, Proceedings of the Fourth
National Outdoor Action Conference on Aquifer Restoration,
Groundwater Monitoring and Geophysical Methods, Las
Vegas, NV, May 1990.
5. Rawls, W. J., Brakensiek, D. L., and Saxton, K. E., Estimation
of soil water properties, Trans. Am. Soc. Agric. Eng., 1316,
1982.
6. Jury, W. A., Winer, A. M., Spencer, W. F., and Focht, D. D.,
Transport and transformations of organic chemicals in the
soil-air-water ecosystem, Rev. Environ. Contam. Toxicol., 99,
120, 1987.
7. Lyman, W. J., Reehl, W. F., and Rosenblatt, D. H., Handbook
of Chemical Property Estimation Methods: Environmental
Behavior of Organic Compounds, McGraw-Hill, New York,
1982.
8. Munz, C. and Roberts, P. V., Air-water phase equilibria of
volatile organic solutes, J. AWWA, 75(5), 62, 1987.
Remediation Engineering
9. Knox, R. C., Sabatini, D. A., and Canter, L. W., Subsurface
Transport and Fate Processes, Lewis Publishers, Boca Raton,
FL, 1993.
10. Weber, W. J., Jr., Physiochemical Processes for Water Quality
Control, John Wiley & Sons, New York, 1972.
11. Weber, W. J., Jr., McGinley, P. M., and Katz, L. E., Sorption
phenomena in subsurface systems: Concepts, models and
effects on contaminant fate and transport, Water Res., 25, 499,
1991.
12. Hassett, J. J., Means, J. C., Banwart, W. L., and Wood, S. G.,
Sorption properties of sediments and energy related pollut-
ants, U.S. Environmental Protection Agency, EPA/600/3-80-
041, 1980.
13. Sulfita, J. M., Microbial ecology and pollutant biodegrada-
tion in subsurface ecosystems, Chapter 7, in Transport and
Fate of Contaminants in the Subsurface, U.S. Environmental
Protection Agency, EPA/625/4-89/019, 1989.
14. Kobayashi, H. and Rittman, B. E., Microbial removal of haz-
ardous organic compounds, Environ. Sci. Technol., 16, 170A,
1982.
15. U.S. Environmental Protection Agency, Soil Vapor Extraction
Technology, Reference Handbook, EPA/540/291/0-003, 1991.
16. Sims, R. C., Soil remediation technologies at uncontrolled
hazardous waste sites: A critical review, J. Air Waste Manage.
Assoc., 40, 704, 1990.
17. Stonestrom, D. A. and Rubin, J., Air permeability and trapped
air content in two soils, Water Resour. Res., 25(a), 1959, 1989.
18. Ong, S. K. and Lion, L. W., Trichloroethylene vapor sorption
onto soil minerals, Soil Sci. Soc. Am. J., 55, 1559, 1991.
19. Montgomery, J. H. and Welkom, L. M., Groundwater
Chemicals and Desk Reference, Lewis Publishers, Boca
Raton, FL, 1990.
20. William C. Anderson, Ed., Vacuum Vapor Extraction:
Innovative Site Remediation Technology Series, Vol. 8,
American Academy of Environmental Engineers, Annapolis,
MD, 1993.
21. Massmann, J. W., Applying groundwater flow models in vapor
extraction system design, J. Environ. Eng. Div. ASCE, 115(I),
129, 1989.
22. Shan, C., Falta, R. W., and Javandel, I., Analytical solutions
for steady state gas flow to a soil vapor extraction well, Water
Resour. Res., 28 (4), 1105, 1992.
23. Strack, O. D. L., Groundwater Mechanics, Prentice Hall,
Englewood Cliffs, NJ, 1989.
24. Schafer, D., Personal communication, 1995.
25. Kruseman, G. P. and deRidder, N. A., Analysis and Evaluation
of Pumping Test Data, 2nd ed., Publication 4T, International
Institute for Land Reclamation and Improvement, Wageningen,
the Netherlands, 1972.
26. Leeson, A. et al., Statistical analyses of the U. S. air force bio-
venting initiative results, Third International In Situ and On
Site Bioreclamation Symposium, San Diego, CA, April 1995.
27. Simpkin, T. J. et al., The influence of temperature on biovent-
ing, Third International In Situ and On Site Bioreclamation
Symposium, San Diego, CA, April 1995.
28. Reisinger, H. T. et al., Pressure dewatering: An extension of
bioventing technology, Third International In  Situ and On
Site Bioreclamation Symposium, San Diego, CA, April 1995.
29. Vidumsky, J., Personal communication, 1995.
30. McHale, C., Personal communication, 1995.
31. American Institute of Chemical Engineers, Reducing and
Controlling Volatile Organic Compounds, Center for Waste
Reduction Technologies, New York, 1993.
Sparging, Venting, and Vacuum-Enhanced Recovery
32. Vembu, K. and Walker, C. S., Biofiltration holds VOCs, odors
at bay, Environ. Prot., February 1995.
33. U.S. Environmental Protection Agency, Volatile organic com-
pound removal from air streams by membrane separation,
Emerging Technology Bulletin, EPA/540/F-94/503, 1994.
34. Brown, R. A., Airsparging: A primer for application and design,
Subsurface Restoration Conference, U.S. Environmental
Protection Agency, 1992.
35. Brown, R. A., Treatment of petroleum hydrocarbons in ground-
water by air sparging, Section 4, Research and Development,
Wilson, B., Keeley, J., and Rumery, J. K., Eds., RSKERL, U.S.
Environmental Protection Agency, 1992.
36. Sellers, K. and Schreiber, R., Air sparging model for predict-
ing groundwater cleanup rate, Proceedings of the Petroleum
Hydrocarbons and Organic Chemicals in Groundwater:
Prevention, Detection, and Restoration, Houston, TX, 1992.
37. Johnson, R. L., Johnson, P. C., McWhorter, D. B., Hinchee,
R. E., and Goodman, I., An overview of in situ air sparging,
Groundwater Monit. Remed., Fall, 1993.
38. Wei, J., Dahmani, A., Ahlfeld, D. P., Lin, J. D., and Hill, E.,
III, Laboratory study of air sparging: Air flow visualization,
Groundwater Monit. Remed., Fall, 1993.
39. Johnson, R. L., Center for Groundwater Research, Oregon
Graduate Institute, Beaverton, OR, Personal communication.
40. Geraghty & Miller, Inc., Air Sparging Projects Data Summary,
1995.
41. Norris, R. H., Bioremediation of Groundwater and Geologic
Material: A Review of Technologies, Government Institutes,
Rockville, MD, 1994.
42. Moyer, E. E. and Kostecki, P. T., MTBE Remediation
Handbook, Kluwer Academic Publishers, Boston, MA, 2004.
43. Clayton, W. S., Brown, R. A., and Bass, D. H., Air sparg-
ing and bioremediation: The case for in  situ mixing,
Third International Symposium on In  Situ and On Site
Bioreclamation, San Diego, CA, April 1995.
44. Brown, R., Herman, C., and Henry, E., The use of aeration in
environmental cleanups, Presented at HAZTECH International
Pittsburgh Waste Conference, Pittsburgh, PA, 1991.
45. Bohler, J. B., Hotzl, H., and Nahold, M., Air injection and
soil air extraction as a combined method for cleaning con-
taminated sites—Observations from test sites in sediments
and solid rocks, in Contaminated Soil, Arendt, F., Hinsevelt,
M., and van der Brink, W. J., Eds., Springer-Verlag, Berlin,
Germany, 1990.
46. U.S. Environmental Protection Agency, Evaluation of the
state of air sparging technology, Report 68-03-3409, Risk
Reduction Engineering Laboratory, Cincinnati, OH, 1993.
47. Kresge, M. W. and Dacey, M. F., An evaluation of in  situ
groundwater aeration, Proceedings of the Ninth Annual
Hazardous Waste Material Management of Conference
International, Atlantic City, NJ, 1991.
459
48. Boersma, P. M., Diontek, K. R., and Newman, P. A. B.,
Sparging effectiveness for groundwater restoration, Third
International Symposium on In Situ On-Site Bioreclamation,
San Diego, CA, April 1995.
49. Lundegard, P. D. and Andersen, G., Numerical simulation
of air sparging performance, Proceedings of the Petroleum
Hydrocarbons Organic Chemistry and Groundwater:
Prevention, Detection, Restoration, Houston, TX, 1993.
50. Lundegard, D. D., Air sparging: Much ado about mound-
ing, Third International Symposium on In  Situ On-Site
Bioreclamation, San Diego, CA, April 1995.
51. Ahlfeld, D. P., Dahmani, A., and Wei, J., A conceptual model
of field behavior of air sparging and its implications for appli-
cation, Groundwater Monit. Remed., Fall, 1994.
52. Marley, M. C., Li, F., and Magee, S., The application of a 3-D
model in the design of air sparging systems, Proceedings
of the Petroleum Hydrocarbons Organic Chemistry and
Groundwater: Prevention, Detection, Restoration, Houston,
TX, 1992.
53. Marley, M. C., Walsh, M. T., and Nangeroni, P. E., Case study
on the application of air sparging as a complimentary technol-
ogy to vapor extraction at a gasoline spill site in Rhode Island,
Proceedings of the HMCRI 11th Annual National Conference,
Washington, DC, 1990.
54. Ardito, C. P. and Billings, J. F., Alternative remediation
strategies: The subsurface volatilization and ventilation sys-
tem, Proceedings of the Petroleum Hydrocarbons Organic
Chemistry and Groundwater: Prevention, Detection,
Restoration, Houston, TX, 1990.
55. Marley, M. C., Bruell, C. J., and Hopkins, H. H., Air sparg-
ing technology: A practice update, Third International
Symposium on In  Situ On-Site Bioreclamation, San Diego,
CA, April 1995.
56. Klemmer, M., Zahniser, B., and Clark, B., Determination of
air-filled pore space using resisitivity imaging as a tool for
design of air sparging systems, Presented at The International
Conference on Chlorinated and Recalcitrant Compounds,
Monterey, CA, 2014.
57. Acomb, L. J. et al., Newtron probe measurements of air satura-
tion near an air sparging well, Third International Symposium
on In  Situ On-Site Bioreclamation, San Diego, CA, April
1995.
58. Johnston, C. D., Rayner, J. L., and Briegel, D., Effectiveness
of in  situ air sparging for removing NAPOL gasoline from
a sandy aquifer near Perth, Western Australia, J. Contam.
Hydrol., 59, 87–111, 2002.
59. Klemmer, M., Smith, J., Payne, F., Wilson, K., and Whiting,
R., Sulfur hexafluoride tracer used in performance monitor-
ing and optimization of oxygen-enhanced sparging system,
Presented at The International Conference on Chlorinated
and Recalcitrant Compounds, Monterey, CA, 2012.
 9 Soil Treatment
9.1 INTRODUCTION
Interestingly, the focus on soil contamination and its potential
impacts has lagged behind that of groundwater contamina-
tion. However, over the last several years, especially as appre-
ciation of the importance of contaminant behavior in the
vadose zone has grown, there has been a parallel growth in
efforts to evaluate and mitigate the environmental risks that
may be posed by the presence of residual soil contaminants.
It is important that the potential pathways for exposure are
evaluated carefully, particularly when migration routes are
present. For contaminated soils, there are three potential path-
ways for such exposure: transport of soluble contaminants to
groundwater as water infiltrates through the soil, migration
of contaminant vapors through the soil and into structures or
the atmosphere, and direct contact with contaminated soil.
Decisions regarding the need for remediation and the type
and extent of cleanup required should be based on a site-
specific evaluation of the potential risks posed by any of these
potential pathways.
A critical component in characterizing the nature of soil
contamination is the determination of the type and concen-
trations of contaminants present. Careful planning should be
implemented for selecting the proper procedures for analy-
sis of the different types of contaminants, together with the
sampling and handling techniques prior to analysis. The con-
centrations reported must be cautiously evaluated as to their
validity, meaning, utility, and possible limitations. Careful
and reasoned interpretation of the results is necessary if
meaningful decisions are to be made.
Soil remediation while not isolated from the groundwater
approaches discussed in the other chapters has unique consid-
erations and criteria that define success. Soil screening crite-
ria that are linked to exposure to the soil itself are associated
with direct contact and ingestion of the soil. Depending on
the contaminant, the criteria associated with desorption of
a contaminant from soil to either soil vapor or groundwater
can often drive treatment criteria lower than the direct contact
pathway alone. This chapter will discuss a few remediation
technologies as they relate to soil treatment, but it is important
to remember that soil vapor and groundwater contamination
may be the drivers for soil remediation.
As with any remedy selection, the guiding criteria should
be a combination of the drivers for remediation (regulatory
compliance, risk, cost, etc.), subsurface conditions and com-
plexities, and contaminant characteristics that may preclude
certain technologies. Soil heterogeneity and contaminant type
and distribution are critical for remedy selection. Depending
on the age of most contaminant releases, residual contaminant
mass in source areas may generally be in the low permeabil-
ity portions within the vadose zone, as the mass in the high
permeability portion of the subsurface would flush out of the
source area and create a groundwater plume.
Excavation followed by treatment or disposal and a few
in  situ soil treatment options, discussed in this chapter, are
applicable in heterogeneous and low permeability geologic
settings. When most of the conventional remedial technolo-
gies cannot access contaminant mass stored in low perme-
ability soils, these techniques can. The technologies mainly
discussed in this chapter are in situ soil stabilization, thermal
remediation, and phytoremediation. Thermal remediation is a
relatively new technology with a suite of potential implemen-
tation methods, which need to align with site-specific condi-
tions. Phytotechnology, the use of plants for remediation, has
been around for quite some time and is mostly intended to
treat and/or stabilize shallow soil and groundwater. With the
exception of phytotechnology-based remediation, these tech-
nologies are relatively fast and either remove, sequester, or
destroy contamination that is adsorbed to soil. At the same
time, they are intrusive and disruptive, presenting a number
of health and safety and logistical challenges.
Because of the relatively high costs associated with soil
remediation, directly in proportion to the contaminated vol-
ume, understanding the scale of the remedy early on is cru-
cial. Once a remedial approach is selected, the need and the
scope of a reliable predesign investigation (PDI) are deter-
mined based on the potential cost of the remedy. The results
of the investigation and comparison to screening values could
potentially decrease the volume requiring treatment or, at a
minimum, will ensure accurate estimation of potential costs.
The objectives of this type of investigation are both to con-
firm the soil volume that requires treatment and to explore
the subsurface utilities and also to confirm that there are no
significant alterations to the conceptual site model that would
affect implementation.
9.1.1  Screening Criteria
Screening values, intended to be protective of human
health and the environment, are often defined as contami-
nant concentrations in the environmental media in which
no additional regulatory action is warranted. Screening
values are concentrations of chemicals derived from a tar-
get excess risk level (for carcinogens) or hazard quotient
(for noncarcinogens) under generic exposure assumptions.
Screening values developed and used for the same chemi-
cal may vary among states and regions of EPA. If contami-
nant concentrations at a site exceed the screening values,
then additional investigation or evaluation of that contami-
nant may be warranted. Risk-based screening values are
derived from equations combining exposure assumptions
with toxicity data.
461
462
Much like selecting a groundwater remediation strategy,
selecting the right technology for soil remediation requires
consideration of a number of factors. These include:
• Type of contaminants and contaminant chemical
properties
• Geologic and hydrogeologic conditions at the site
• Soil geotechnical and geochemical properties
• Site logistics, subsurface utilities, and infrastructure
• Remediation end points, remedial drivers, and time
frames
• End use of the property
Soil remediation technologies discussed in this chapter are
associated with removing or treating in place grossly con-
taminated soil and include isolation, destruction, extraction,
immobilization, physical separation, and toxicity reduction as
treatment mechanisms. The potential direct exposure path-
ways of soil contamination are as follows:
• Direct ingestion
• Inhalation of volatiles and dust, etc.
• Dermal adsorption
• Ingestion of homegrown produce
• Migration of volatiles into basement
In addition, the potential migration pathways include:
• Groundwater migration
• Surface water migration
• Volatilization and entrainment
• Direct contact
For the direct exposure drivers, there are criteria that dictate
the cleanup objectives and the extent of remediation required.
In scenarios where migration is the remediation driver, there
are often generic criteria and specific regulatory guidance
available that can guide remediation, but often site-specific
criteria should be required to ensure that remediation objec-
tives are achieved.
Soil standards that are designed to be protective of
­groundwater are based on contaminants leaching from the
soil to groundwater. Different soil types combined with con-
taminant properties can create vastly different leaching char-
acteristics. There are a number of models available to help
in determining the leaching estimates. There are also a few
analytical methods such as synthetic precipitation leaching
procedure (SPLP), toxicity characteristic leaching procedure
(TCLP), waste extraction test (WET), and deionized water
waste extraction test that can help with determining applica-
ble soil standards.1,2 Using these analyses, coupled with risk-
based screening guidance derived by either state agencies or
the EPA, can create site-specific screening criteria for soil that
can be protective of all of the potential exposure pathways.
In Chapter 2, we have discussed the general nature of the
processes that affect contaminant pathways in soils and also
the potential for natural assimilation or degradation of the
Remediation Engineering
contaminants. Careful definition and evaluation of poten-
tial risks that are uniquely associated with each site has to be
emphasized. In summary, the potential risks at any given site
are the result of:
• Type and extent of the contamination
• Site-specific conditions that influence possible routes
of contaminant exposure
• Proximity of potential receptors to the contaminated
soil
The unique potential risks at a given site will in turn require
that careful consideration is given to the different remedial
solutions that can effectively control that risk. It is important
to appreciate that sufficient flexibility is required within the
regulatory programs to allow for the design of site-specific
cleanup goals and technical strategies to achieve them.
9.1.2  Sorptive Processes
The efficiency of remediation of contaminated soils will be
influenced by the soil matrix as well as the properties of the
contaminants present at the site. Thus, chemical properties of
the contaminants of concern (COCs) need to be considered
when selecting a soil remedy. Contaminants interact with dif-
ferent soil types in different ways based on their characteris-
tics. The following description of sorptive interactions needs
to be understood as part of a conceptual site model that is
driving soil remediation.
Contaminants become strongly sequestered as they per-
sist in the soil matrix for a long period of time. This process
is sometimes referred to as “aging” and leads to decreasing
availability of the contaminants, which has an impact on the
remedy selection. It is also important to note as the size of soil
particles decreases, the contaminants become more strongly
sorbed to the soil’s matrix, probably due to the accompanying
increase in surface area. The sorption strength is also affected
by hydrophobicity of the contaminants. Further, the organic
content of the soil is often regarded as the most important soil
parameter for adsorption (Figure 9.1).
Sorptive interactions of interest also occur between hydro-
phobic organic compounds dissolved in groundwater and solid
or colloidal organic matter of the aquifer matrix or between dis-
solved cations and points of negatively charged aquifer miner-
als (cation exchange). The sorption reactions are classified as
adsorption or absorption, based on whether the organic matter
behaves like a solvent (absorption) or, alternatively, provides spe-
cific binding sites that immobilize (adsorb) the dissolved mol-
ecules. The energy released in absorption is relatively low and
the process is best characterized as fully reversible equilibrium
partitioning of the solute between the aqueous and organic mat-
ter phases. There is an implicit assumption that absorbed solute
molecules move freely in the organic matter phase. Adsorption
is the more energetic reaction, an exothermic binding reaction
between a solute molecule and a binding site on the organic mat-
ter. Adsorbed solute molecules are effectively pinned in place
and do not move freely through the binding matrix.
Soil Treatment 463

100 the near-surface water. Since clay minerals are frequently

Toxaphene
the dominant source of ion exchange in the subsurface, it is
Naphthalene
80 important to have a fundamental understanding of clay miner-
PCE alogy and the source(s) of charge deficiencies in clay minerals.
1,1,1-TCA
Percent sorbed

60 TCE
9.2  SOIL EXCAVATION
Benzene

40 cis-DCE
Vinyl chloride
20
0 disposal or treatment methodology is the other critical design
0.000 0.002 0.004
Organic carbon fraction ( foc )
FIGURE 9.1  Sorbed (nonaqueous) fraction of selected hydropho-
bic organic compounds expressed as a function of aquifer organic
carbon content.
Adsorption reactions may occur between dissolved hydro-
phobic organic molecules and inorganic aquifer matrix min-
erals or organic matter broadly classed as “hard carbon”
forms. Materials that fall into the hard carbon class include
coal fragments and pieces of wood char and soot from for-
est fires, materials that are unlikely to be measured in total
organic carbon analyses.
Ion exchange is a specific category of adsorption. Owing
to the ubiquitous phenomenon of ionizable surface groups on
wet particles, virtually, every solid presents a charged surface
to the aqueous solution. If this surface charge is of opposite
sign to that exhibited by a contaminant’s functional group,
then there will be an electrostatic attraction between the con-
taminant in the bulk solution and the particle surface. Such
solutes will accumulate in the thin film of water surrounding
the particle as part of the population of charges in solution
balancing the charges on the solid surface. Conversely, solutes
with charges of like sign as the surface will be repulsed from
One of the most traditional and simple approaches to soil
remediation is via excavation. Traditionally used as a source
removal technology, excavation is the most direct, expedi-
Tetrahydrofuran ent, comprehensive, and absolute approach to soil treatment.
1,4-Dioxane Once the excavation volume has been determined, the soil
0.006 0.008 0.010
parameter.
Excavation of contaminated soil from a site involves dig-
ging it up for “ex situ” (aboveground) treatment or for disposal
in a landfill or treatment at an incineration plant. Excavation
may also involve removing old drums of contaminants and
other buried debris that might be contaminated. Removing
these sources of contamination keeps people from coming
into direct contact with the waste material and also helps to
speed up the cleanup of the contaminated groundwater by
eliminating the potential migration routes.
Before excavation can begin, the contaminated areas and
volume of contaminated soil must be reliably identified. This
requires researching past site history and activities to iden-
tify what contaminants may have been released and where.
Contaminated soil is excavated using standard construction
equipment, like backhoes and excavator track hoes shown in
Figure 9.2 (a) and (b). The equipment chosen depends on how
large and deep the contaminated area is and whether access
is limited by the presence of buildings or other structures that
cannot be moved. Long-reach excavators can reach as deep as
100 ft belowground, but excavations are generally limited to
much shallower depths due to safety concerns and difficulty
keeping the hole open. Sometimes, soil is excavated below the
water table, which requires walling off the contaminated area
and pumping out the water to keep dry during excavation.

(a) (b)

FIGURE 9.2  (a) Excavation of sub-surface soils for the purpose of remediation. (b) Excavation activities at a remediation site.
464
If excavated soil is to be disposed of in a landfill, it may
be placed directly on a dump truck for transport. If it is to be
disposed of elsewhere on the site or treated, it first may be
stockpiled on plastic tarps or in containers. The soil is then
covered with tarps to prevent wind and rain from blowing or
washing it away and to keep workers from coming into con-
tact with contaminated soil. Excavation is complete when test
results show that the remaining soil around the hole meets
established cleanup levels.
The excavated soil may be cleaned using a mobile treat-
ment facility brought to the site or disposed off-site. If the soil
is treated on-site, treated soil may be used to fill in the exca-
vated area. Clean soil obtained from other locations may be
needed to fill in holes as well. After an excavation is filled in,
the area may be landscaped to prevent soil erosion and make
the site more attractive.
Off-site disposal and ex-situ treatment are used to dis-
pose or treat the excavated soil. Handling contaminated soil
requires a focus on the health and safety of the site workers
as well as nearby residents or buildings. To this end, dust and
air monitoring is often conducted to ensure that no impacts
migrate off-site. In addition, this monitoring helps determine
the level of personal protective equipment that is required for
site workers.
Excavating contaminated soil may take as little as one day
or as long as several months. There are a number of factors
that can result in an increased complexity and costs associ-
ated with excavation. The most common of these logistical
challenges are listed in the following and will vary from site
to site:
• The contaminated area is large, very deep, or below
the water table.
• If the excavation extends below the water table, a
dewatering system and subsequent treatment are
required.
• The contaminated soil contains a lot of rocks and/
or debris.
• The presence of buildings or other site activities can
limit the access to certain portions of soil that need
to be excavated and can limit the ability to move
around the site efficiently.
• If the site is remote or not proximal to an appropri-
ate disposal facility, on-site treatment (if feasible) is
needed.
Handling contaminated soil requires precautions to ensure
safety. Site workers are trained to follow safety procedures
while excavating soil to avoid contact with contaminants
and prevent the spread of contamination off-site. Site work-
ers typically wear protective clothing such as rubber gloves,
boots, hard hats, and coveralls. These items are either washed
or disposed of before leaving the site to keep workers from
carrying contaminated soil off-site on their shoes and cloth-
ing. The tires and exteriors of trucks and other earth-moving
equipment are also washed before leaving the site so that the
soil is not tracked through neighboring streets.
Remediation Engineering
Workers monitor the air to make sure dust and contami-
nant vapors are not present at levels that may pose a breathing
risk, and monitors may be placed around the site to ensure
that dust or vapors are not leaving it. Site workers close to
the excavation may need to wear “respirators,” which are face
masks equipped with filters that remove dust and contami-
nants from the air. Contaminated soil is usually covered until
it can be treated or disposed of to prevent airborne dust or
being washed away with rainwater. Contaminant vapors may
be suppressed with foams or other materials.
9.2.1 Ex Situ Soil Treatment
Ex situ soil treatment is most often selected because it is faster
than in situ treatment (IST), and there is a higher degree of
certainty about the completeness of the treatment because of
the ability to handle and sample the soil more easily. This
requires excavation of the soil that often comes at a higher
cost, more equipment, more disruption, and potentially higher
potential for exposure to the contaminants. The same pro-
cesses used as part of in situ remediation are used for ex situ
soil treatment as well including thermal, biological, chemical,
and physical. Some of these methods are discussed in the fol-
lowing sections.
9.2.1.1 Disposal
Soil is classified by the EPA as either hazardous or nonhazard-
ous, depending on concentrations of contaminants present in
soil and their leachability from the soil. The primary leaching
method, TCLP extraction, is meant to simulate the acidic con-
ditions present in a landfill. Other parameters that are often
required to be compliant with RCRA land disposal restriction
regulations include pH or Eh, speciation of metals, alkalin-
ity or water hardness, BTU content if a thermal treatment is
being considered, and soil moisture. Once the classification of
the soil is determined, the landfills that can accept the mate-
rial within the area of the site need to be vetted—and in the
case of extreme excavation volumes, it needs to be determined
if the landfill can accept the soil. The accepting facility will
often have criteria that have to be met before receiving the
waste soil.
The RCRA determination of whether hazardous or non-
hazardous is the most critical for most environmental sites
and should be determined as part of the remedy screening
process as it can drastically increase the cost of disposal. Part
of this determination is whether the waste is exempt from all
or some RCRA regulations as imposed by the EPA or autho-
rized state. These exemptions are generally found in 40 CFR
261.31-261.33.3
When reviewing these lists, the generator must also con-
sider the “derived from” and “mixture” rules. In short, if
a waste is derived from the storage or treatment of a listed
waste, it is also a listed waste (see 40 CFR 261.3 for the full
requirements). If the waste is an RCRA listed waste as gener-
ated or as a result of either the derived from or mixture rules,
then it must be managed as a hazardous/mixed waste. When
determining if a waste is an RCRA listed waste, it is important
Soil Treatment
to note that chemical analyses do not make the determination,
but instead it is based on knowledge of the waste and com-
parison of the waste to specific listings found in the federal
regulations or a state equivalent.
If a waste is not a listed waste, it must be tested to deter-
mine if it exhibits a characteristic of a hazardous waste based
on ignitability, corrosivity, reactivity, and toxicity (see 40
CFR 261.21-261.24 for requirements).3 If the waste exhibits a
characteristic of a hazardous waste, then it must be managed
as a hazardous/mixed waste. If the waste is neither listed nor a
characteristically hazardous, then it is not a hazardous/mixed
waste and can be managed as a nonhazardous waste.
9.2.1.2 Incineration
Incineration is a high-temperature (870°C–1600°C) oxidation
of many forms of waste. For contaminated soils, incinera-
tion chemistry is critically important as the energy content
of the materials, and the oxidation mechanisms have sub-
stantial impact on the selection of a specific incinerator for
a task. The second topic, design considerations, details how
physical properties of waste affect selection and design of an
incinerator.
One of those design aspects is organic destruction effi-
ciency, which is commonly advertised as performance cri-
teria for an incinerator type. Incineration, however, does
not destroy metals. Metals will produce different residuals
depending on the volatility of the compounds, the presence of
certain compounds (e.g., chlorine), and the incinerator operat-
ing conditions. Improperly operated incinerators also have the
potential to create dioxins and furans. Incineration of large
volumes of contaminated soils may be cost prohibitive.
Incineration may be performed on- or off-site. There may
be significant considerations regarding the compliance of
incineration with multiple regulations. On-site incineration
may be performed with a transportable incineration unit; how-
ever, space availability and public opposition may make this
option inappropriate. Whenever incineration is considered as
an option to fulfill remediation goals, particular efforts should
be made to provide the community with good information on
incineration and to be responsive to any concerns raised by
the community. Commercial incineration facilities (i.e., units
permitted for the incineration of hazardous wastes, includ-
ing incinerators and cement kilns) may be used when off-site
incineration is desirable. However, only a limited number of
these facilities are available nationwide.
Common incinerator types include:
• Rotary kiln
• Infrared furnaces
• Liquid injection
• Fluidized bed
• Multiple hearth
They all operate on the similar design basis of having a com-
bustion source, air intake, ash output, and a secondary com-
bustion chamber to address flammable constituents in the
off-gas from primary combustion.
465
The rotary kiln is the most versatile of incinerators, capa-
ble of burning a broad range of hazardous and nonhazard-
ous liquids, solids, and slurries. It burns liquid or solid wastes
efficiently because, as the cylindrical combustion chamber
rotates, wastes become well mixed with oxygen. However,
gaseous wastes are not usually processed in kilns because
they must be fed at a higher rate and the residence time avail-
able is generally insufficient for complete oxidation. Liquid
and solid wastes can be burned simultaneously.
In the infrared conveyor furnace, energy in the infrared
region is used to heat waste to a specific temperature where
desorption and/or incineration of the organic contaminants
occurs. The gases that are exhausted from the furnace carry
the desorbed contaminants and are combusted in a second-
ary combustion chamber. These systems have been used in
a number of operations, ranging from pilot-scale units used
to obtain TSCA permits or evaluate the technology to com-
mercial incineration of large quantities of contaminated soil.
A liquid injection incinerator is the most common type
used for the incineration of hazardous wastes in the liquid
form. With this technology, liquid, gaseous, or slurry waste
is injected into the combustion chamber through a nozzle or
burner. The nozzle mixes the liquid with air, atomizing it into
a suspension of droplets that is quickly vaporized. Before a
waste is fed into a liquid injection incinerator, pretreatment in
the form of filtration, degassing, neutralizing, or mixing may
be required, especially to reduce particles or to modify the
viscosity of the liquid.
The fluidized bed technology promotes turbulence and
facilitates superlative mixing of the waste with hot air and
hot media. The sustained agitation of the media allows larger
waste particles to remain suspended until the combustion
is complete, thus enhancing combustion efficiency. Forced
draft air is introduced at the bottom of the combustion cham-
ber. As the air rises through a distribution plate and upward
through the bed, it promotes strong agitation and causes the
bed to mimic the physical properties of a liquid. The waste
is injected radially into the preheated media, and combus-
tion takes place within the bed as heat is transferred from the
media to the waste.
A multiple hearth incinerator has been utilized for more
than 60 years to burn sewage sludge. This technology consists
of horizontal refractory-lined hearths arranged in a vertical
structure. Rabble arms and teeth rotate on a central shaft to
agitate and convey the waste through the incinerator. The liq-
uid and gaseous wastes are injected into the top of the main
chamber. The waste material enters the top hearth, and it is
heated to combustion temperature by means of several igni-
tion burners.
9.2.1.3  Thermal Desorption
Ex situ thermal desorption is a physical mass transfer pro-
cess that uses a rotary kiln to heat the soils to volatilize con-
taminants, allowing the contaminants to be transferred from
the soil to a gas stream. Thermal desorption systems typi-
cally operate at temperatures between 300°F and 1000°F
depending on the site-specific conditions. The operating
466
temperature and residence time in the rotary kiln are depen-
dent upon the boiling point of the contaminants, moisture
content of material being treated, type of soils, and soil
cleanup requirements.
Ex situ thermal desorption is a multistep process. Once the
contaminated materials are excavated from the subsurface,
they are sent through a preprocessing step to prepare them for
treatment in the thermal unit. The preprocessing step com-
monly consists of screening oversized material, removing
metal, blending high- and low-concentration materials, and,
if necessary, moisture conditioning (i.e., addition of lime or
other drying agents). Following preprocessing, the material is
placed into the thermal unit, where heat is used to volatilize the
contaminants as well as any water present in the soil matrix.
A sweep gas is used to capture the volatilized contaminants
and water vapor, which are subsequently treated through the
off-gas treatment system. Once the contaminated material has
been treated at the specified temperature and residence time,
the soils are removed from the unit and stockpiled pending
sampling and analysis. The sweep gas containing the organic
vapors is treated using condensation, collection (i.e., vapor
phase carbon), or combustion (i.e., afterburner). Typical off-
gas treatment systems also include a baghouse for removal of
particulates that become entrained within the off-gas during
the treatment process.
9.2.1.4  Land Farming and Biopiles
Land farming and biopiles rely on biological degradation
of contaminants and volatilization. This approach is most
applicable for aerobically biodegradable contaminants—such
as petroleum hydrocarbons. Similar to in  situ groundwater
­remedies, proper biogeochemical conditions need to be main-
tained to optimize treatment. Both approaches usually involve
stimulating the microbial ecology via aeration and/or addition
of nutrients, minerals, and water/moisture.
The principles are the same between land farming and
biopiles, and the differentiation between the two is based on
a few implementation approaches, which are often selected
based on the contaminants present, the volume of soil to be
treated, and the space available.
(a)
FIGURE 9.3  (a) Land farming of petroleum contaminated soils at an old terminal site in New England. (b) Treatment of petroleum con-
taminated soils via bio-piles.
Remediation Engineering
• Land farming involves spreading soil in a thin (nor-
mally less than 1.5 m) layers, and aeration is achieved
by routine mixing (Figure 9.3a).
• Biopiles are often taller (up to 6 m in height) (Figure
9.3b), covered and/or lined to limit leaching, and
normally have active venting via piping and blow-
ers to stimulate air/oxygen flow through the pile.
Temperature can also be increased in biopile to
enhance the degradation rates.
For petroleum hydrocarbons, the lighter fraction of gasoline
constituents often volatilize during excavation and handling,
and the longer chained carbon compounds (often referred
to as “heavier” or middle and heavy distillates) remain
adsorbed to the soil and are bioavailable. These heavier
hydrocarbons, such as those found in heating and lubricating
oil and to a lesser degree in diesel and kerosene, require a
long period of time to degrade. Some critical design param-
eters for aerobic biodegradation using either biopiles or land
farming are:
• pH greater than 5 and less than 8, ideally between
6.5 and 7.5
• Soil moisture between 10% and 35%—with biodeg-
radation rates decreasing on both ends of that range
• Temperature >45°F—with biodegradation rates
increasing with increasing temperature
• Total petroleum hydrocarbon (TPH) concentrations
<50,000 ppm—with no visible nonaqueous phase
liquid (NAPL)
• Sufficient nutrients, such as nitrogen, to promote
microbiological activity
• Uniform oxygen availability throughout the soil
treatment volume
When these parameters are met, average remediation time
frames range from 6 weeks to 18  months. Achieving 100%
treatment uniformly across the entire volume and concentra-
tions less than 0.1 ppm may be difficult to achieve using this
technology within a reasonable time frame.
(b)
Soil Treatment 467

9.2.2 Design Considerations soil. Obviously, stability calculations should be based on the

smallest shear strength to ensure safety, thus safety factors are
9.2.2.1  Soil Volume normally applied and range from 1.3 to 2.
As discussed earlier, various criteria and remedial objectives
can drive the soil volume requiring excavation. Cost and scale
of the excavation can vary widely depending on the soil vol- 9.3  IN SITU THERMAL REMEDIATION
ume. The economics of treatment and disposal can change In  situ thermal remediation technologies have been proven
drastically with increasing soil volumes. Large soil volumes to be effective at eliminating NAPLs, which may be either
can make on-site treatment more feasible. lighter than water (i.e., LNAPLs) or more dense than water
Soil excavation involves with dealing with three primary (i.e., DNAPLs), and residual source mass (i.e., mass trapped
states in which the soil exists: natural (in place), loose (after in the aquifer matrix at less than residual saturation levels).
excavation), and compacted. When soil is excavated, it typi- Frequently, thermal remediation practitioners also report
cally increases in volume so that the soil contained in one cubic significant contaminant concentration reductions in soil and
yard in place will, after excavation, occupy more than one cubic groundwater due to the removal of source mass, especially at
yard. This increase in volume due to excavation is called swell. projects with chlorinated volatile organic compound (CVOC)
Similarly, when soil is compacted, it reduces in volume. It is impacts. When properly implemented, thermal strategies have
important in excavation calculations to convert all volumes to reduced dissolved and adsorbed phase CVOC concentrations
a common unit of measure. The in place (bank) cubic yard is to near laboratory detection limits. For many CVOCs and non-
commonly used for this purpose. Soil volume change due to chlorinated volatile organic compounds (VOCs), vaporization
excavation and compaction is presented in Table 9.1.4 is the dominant removal mechanism, because vapor pressures
of the contaminants increase exponentially with increasing
9.2.2.2  Soil Stability temperature and approach 1 atm (760 millimeters [mm] of
During any excavation, safety considerations need to be con- mercury [Hg]) near to the boiling point of water (100°C). In
sidered. One of the key safety considerations is the potential addition, the Henry’s law constants for VOCs and CVOCs
for the soil to slide from a higher location to a lower one, as an with low aqueous solubility also increase with temperature,
excavation proceeds. With equipment, buildings, and people leading to the increased potential for the contaminant to parti-
all potentially near the edge of an excavation, the damage tion from the aqueous phase into the vapor phase. The com-
associated with sliding soil can be significant. bination of increased contaminant volatility and preference
The basic principle is that once the shear stresses devel- for the vapor phase near the boiling point of water means that
oped in the soil are greater than the shear strength of the these chemicals can be rapidly and efficiently removed from
soil—sliding will occur. While simple in concept, the num- the subsurface if the treatment zone is uniformly heated near
ber of potential variables and possible planes over which to or above 100°C.
sliding can occur can complicate slope stability calculations. For effective treatment within a prescribed heating period,
In addition, the shear strength of a soil can vary over time remedial strategies must achieve effective pneumatic and
based on soil moisture and other physical properties of the hydraulic control in the subsurface. Also, the design process
must consider that the extracted contaminants could be pres-
ent in multiple phases (i.e., LNAPLs, DNAPLs, dissolved,
TABLE 9.1 and gaseous), and at elevated temperatures that could exceed
Typical Soil Volume Conversion Factors 100°C. Likewise, the aboveground treatment system needs to
be capable of handling peak contaminant loads when treat-
Converted to
ment zone temperatures approach the maximum design crite-
Soil Type Initial Soil Condition Bank Loose Compacted ria. Each treatment system component (unit processes, vessels,
Clay Bank 1.00 1.27 0.90 controls, piping, pumps, etc.) must be able to withstand very
Loose 0.79 1.00 0.71 rigorous conditions not normally found on traditional reme-
Compacted 1.11 1.41 1.00 diation projects such as elevated temperatures, potentially
Common earth Bank 1.00 1.25 0.90 flammable/explosive vapor streams and environments, highly
Loose 0.80 1.00 0.72 corrosive liquid and vapor streams, and chemical incompat-
Compacted 1.11 1.39 1.00 ibilities due to rigorous process conditions (i.e., the combi-
Rock (blasted) Bank 1.00 1.50 1.30 nation of elevated temperature, pressure/vacuum, and solvent
Loose 0.67 1.00 0.87 effects of the constituents of concern).
Compacted 0.77 1.15 1.00 Aquifer minerals and metals also could be present in the
Sand Bank 1.00 1.12 0.95
extracted groundwater that will need to be appropriately
Loose 0.89 1.00 0.85
handled. For example, sites with elevated dissolved iron con-
Compacted 1.05 1.18 1.00
centrations will pose specific challenges for the efficient and
Source: Nunnally, S.W., Managing Construction Equipment, Prentice Hall, effective handling of the aqueous waste streams to minimize
Inc., Englewood Cliffs, NJ, 1977. biological and precipitation fouling of equipment and piping
and to meet typical discharge standards. In addition, some
468
sites may have elevated elemental mercury concentrations in
the soil. If these soils are heated to temperatures greater than
300°C (e.g., in the immediate vicinity of thermal conduction
heaters), the elemental mercury could be volatilized from
the soil, resulting in concentrations of concern in the vapor
stream, which would require specialized treatment steps for
effective removal.
If any of the extraction and treatment system compo-
nents fail during implementation and heating of the soil, then
extended treatment times could result and, in some cases, the
potential for uncontrolled releases to the atmosphere or sur-
rounding groundwater system could increase to unacceptable
levels (via loss of pneumatic or hydraulic control). Depending
on the criticality of the targeted remedial time frame and
the hazards associated with potential uncontrolled releases,
redundant systems are often used in the treatment system
and/or backup systems should be readily available to help
ensure project success.
The target temperature in the treatment zone is dependent
on several factors including the chemical contaminants, pres-
ence of LNAPLs or DNAPLs, characteristics of the aquifer
matrix, heterogeneity of subsurface soils, required duration
of heating, and remedial goal objectives. However, the tar-
get temperature should be above boiling point of the soil and
groundwater system, which needs to account for the pressure
associated with the ambient hydrostatic head to ensure that a
phase change to the vapor state is achieved. For example, the
boiling point of the groundwater system at the water table at
1 atm of pressure is 100°C, whereas, the boiling point of the
same system 30 ft below the water table is 118°C. Therefore,
if the treatment zone extends to 30 ft below the water table,
the temperature at the bottom of the treatment zone needs to
achieve 118°C before water within the soil pores boils and
generates a vapor phase.
For most sites contaminated with VOCs or CVOCs and
that have stringent remedial standards, then it is typically
necessary to input enough energy to boil off approximately
700
600
Pore volumes of steam generated
500
400
300
200
100
0 0
0 20
FIGURE 9.4  Pore volumes of steam generated in situ at a thermal remediation site in low permeable clay.
Remediation Engineering
20%–30% of the pore water from the vadose and saturated
zones.5 Boiling off 20%–30% of the pore water within the
targeted treatment zone will typically result in the in  situ
generation of 500–600 pore volumes of steam. Figure 9.4
presents data from a site in low permeability clay where
the remedial goals were achieved for the CVOCs following
boiling of approximately 30% of the pore water and genera-
tion of 600 pore volumes of steam.5 Designing energy input
and extraction systems that are capable of delivering enough
energy to the treatment zone to boil off 20%–30% of the pore
water while maintaining pneumatic and hydraulic control is
therefore critical to successfully achieving the remedial stan-
dards and remediating these sites. Sites with other organic
chemicals with boiling points higher than VOCs and CVOCs
(e.g., polychlorinated biphenyls [PCBs], dioxins, polycyclic
aromatic hydrocarbons [PAHs], and other semivolatile com-
pounds [SVOCs]) can also be effectively treated using thermal
remediation; however, all of the water within the treatment
zone must first be boiled off so that the soil can be heated to
sufficiently high enough temperatures to volatilize and desorb
these compounds (e.g., 150°C–350°C).
During operation of in  situ thermal remediation systems,
a robust monitoring program is required to ensure that design
targets for in situ temperatures, water levels, and vacuums are
achieved throughout the horizontal and vertical extents of the
treatment zone. In addition, sampling of the various process
streams is also required to ensure that the contaminant mass
and energy balances meet the performance standards developed
during the design process. The actual mass of contaminants is
often not known and/or cannot be calculated with a reasonable
degree of certainty, so multiple lines of evidence are typically
used to ensure that an in  situ thermal remediation project is
progressing as planned and that ultimately has achieved the
remedial end points. Periodic soil and g­ roundwater samples
are often collected within the treatment zone and from the pro-
cess streams, to ensure timely progression toward the remedial
objectives. Close attention to these factors will help ensure the
120
Average subsurface temperature (°C)
100
80
60
40
PVs of steam 20
AVG temp. of TTZ
40 60 80 100 120 140
Days of operations
Soil Treatment
thermal remediation strategy achieves its remedial objectives
within its intended time frame.
The following sections include some of the more important
considerations during the design and implementation phases
of in situ thermal remediation projects. The first is an initial
introduction on the modes of energy input used for the various
thermal remediation strategies. The primary treatment and
removal mechanisms are then discussed to provide the reader
with a strong overview of the processes that occur below-
ground. Then an introduction to the primary in situ thermal
treatment technologies is provided, followed by a summary
of the key aspects that should be considered when selecting
the appropriate technology or technologies for a site. Finally,
an overview of the typical monitoring requirements and data
analyses for a thermal remediation project are presented. This
knowledge should benefit remediation system designers, prac-
titioners, and/or responsible parties during the various phases
of all thermal remediation projects.
9.3.1 Energy Input and Heating Mechanisms
Input of energy into the subsurface is required to increase
the temperature of the subsurface media, and several forms
of energy transfer are used to elicit subsurface temperature
increases. The different in situ thermal remediation technolo-
gies available today in the market place are typically opti-
mized for one or several of these heat transfer mechanisms.
The selection of the most appropriate technology for any par-
ticular site will be based on the ability to optimize one or
several of these heating mechanisms for the given site geology
and hydrogeology.
9.3.1.1 Conduction
Thermal conduction is typically considered the most basic
form of heat transfer. Thermal energy from conductive
heating is transmitted by direct contact with and molecu-
lar communication between adjacent molecules, without
significant movement of the molecules.7 During conductive
heat transfer, the temperature difference (i.e., the energy
level) is transmitted between adjacent bodies, which can be
solids, liquids, or gases so long as they are in direct physical
contact with one another. For in  situ thermal remediation
projects, the input of energy typically occurs from heated
probes or wells that are maintained at higher temperatures
relative to the cooler surrounding soil. Therefore, the ther-
mal conductivity of the soil is an important criterion for heat
transfer to soil on thermal remediation projects because it
governs the amount of energy that can be transferred from
the probe into the soil for a particular temperature differ-
ential. The rate of heat energy flux (Q) from the probe is
dependent on the thermal conductivity (k) of the body (i.e.,
soil) and the temperature gradient along the energy flow
path (ΔT/Δx) according to
k * DT
Q= (9.1)
Dx
469
9.3.1.2 Convection
With thermal convection, energy is primarily transmitted
through displacement (i.e., physical circulation of mol-
ecules) of the heated body.7 Therefore, thermal convection
can only occur with fluids (i.e., liquids or gases). Fluids that
contact heated solid surface, such as a fin and tube heat
exchanger, transfer heat though conductive processes, and
then are swept away to participate in convective heating
processes. Likewise, direct injection of energy associated
with fluids or vapors that are at higher temperatures than
the soil (e.g., steam or hot air) is convective heat transfer.
Energy can also be transferred to the subsurface via a phase
change (e.g., condensation of steam), which utilizes a com-
bination of thermal convection and thermal conduction.
The rate of heat energy flux per unit time (q) from a solid
to a convective fluid is dependent on the convective heat
transfer coefficient (hc), the area of the heat transfer (A), and
the temperature differential (ΔT) between the surface and
the bulk fluid according to
q = hc * A * DT (9.2)
9.3.1.3  Joule (Electrical Resistance) Heating
Joule heating, also known as electrical resistive heating, is
created by the resistance of a body to transmit electrical
energy. Resistive losses in an electrical wire, for example,
are generally a negative attribute, as this results in the heat-
ing of wire and reduces the amount of energy available to do
work at the end of the wire. An example of where resistive
losses and Joule heating are useful would be a toaster oven.
The electrical resistance heating (ERH) used for thermal
remediation of soil and groundwater at impacted sites takes
advantage of Joule heating and the relatively poor electrical
conductive properties of soil to generate heat similar to a
toaster oven. For in situ thermal remediation projects opti-
mized for electrical resistive heating, the subsurface can be
directly heated by applying a voltage potential across the
soil between a series of electrodes. A portion of the electri-
cal current is converted to heat energy due to the electrical
resistivity of the soil water matrix. Joule’s law provides the
relationship between the amount of electrical energy con-
verted into heat (Q), when a time invariant current (I) flows
through an electrical conductor with resistance (R) for a time
duration (t):
Q = I 2 Rt (9.3)
The International System of Units (SI) unit for energy is
the Joule (J), named after James Prescott Joule. This unit
of energy is applicable to mechanical energy (or work), heat
energy, and electrical energy. For mechanical energy, 1 J = 1
Newton (N) meter (m) = 1 kilogram (kg) · m2/second2. Using
the SI relationships, the equivalent is 1 J = 1 Volt (V) · Ampere
(A) · second (s).
470
For electrical energy, given the time invariant current,
the Power (P) consumed by a resistive load is given by P =
Qt, and therefore, the power consumed by a resistive load
is P = I2 R.
The (derived) SI unit for power is the Watt (W), named
after James Watt, and is measured in Joules per second:
1 W = J/s . (9.4)
Ohm’s law equivalently states the potential difference (V)
across an electrical conductor (in this case between two elec-
trodes in the subsurface) is related to the current I and the
electrical resistance R by
V = I × R (9.5)
This yields the more generalized form of electrical power:
P = V × I (9.6)
9.3.1.4 Combustion/Smoldering
The combustion/smoldering technology has been recently
introduced as a viable remedial strategy for soils impacted
with NAPLs that have a moderate to high fuel value (e.g.,
fuel oil, creosote, coal tar). During the in  situ combustion/
smoldering process, hot air (e.g., 400°C) is injected into the
subsurface (above and/or below the water table) to initiate
combustion or smoldering of the NAPL ganglia present in
the pore spaces and energy is released from the fuel NAPL
sources as it burns slowly belowground. With continued
injection of air, the energy released from the combustion
process progressively heats up the surrounding soil matrix
and fuel, resulting in propagation of the combustion front,
due to conductive and convective heat transfer processes.
Following initial ignition of the fuel, no additional energy
input is required to the subsurface, as the energy required
for the combustion and destruction of the NAPLs is derived
from the self-combustion of the fuel hydrocarbons contained
in the NAPL. The process can be controlled by the varying
injection pressure and rate of air injected at the igniter well.
The radius of influence of an igniter well is governed by the
distribution of NAPL around the well, the permeability and
anisotropy of the soil, and the air injection pressure and rate.
Typical radius of influence (ROI) for an igniter well ranges
between 6 and 12 ft. For a full-scale project, a network of
igniter wells are installed throughout the treatment zone, the
spacing of which is based on the ROI and which are operated
sequentially to remediate the entire site.
Proof-of-concept experiments and several field pilot tests
have demonstrated that a self-sustaining in  situ smolder-
ing process can be initiated. For sites with heavy oils in
coarse-grained soils, for example, pilot tests have been able
to achieve relatively complete NAPL removal. Initial lab
and field experiments have suggested that the process could
be applicable to soils with moderate to high permeability
Remediation Engineering
and for relatively nonvolatile NAPLs with moderate to high
fuel values.
9.3.1.5  Radio Frequency or Microwave Heating
Dielectric materials present in the subsurface (e.g., polar
compounds such as water) can be directly heated bypass-
ing high-frequency oscillating radio waves or microwaves
through the subsurface between buried antennae. The oscil-
lating electromagnetic fields cause the molecules of the
polar compounds to vibrate rapidly, increasing the kinetic
energy and temperature of the subsurface materials. In the
subsurface at a contaminated site, the bulk of the energy is
absorbed by the water, and little direct heating of the solid
portion of the matrix or nonpolar contaminants occurs.
Thus, the primary mode of heating is the conduction of
energy from heated water to the surrounding matrix and
convection and condensation of any steam that is produced.
Although there have been some field demonstrations of this
approach, its commercial application appears limited due to
the high cost of the antennae arrays and low energy transfer
efficiencies. Therefore, this approach is not discussed fur-
ther in this chapter.
9.3.2 Energy Transport and Storage Mechanisms
As a site is heated and subsurface temperatures increase,
energy can be transported within the subsurface by heat
conduction in the porous and solid matrix as well as heat
transport by fluid motion. The terms “convection” and
“advection” are often used interchangeably to describe
energy transport due to movement of heated fluids.
Convection actually includes heat diffusion as well as advec-
tion; however, heat transport by fluid diffusion tends to be
minor compared to convection and conduction. In general,
heat convection is the most effective transport mechanism
in materials with moderate to high permeability, such as
sand and gravel, while conduction is the dominant process
in materials with lower permeability such as silt, clay, and
low porosity/permeable bedrock.
9.3.2.1 Thermal Conductivity and
Thermal Diffusivity
Thermal conductivity is a measure of the ability of a material
to conduct heat. Thermal diffusivity is a measure of material’s
ability to conduct heat relative to its ability to store heat (i.e.,
thermal conductivity divided by heat capacity; see next sec-
tion). Heat can migrate relatively quickly through a material
with high thermal conductivity, while heat flow into a mate-
rial with high thermal diffusivity will result in a relatively
rapid temperature increase. Typical values of thermal conduc-
tivity are shown in Table 9.2.
The thermal conductivity of solids and fluids can vary with
temperature, and representative values should be selected for
the temperature range of interest. Measured thermal con-
ductivity of porous materials is a combination of conduction
and convection occurring within the pore fluids. The change
Soil Treatment 471

conductivity of the soil particles and the fluid contained in

TABLE 9.2 the pore space:
Thermal Conductivity Values (Watts per Meter‐Kelvin)
kbulk = k particle (1- n) + k fluid (n) (9.7)
Temperature (°C)
Material/Substance 25 125 225 where n is the soil porosity (unitless).
Common building materials
Aluminum 205 215 250 9.3.2.2  Heat Capacity
Asbestos-cement board 0.744 The specific heat of a material is the energy required to raise
Asphalt 0.75 the temperature of a unit mass by one degree and is typically
Cellulose acetate, molded, sheet 0.17–0.33 expressed as kJ/kg/K or the kJ required to increase 1 kg of
Cement, Portland 0.29
soil or material 1 K, where kJ is kilojoules, kg is kilograms,
Cement, mortar 1.73
and K is Kelvin. The product of the specific heat and density is
Copper 401 400 398
Carbon steel 54 51 47
referred to as the heat capacity and provides a measure of the
Fiber insulating board 0.048 material’s ability to store heat. Heat capacity is expressed as
Fire–clay brick 500°C 1.4 kJ/m3/K or the kJ required to increase the temperature of 1 m3
Glass, window 0.96 of soil or material by 1 K, where kJ is kilojoules, m3 is cubic
Gypsum board 0.17 meters, and K is Kelvin. The heat capacity of soils and fluids
Hardwoods (oak, maple) 0.16 change with temperature; however, the range of variation for
Iron, cast 55 heat capacity of different soils is generally small compared
Plaster light 0.2 to the variability of other parameters such as permeability.
Plastics, foamed (insulation materials) 0.03 Similar to thermal conductivity, the bulk heat capacity of a
Plywood 0.13 soil is the combined heat capacity of the soil particles and the
Subsurface materials fluid in the pore space.
Clay, dry to moist 0.15–1.8
Clay, saturated 0.6–2.5 9.3.2.3  Heat of Vaporization
Granite 1.7–4.0
The heat of vaporization (kJ/kg) is the amount of energy
Gravel 0.7
required to vaporize a unit mass of material, that is, to boil a
Ground or soil, moist area 1
Ground or soil, dry area 0.5
kilogram of liquid until it is entirely converted to gas. If the
Limestone 1.26–1.33 conversion takes place at the liquid boiling point, the energy
Rock, solid 2–7 input does not result in a temperature increase. The total heat
Sand, dry 0.15–0.25 required to vaporize a liquid that is originally at ambient tem-
Sand, saturated 2–4 perature will be the sum of the heat required to raise the liq-
Sandstone 1.7 uid to its boiling point (product of specific heat, temperature
Soil, clay 1.1 increase, and mass) and the total heat required to vaporize
Soil, with organic matter 0.15–2 the liquid (product of heat of vaporization and mass). When
Soil, saturated 0.6–4 considering liquids present in the subsurface, the total heat
Water 0.58 required to vaporize a specific volume or mass of liquid is the
Water, vapor (steam) 0.016
sum of the heat required to raise the liquid and the surround-
Common contaminants at remediation sites ing matrix (porous media or bedrock) containing the liquid to
Alcohol 0.17
the boiling point, plus the heat required to vaporize the mass
Benzene 0.16
of liquid.
Engine oil 0.15
Gasoline/kerosene 0.15
9.3.2.4  Heat of Condensation
Methanol 0.21
Oil, machine lubricating SAE50 0.15
The heat of condensation (kJ/kg) is the amount of energy
released when a gas phase condenses into a liquid. For
Other
example, when steam is injected into the subsurface at the
Air, atmosphere (gas) 0.024
start of a project, energy or heat is initially transferred to
Source: Engineering ToolBox, http://www.engineeringtoolbox.com/thermal-­ the matrix and liquids as the steam condenses and con-
conductivity-d_429.html. verts to a liquid. Energy and heat are also transported in
the subsurface due to thermal conduction and convection
associated with the hot condensed water. The steam con-
in measured thermal conductivity may be influenced by densation front moves out radially from the steam injec-
increased convection with temperature. Additional thermal tion well over time as the subsurface near the well achieves
conductivity values are available in the published literature, the boiling point of water. In this way, energy delivery is
for soil materials7,8 and for fluids.9 Note that the bulk ther- efficiently targeted to the water and matrix still below the
mal conductivity (kbulk) for a soil is the combined thermal boiling point.
472 Remediation Engineering

9.3.3 Treatment and Removal Mechanisms removal of such compounds (i.e., achievement of stringent drink-
ing water standards) using thermal, typically requires boiling off
The primary removal mechanism for most thermal treatment and/or flushing at least one entire pore volume of water.
technologies is volatilization and phase change from a liquid to
a gas phase. For VOCs and some SVOCS, heating the soil and 9.3.3.3 Boiling at NAPL–Water Interface: Formation
groundwater within the treatment zone to 100°C (i.e., the boiling of Low-Boiling Point Azeotropes
point of water) will generate a gas phase consisting of water and
The separation of two or more organic chemicals by frac-
the organic chemical(s) in the soil pores. This gas phase facili-
tional distillation can be difficult when the components have
tates the volatilization, partitioning, and transport of the chemical
similar boiling points.10 An azeotrope is a constant boiling
mass through and out of the treatment zone. Higher temperatures
mixture with two or more liquids (e.g., water and trichloro-
are required for higher molecular weight chemicals that have
ethene [TCE] DNAPL) whose fractions cannot be changed
boiling points significantly higher than water, but the primary
by simple distillation. When an azeotrope is boiled, the vapor
removal mechanism is the same: volatilization and phase transi-
has similar proportions of the constituents as the unboiled
tion. Thus, the removal effectiveness is largely dependent on the
mixture. However, many organic compounds found at reme-
ability to uniformly achieve the required temperature throughout
diation sites, especially CVOC-based DNAPLs, form a het-
the treatment volume and sometimes above the targeted volume
erogeneous azeotrope, with an eutectic boiling point that is
to ensure sufficient treatment is uniformly achieved and that the
typically lower than the boiling point of the pure compound.11
mobilized chemical mass is efficiently removed from the subsur-
Therefore, CVOC-based DNAPLs in contact with liquid
face and does not condense in cool regions.
water will begin to coboil at lower temperatures, promoting
Other removal mechanisms include enhanced direct physi-
more effective removal of the DNAPL in groundwater. Due
cal removal due to favorable changes in LNAPL/DNAPL fluid
to Raoult’s law, the vapor pressures of the two components
properties such as viscosity and thermally enhanced autode-
heterogeneous azeotropes systems are additive, such that they
composition reactions such as hydrolysis of chlorinated eth-
coboil at a temperature below the boiling points of each of the
anes.9 At some high-temperature sites and applications, direct
pure substances. Table 9.3 provides a comparison of the pure
in situ thermal degradation such as oxidation and/or pyrolysis
substance boiling points and the heterogeneous azeotrope
can also be significant or, as in the case of the smoldering
with water boiling point for several CVOCs typically found
technology, the primary removal mechanism.
at many thermal remediation sites. Figure 9.6 provides an
9.3.3.1  Vaporization and Volatilization example of a water tetrachloroethene (PCE) DNAPL system.
For thermal treatment of CVOC-based DNAPL, the dominant
mechanism is vaporization, as illustrated in Figure 9.5, show-
ing how boiling leads to steam formation and gas flow rich in TABLE 9.3
contaminant vapors out of the pore matrix. Note the continu- Comparison of Pure Substance Boiling Points and
ous gas phase in the right image where pore fluids are boil- Heterogeneous Azeotrope with Water Boiling Point
ing and creating steam, which sweeps up and out to recovery
Chlorinated Pure Substance Heterogeneous Azeotrope
wells screened in the vadose zone.
Solvent Boiling Point (°C) with Water Boiling Point (°C)

9.3.3.2  Preferential Partitioning into Vapor Phase PCE 121 88

Henry’s law constants for organic chemicals that are sparingly TCE 87 73
1,1,2-TCA 114 86
soluble or immiscible in water increase substantially as a function
CT 77 67
of temperature. This leads to preferential partitioning from the
CF 61 56
aqueous phase to the vapor phase at elevated temperatures. This
MC 40 39
doesn’t occur for miscible compounds such as acetone, alcohols,
MTBE, and 1,4-dioxane. Because of their high solubilities in Source: Todd, J.P. and Ellis, H.B., Applied Heat Transfer, Harper and Row
water and low Henry’s constants, even at elevated temperatures, Publishers, New York, 1982.
they will preferentially remain in the water phase. Effective

1 mm

FIGURE 9.5  Steam formation at the pore scale at a thermal remediation site. (Courtesy of Terra Therm, Inc., Massachusetts, USA.)
Soil Treatment 473

800
1 atm
700 Vptotal =Vpwater + VpNAPL
88°C
600

Total pressure
Vapor pressure (mm Hg) 500
Vapor pressure PCE
400 Vapor pressure of
water
PCE
300

200

100
121°C
0
0 10 20 30 40 50 60 70 80 90 100 110 120 130
Temperature (°C)
88°C

FIGURE 9.6  Water-PCE DNAPL Co-boiling point. (Arcadis, Risk from soil gas at fuel service stations, Internal communication, 2015.
© 2015 Arcadis.)

9.3.3.4  Fluid Property Changes
Many of the physical properties of VOC-based NAPLs and
CVOC-based DNAPLs change as a result of temperature
increase during the life cycle of an in situ thermal remedia-
tion project. For example, vapor pressure increases expo-
nentially with increasing temperature. Effective solubilities
also typically increase, albeit linearly with increasing tem-
perature. Conversely, the relationship between temperature
and viscosity is inversely proportional for all substances.12
However, DNAPL density, viscosity, surface tension,
and solubility typically varies less than the properties of
LNAPLs from fuel hydrocarbons. The temperature depen-
dence of these physical properties generally promotes the
improved performance of in situ thermal remediation proj-
ects. Figures 9.7 and 9.8 summarize some of the physical
and chemical property changes that can occur during heat-
ing for LNAPL and water, TCE, and PCE, respectively.
Figure 9.9 provides a summary of the strong temperature
dependence of vapor pressure for a range of VOCs, SVOCs,
PAHs, PCBs, and dioxins.
The formation of steam from boiling groundwater also
promotes in situ steam stripping, which helps to remove the
contaminants from saturated and vadose zone soils and pro-
vides a mechanism for advection for the mobilized substances
from its prior adsorption site.
9.3.3.5 Temperature-Activated
Autodecomposition Reactions
Temperature-activated autodecomposition reactions (TAADR)
such as hydrolysis and dehydrohalogenation represent a highly
effective and less energy intensive in  situ thermal reme-
diation approach to remove chlorinated alkanes, especially
1,1,1-trichloroethane (1,1,1-TCA) from the subsurface.13 For
chlorinated alkanes, TAADR predominantly involves reac-
tions that can be classified into two pathways that can occur
simultaneously. The first is hydrolysis, which is defined as the

Fuel oil, 14 gravity No. 5 fuel oil

400 14
350 12
300 10
Viscosity (cSt)
Viscosity (cp)

250
8
200
6
150
4
100
50 2

0 0
20 60 100 140 0 20 40 60 80 100 120 140
Temperature (°C) Temperature (°C)

FIGURE 9.7  Viscosity reductions of oil with increasing temperatures.

474 Remediation Engineering

1.6 7
TCE

Henry’s law constant (—)

1.4 6 PCE

Vapor pressure (atm)

1.2 5
1.0 H2O
4 TCE
0.8
3
0.6
PCE 2
0.4
0.2 1
0.0 0
0 20 40 60 80 100 0 20 40 60 80 100
(a) °C (b) °C

FIGURE 9.8  (a) Temperature dependence of vapor pressure for TCE, PCE, and H2O. (b) Temperature dependence of Henry’s Law constant
for TCE, PCE and H2O.

Target temperature: 100°C >100°C

700
Vapor pressure (mm Hg)

600
hene

0)
ne

ne

–126
roethe

thale
Trichloroet

500

(1242
Naph
Perchlo

400

PCBs
s
PAH

ins
300
Diox

(after TerraTherm)
200

100

0
0 100 200 300 400 500
Temperature (°C)

FIGURE 9.9  Vapor pressures increase exponentially during heating. (Courtesy of Terra Therm, Massachusetts, USA.)

decomposition of a dissolved chemical compound by reaction 9.3.4 Thermal Treatment Technologies

with water.14 The hydrolysis reaction typically proceeds by the
nucleophilic substitution of a halogen with a hydroxyl anion. 9.3.4.1  Electrical Resistance Heating
The following equation shows the hydrolysis reaction of 1,1,1- ERH is the process of passing electricity through the soil
TCA to produce 2-chloropropanol, which further degrades to between electrodes installed in the ground and heating the
acetic acid: soil by Joule heating (Figure 9.10). Both the saturated and
vadose zones can be heated with ERH providing that suffi-
C2H 3Cl3 + H 2O ® C2H 3Cl 2OH + HCl (9.8) cient soil moisture and electrical conductivity exists for effi-
cient and safe current flow.15,16 For ERH treatment, electrodes
The second is dehydrohalogenation, which proceeds by the and vapor extraction wells are typically installed in a trian-
elimination of a halogen bonded to one carbon atom with the gular grid pattern across and surrounding the targeted area,
simultaneous removal of a hydrogen bonded to a neighboring and phase-separated alternating current electricity is applied
carbon atom. As a result of the elimination of the halogen to the electrodes.
and hydrogen, a double bond is formed between the partici- Two types of ERH, three-phase and six-phase soil heat-
pating carbon atoms, replacing the original single bond. For ing, were developed and later demonstrated in the field. Due
1,1,1-TCA, sequential hydrolysis, elimination, and a dehy- to the flexibility of the electrode arrays used for three-phase
dration step produce both acetic acid and 1,1-dichloroethene ERH in accommodating the variable shapes and sizes of
(1,1-DCE). A summary of compounds susceptible to and not treatment areas, three-phase heating is the dominant form
susceptible to TAADR reactions are included in Table 9.4, of ERH used commercially to remediate full-scale sites.
including their estimated half-lives at varying temperature Six-phase ERH is sometimes used for small (i.e., one single
ranges. array of six electrodes arranged in a hexagonal pattern with
Soil Treatment 475

TABLE 9.4
Summary of Calculated Half-Lives for Various Chlorinated Ethanes at Varying Temperatures
Half-Life (Days)
Compound 10°C 20°C 40°C 60°C 80°C 95°C
Relatively recalcitrant compounds
1,2-Dichloroethene (1,2-DCE) 1.3E+14 2.0E+13 6.4E+11 3.2E+10 2.2E+06 3.6E+08
Tetrachloroethene (PCE) 5.2E+12 8.7E+11 3.4E+10 2.0E+09 1.6E+08 2.9E+07
1,1-Dichloroethene (1,1-DCE) 7.5E+11 1.1E+11 3.7E+09 1.8E+08 1.3E+07 2.1E+06
Trichloroethene (TCE) 7.1E+09 1.1E+09 4.1E+07 2.2E+06 1.6E+05 2.8E+04
Compounds potentially susceptible to heat-activated
autodecomposition reactions
Chloroform (CHCl3) 6.9E+06 1.4E+06 8.0E+04 6.1E+03 590 120
1,1,2-Trichloroethane (1,1,2-TCA) 3.4E+05 9.6E+04 9.4E+03 1.2E+03 190 56
1,2-Dichloroethane (1,2-DCA) 2.5E+05 5.5E+04 3.6E+03 330 39 9.3
1,1-Dichloroethane (1,1-DCA) 2.3E+05 4.8E+04 2.7E+03 210 23 5.0
Carbon tetrachloride (CC14) 1.7E+05 3.2E+04 1.6E+03 110 11 2.2
1,1,1,2-Tetrachloroethane (1,1,1,2-TCA) 1.3E+05 3.3E+04 2.7E+03 302 43 11
Chloroethane (CA)1 8.1E+03 1.9E+03 130 13 1.6 0.39
1,1,1-Trichloroethane (1,1,1-TCA 4.6E+03 860 41 2.8 0.26 0.052
1,1,2,2-Tetrachloroethane (1,1,2,2-TCA 840 270 35 5.7 1.2 0.39
1,2-Dichloropropane (1,2-DCP) 16 3.2 0.18 0.014 0.0015 3.2E−04

Sources: Washington, J., Groundwater, 33(3), 1995; Jeffers, T.H. et al., Biosorption of metal contaminants using immobilized
biomass: Field studies, Report of investigations 9461, Bureau of Mines, U.S. Department of the Interior, 1993.

Contaminant vapors and steam

100–1000 V 100–1000 V
+/– +/–

Rate and Groundwater

uniformity of flux < 1 ft/day
heating governed
by soil resistivity

Varies by a factor
of ~200

FIGURE 9.10  Traditional ERH using continuous long electrode. (Courtesy of Terra Therm, Inc., Massachusetts, USA.)

a central neutral) project or pilot tests, but the complexity of
designing and laying out large six-phase electrode arrays is a
significant impediment to the applicability of this approach
to full-scale sites.
As the electric current passes through the targeted subsur-
face soil volume between the electrodes, the treatment zone’s
resistance to the current flow causes the formation to heat up
(both soil and water). This results in an increase in temper-
ature until the boiling point of water (e.g., 100°C at 1 atm)
or the two-component, NAPL–water system boiling point is
reached at the target depth and in situ pressures.
After reaching the in  situ boiling temperature, fur-
ther energy input is applied to cause a phase change of the
groundwater and any NAPL to steam (water and contaminant
vapor) within the soil matrix pores, in both the vadose and
saturated zones. Boiling and vaporizing the liquid (water and
NAPL) contained in one soil pore results in the formation of
approximately 1600 pores of steam. The steam and contami-
nant vapors produced at the pore scale push outward and rise
upward due to buoyancy effects until it reaches the vadose
zone, where it is extracted through a series of screened vapor
extraction wells for aboveground treatment. The formation
476
FIGURE 9.11  Example electrode for ET-DSP. (Courtesy of McMillan-McGee Corp.)
of steam also results in steam stripping, which helps remove
adsorbed contaminants from saturated and vadose zone soils.
The unsaturated soil zone in the vicinity of the electrodes
within the treatment area is held under neutral or slightly neg-
ative pressure by inducing a vacuum on the network of extrac-
tion wells, causing the volatilized CVOCs and steam to be
collected and preventing migration of contaminates outside
of the treatment zone.
Because heating of soil using ERH relies on the presence of
soil moisture for electrical conductivity and current flow, the
maximum treatment temperature is generally limited to about
100°C (dependent on the depth below the water table and the
hydrostatic pressure). In addition, ERH typically requires
the addition of water and sometimes a conductive solute
(e.g., potassium chloride [KCl]) at the electrodes to maintain
electrical continuity. When water is added to the electrodes,
groundwater extraction must be incorporated into the overall
design to maintain hydraulic control during heating.
Electro-Thermal Dynamic Stripping Process™
(ET-DSP™) is a thermal heating process patented by
McMillan-McGee Corp, Calgary, Alberta, Canada, that
combines ERH with active steam generation and convection
heating, by incorporating a water injection system at the elec-
trodes to generate steam in  situ. ET-DSP uses finite-length
electrodes, typically 6–12 ft long, which are engineered to
maximize the power density distribution within the treatment
Rate and
uniformity of
heating governed
by thermal
conductivity
Varies by a factor
of ~4
FIGURE 9.12  Thermal conduction heating (TCH) using electric heaters. (Courtesy of TerraTherm, Inc., Massachusetts, USA.)
Remediation Engineering
volume (Figure 9.11). This provides uniform heating across
the entire length of each electrode and results in more uni-
form subsurface heating across the entire treatment volume.
ET-DSP also manages the power delivered to individual
electrodes through a process called time distributed control,
which allows discrete targeting of specific areas for heating
on a minute-by-minute basis, thereby optimizing the applica-
tion of electrical energy.
When the temperature achieves the boiling point of water,
steam is generated in  situ and extracted via recovery wells.
Laboratory studies demonstrated that thermodynamic changes
induced by ERH can lead to very effective removal of CVOCs
from silts and clays.18 Since the late 1990s, more than 300
commercial full-scale implementations of both three- and six-
phase ERH have been completed,19,20 some by the trade name
ET-DSP.21 Most of these applications have been for treatment
of CVOCs, because ERH heating is limited to achieving the
boiling point of water. Once the water has boiled off, elec-
trical conductivity becomes negligible and further heating
ceases and achieving higher temperatures is impossible.
9.3.4.2  Thermal Conduction Heating
Thermal conduction heating (TCH), also named in situ ther-
mal desorption, is a soil remediation technology in which
heat and vacuum are applied simultaneously to the subsurface
to heat both soil and water (Figure 9.12). A network of steel
Contaminant vapors and steam
Groundwater
flux < 1 ft/day
Soil Treatment
heater wells consisting of continuous, sealed steel casings are
installed using conventional drilling techniques through the
entire treatment interval. The most common form of TCH
heater utilizes electrical current applied to electric heating
elements within the casings to create the heat source. Gas
fired heaters are also now commercially available. The heaters
(electric or gas) used in TCH systems are capable of achiev-
ing temperatures approaching 600°C–700°C at the heaters
(Figure 9.13). Heat flows into the soil primarily by thermal
conduction due to the large temperature gradient between the
heaters and the surrounding soil.
For VOC sites, the soil and water are heated to the boiling
point of water (100°C at 1 atm). As the soil is heated, water is
boiled and DNAPL constituents in the soil are coboiled and
vaporized. The resulting steam and vapors are drawn toward
extraction wells for removal and aboveground treatment.
Unlike ERH, TCH can also be used to heat soil to tempera-
tures greater than 100°C for removal of higher boiling point
chemicals such as SVOCs and PAHs, PCBs, and dioxins (e.g.,
250°C–325°C). To achieve temperatures above 100°C first
requires boiling off the water present in the subsurface. This
can be readily achieved in the vadose zone if surface water
infiltration is managed and limited and below the water table
if groundwater flux can be limited.
Compared to fluid injection processes, the conductive heat-
ing process is very uniform in its vertical and horizontal sweep
(i.e., the entire treatment zone is uniformly heated). This is
GTR thermal control unit
Inlet. air
Natural gas, propane,
or other fuel
FIGURE 9.13  Thermal conduction heating using gas/fuel fired heaters. (Courtesy of G.E.O., Inc., http://www.georemco.com/.)
477
because the thermal conductivity of a wide range of soil types
varies by only a factor of about four over the complete range
of soil types (sand, silt, clay, gravel, and even bedrock) and
moisture contents. Thus even in highly heterogeneous set-
tings, TCH heating can be robust and highly predictable if
designed, constructed, and implemented properly.
Compared to fluid injection processes, which in hetero-
geneous soil tend to be limited by preferential flow through
high permeability zones and bypassing of lower permeability
regions, the TCH process is much more uniform. More than
75 TCH projects have been completed to date.
9.3.4.3  Steam-Enhanced Extraction
Steam is best applied for heating subsurface zones on the
higher range of permeability and has seen extensive use in
enhanced oil recovery (Figure 9.14). Steam is generated
aboveground and injected via wells screened over targeted
portions of the treatment zone. Steam-enhanced extraction
(SEE), the ISTR process combining steam injection, aggres-
sive fluids extraction, and cyclic depressurization, has been
utilized in a number of field demonstrations and full-scale
cleanups.
The injection of steam heats the soil and groundwater to
the boiling point of water and enhances the release of contam-
inants from the soil matrix by decreasing viscosity, increasing
removal rates due to volatilization, and increasing recovery
rates due to steam stripping. Steam injection may also destroy
Contaminant vapor
and steam
Clean air
exhaust
478
Steam
Rate and uniformity
of heating
governed by soil
permeability
varies by a factor of
102–104
FIGURE 9.14  Steam enhanced extraction. (Courtesy of TerraTherm, Inc., Massachusetts, USA.)
some contaminants. As steam is injected through a series of
wells within and around a source area, the steam zone grows
radially around each injection well. The steam front drives
the contamination to a system of multiphase extraction wells
in the saturated zone and soil vapor extraction wells in the
vadose zone.
SEE is applicable to many compounds including VOCs;
CVOCs; various fuel hydrocarbons including benzene, tolu-
ene, ethylbenzene, and total xylenes (BTEX); some SVOCs
including naphthalene, creosote, and pentachlorophenol; and
various NAPLs. SEE is applied by injecting energy (as steam)
into the subsurface using wells or temporary steam spears
to heat soils and water to its boiling point of 100°C. The
increased temperature increases the vapor pressures of the
contaminants to drive the constituents into the vapor phase
so that they are removed with the steam. The combination
of increased temperature and vapor pressures and the pres-
ence of a pervasive and well connected steam phase provide
for rapid partitioning of contaminants from the NAPL and
dissolved and sorbed phases into the steam to promote effec-
tive removal of the contaminants from the subsurface. As the
steam is injected and the steam front forms around each injec-
tion well, hot water and NAPL will be pushed and pulled to
the extraction wells for removal.
A network of steam injection wells typically include a series
of targeted steam injection points, with screened intervals of
2–4 ft around and within the treatment zone. Depending on
the depth, permeability, anisotropy, and geology of the treat-
ment interval, more than one steam injection  interval may
be used. The spacing between steam injection wells is deter-
mined by the permeability, anisotropy (the ratio of horizontal
to vertical hydraulic conductivity), and depth of steam injec-
tion. Typical spacings between steam injection wells range
from 20 to 40 ft. The treatment zone is surrounded by steam
injection wells to push contaminants into the treatment zone
for removal (i.e., outside-in approach). A network of multi-
phase extraction wells are then used to remove water, steam,
Remediation Engineering
Contaminant vapors, steam, and liquids
Steam
K > 5 × 10–4 cm/s
NAPL, and the contaminants contained in each of these flu-
ids, from within the treatment zone and provide hydraulic
and pneumatic control. Typically, groundwater is extracted
at twice the rate of the amount of water that is injected as
steam to maintain hydraulic control. Pressure cycling of the
steam injection rate is often utilized as part of system opera-
tions to enhance removal of volatile contaminants from low
permeability materials (e.g., silt and clay layers or stringers)
interbedded within the permeable portions of the SEE treat-
ment zone. Pressure cycling is the process where, following
breakthrough of steam at the extraction wells (i.e., steam
temperature is attained throughout the treatment zone), the
steam injection system is significantly reduced (e.g., a 90%
reduction in injection pressures and rates) while maintain-
ing vacuum extraction. The reduction of pressure thermody-
namically destabilizes the system, forcing the temperature to
drop in the treatment zone and within the low permeability
materials to bring the system back into stability. To reduce
temperature and restore thermodynamic stability, the sys-
tem loses heat by evaporation of residual moisture present in
the lower permeability materials. Any volatile contaminants
sorbed or diffused into the low permeability materials are
volatized with the water and forced out into the permeable
portions of the treatment zone, where they are removed by
the vacuum extraction system. Also, steam injection can be
used in conjunction with ERH and TCH to treat permeable
portions of a site where these technologies would be limited
due to excess groundwater flux.
The following are some of the positive attributes for using
SEE at thermal remediation sites:
• Highly effective for VOCs, CVOCs, and lighter
SVOCs in permeable soils
• Can be very effective for removal of NAPL
• Very efficient delivery of energy to the subsurface
resulting in shorter heat-up times and lower costs for
energy
Soil Treatment 479

Temperature
Ignition well
controller
(during
ignition only)
Vapor cap Vapor Data
(if necessary) treatment logger Injection air

Vapors collected
under vacuum

Heater element
Clean
(used only for
initial ignition)

Thermocouple
Preheating zone probes
Coal tar Combustion front
Clean zone

Clay

FIGURE 9.15  Self-sustained active remediation (STAR). (Courtesy of Savron, Guelph, Ontario, Canada.)

• Wider spacing between steam injection wells (20–
40 ft), which reduces installation costs and access
limitations
The following are some of the potential negative attributes
for SEE:
• Applicability limited to more permeable strata (>10 –4
centimeter per second (cm/s) or 0.1 Darcy).
• Not generally suitable for shallow depths or shallow
unsaturated zones, due to limits on steam injection
pressures, delivery rates, and extent of horizontal
distribution.
• Must be combined with sufficient groundwater extrac-
tion and treatment to maintain hydraulic control.
• Requires moderate degree of anisotropy to be effec-
tive (e.g., >5 K h:Kv).
• Interbedded sands and silts or sands and clays may
require additional heating technology (e.g., ERH
or TCH) to heat low permeability strata if they are
thicker than 1–2 ft.
• Optimal designs provide a ring of steam injection
wells in clean areas surrounding the treatment
zone to push contaminants into the treatment zone,
ensuring containment, capture, and removal. This
requires good delineation of the extent of contami-
nants and access for installation of the steam injec-
tion wells.
9.3.4.4  Smoldering Combustion
Smoldering combustion is a remediation technology that
can be used to treat sites contaminated with high fuel value
contaminants such as coal tar and petroleum hydrocarbons.
The technology was developed and is commercially offered
by Savron as self-sustaining treatment for active remediation
(STAR)22 (Figure 9.15). The process is “self-sustaining” fol-
lowing a short duration, low energy input “ignition event”
where the energy of the reacting contaminants is used to
preheat and initiate combustion of contaminants in the adja-
cent area. The combustion front will propagate through the
contaminated zone provided a sufficient flux of air/oxygen is
supplied, and the minimal contaminant concentration (fuel
content) exists without any further external energy addition
following ignition. In this way, STAR is self-targeting, such
that the reaction naturally tracks through the subsurface
zones occupied by NAPL, assuming the NAPL is present
as a continuous or semicontinuous source zone, and self-
terminating, such that the reaction naturally ceases when no
NAPL remains. Another potential benefit is that with STAR,
the conveying of NAPL or contaminated groundwater to the
surface for treatment is not required.
9.3.4.5 Low-Temperature In Situ Thermal
Remediation
Low-temperature in  situ thermal treatment is fast evolv-
ing as a field of remediation. In many cases, applications of
this approach largely involve raising the temperature of the
480
contaminated media by few degrees and consequent enhance-
ment of biodegradation. A generally accepted rule is that
biodegradation rates double for every 10°C increase above
the baseline natural temperature of the subsurface. Low-
temperature thermal approaches usually rely on mesophilic
(20°C–40°C) or thermophilic (40°C–80°C) microbial activ-
ity. For many years, scientists and practitioners have been pur-
suing low-temperature thermal degradation process in many
different ways: (1) on the heels of traditional high-temperature
thermal remedial approaches such as ERH, (2) by exploiting
aquifer’s energy storage for heating and cooling buildings in
urban settings to enhance biodegradation at less than 25°C,
(3) hot water recirculation (80°C) to facilitate temperature
activated autodecomposition, (4) low-temperature heating
(30°C–40°C) with forced aeration to enhance biodegradation,
and (5) enhanced natural source zone LNAPL depletion at
35°C. All of the approaches mentioned here share the prem-
ise that biodegradation or abiotic destruction of contaminants
can be enhanced by using a less energy-intensive approach,
compared to traditional energy-intensive thermal remedia-
tion approaches such as ERH and TCH. Even though rela-
tively less energy intensive, the low-temperature techniques
mentioned earlier still employ conventional energy sources to
increase the temperature of the contaminant media.
Use of renewable energy capture and its use to enhance
environmental site restoration are also gaining momen-
tum. Thermal in  situ sustainable remediation (TISR) is
another technique currently being developed and have seen
some encouraging preliminary results. Pilot study using
TISR to enhance biodegradation by use of solar collectors
and a closed-loop heating system to increase subsurface
Solar
collectors
Closed-loop
heating fluid
Borehole heat
exchangers
9 21 33 42
FIGURE 9.16  Process layout showing solar collectors and borehole heat exchangers installed in the contaminant treatment zone. (Courtesy
of Davinder Randhawa.)
Remediation Engineering
temperatures and subsequent degradation has been very
encouraging.
TISR relates to heating of target contaminant treatment
zones in the groundwater and the soil by thermal conduction
and advection and subsequent enhancement of physical, bio-
logical, and chemical processes to attenuate, degrade, and
remove contaminants from the target contaminant treatment
zones. TISR provides a system and method that collects solar
heat or other heat and transfers that heat via a closed loop
and a set of borehole heat exchangers (BHEs) to subsurface
soil in the proximity of the target contaminant treatment
zones. TISR is aimed at increasing the ambient groundwater
temperature up to 40°C using renewable energy and thereby
potentially enhancing hydrolysis or enhanced biodegrada-
tion rates by three to five times. Figure 9.16 shows the pro-
cess layout.
Each BHE comprises thermally conductive, high surface
area heating element/coil placed within a targeted heating
interval to accomplish effective heat conductance to the soil
and groundwater in the subsurface and also directly to the
target contaminant zone. Vertical thickness of the target
contaminant zone is a factor in determining the length of
each BHE. Upper sections of the BHE may be insulated to
minimize heat transfer to upper layers of soil in the subsur-
face and to focus delivery of thermal energy to the target
contaminant zone.
9.3.4.6 Thermal Technologies Available
in North America
Table 9.5 presents a summary of the primary thermal contrac-
tors and treatment technologies available in North America.
Circulation pump
Water level
Contamination
51 63 72°C
Soil Treatment 481

TABLE 9.5
Thermal Technology Providers in North America
Low
Thermal Contractors North Temp TCH TCH/ERH Ex Situ
America Thermal Electric TCH Gas ERH ET-DSP SEE with SEE STAR Options
McMillan-McGee Maybe Maybe Maybe Yes Yes Maybe Maybe No No
http://www.mcmillan-mcgee.com/ W/TT W/GEO
mcmillan-mcgee/index.php
TerraTherm Maybe Yes No Yes Yes Yes Yes No Yes
http://www.terratherm.com/
TRS Group Maybe No No Yes No No Maybe No No
http://www.thermalrs.com/
GEO Maybe No Yes No No No Maybe No Yes
http://www.georemco.com/#!gas-
thermal-remediation/c12n5
Savron No No No No No No No Yes Yes
http://savronsolutions.com/
CES (Current Environmental Maybe No No Yes No No No No No
Solutions)
GRS (Global Remedial Solutions a Maybe No No Yes No No No No No
PNE Corp) http://pnecorp.com/grs/
Arcadis Yes Yes
John.LaChance@arcadis.US.com

9.3.5 Thermal Technology Selection and
Design Considerations
Often site owners or consultants fail to consider all the options
for thermal treatment and rely on one concept and cost when
making a decision. It is important to realize, for instance,
that ERH and ISTD often apply to the same sites and can
both provide equal performance, providing they are designed,
constructed, and operated properly. The decision to use one
technology over another should be decided based on careful
consideration of the following:
• COCs and remedial objectives
• Target treatment temperature necessary to achieve
remedial objectives for COCs
• Site geology and depth
• Hydrogeology and groundwater flux
• Utilities and infrastructure available at the site
Figure 9.17 presents a flowchart that can be used as a pre-
liminary guide to identify potential thermal technologies for
a site. Tables 9.6 through 9.8 provide a screening of the appli-
cability of the commercially available thermal technologies
for various COCs, remedial objectives, geologic settings, and
groundwater flow conditions, respectively.
When comparing different thermal technologies or the
same technology from different thermal providers for a site,
it is important to identify the “best value” among the designs
and proposals. This requires first preparing clear and decisive
technical specifications for the key components of the remedy
so that all designs and bids are prepared with equivalent design
elements and performance expectations. This will allow an
apples-to-apples comparison of the designs and cost proposals
so that they can be ranked and the best value option identified.
Some of the key technical aspects that should be clearly identi-
fied in the technical specifications include the following:
• Heating and temperature performance expectations
• Clear identification of treatment zone, horizon-
tally and vertically (e.g., 1 ft below ground sur-
face [bgs] to 30 ft)
• Minimum temperature of 100°C at 90% of the
temperature monitoring points within the treat-
ment zone
• No temperature monitoring point below 90°C
• Requirement for an insulated vapor cap covering and
extending beyond the treatment zone
• Multiphase or groundwater extraction wells to ensure
hydraulic control during treatment
• Minimum energy input based on preliminary
energy balance for the site accounting for conduc-
tive and convective heat losses to top, sides, and
bottom of treatment zone, energy extracted as
vapor and liquid, groundwater flux, and boiling off
a set percentage of the pore water in the treatment
zone (e.g., 20%–30%)
The various designs and proposals can then be ranked, irre-
spective of the specific heating technology, based on con-
sideration of health and safety, robustness of heating design,
robustness of extraction and treatment design, probability
of system meeting performance objectives, and probabil-
ity of meeting performance objectives within desired time
frame.
482 Remediation Engineering

Start

Are the COCs No

volatile?
Primary factors affecting selection
of treatment technology/approach
– BP/VP of COCs Yes
– Cleanup criteria No Stringent COC Yes
soil treatment TCH > 100°C
– Groundwater flux criteria?
– Bedrock
– Stratigraphy

No Is bedrock
Is there a high- Yes
present in the TCH 100°C
flow aquifer?
treatment zone?

Yes No

No Is there a thick TCH, ERH, or ET-DSPTM

SEE
clay layer? (100°C)

Yes

SEE combined with TCH,

ERH or ET-DSPTM (100°C)

FIGURE 9.17  Identification and selection of potential thermal technologies. (Courtesy of TerraTherm.)

TABLE 9.6
For Various Contaminants of Concern
Target Low Temp. TCH TCH TCH/ERH
COCs and Treatment Objectives Temperature Thermal Electric Gas ERH ET-DSP SEE with SEE STAR
VOCs (e.g., BTEX) 100°C No Yes Yes Yes Yes Yes Yes Maybe
CVOCs (e.g., PCE, TCE, TCA, DCE) 100°C No Yes Yes Yes Yes Yes Yes Maybe
CVOCs—enhance hydrolysis/ 25°C–40°C Yes Yes Yes Yes Yes No No No
biodegradation
SVOCs 100°C–250°C No Yes Yes Yes Yes Yes Yes Maybe
For example, naphthalene and Up to Up to Up to Up to
chlorobenzene 100°C 100°C 100°C 100°C
PAHs, PCBs, dioxins 250°C–350°C No Yes Yes Yes Yes Yes Yes Maybe
Miscible VOCs (low Henry’s constant), 100°C No Yes Yes Yes Yes Yes Yes No
1,4-dioxane, MIBK, MEK, acetone Boil off 1 PV
TPH/creosote/coal tar—remove mobile 50°C–100°C Maybe Yes Yes Yes Yes Yes Yes Yes
NAPL
TPH/creosote/coal tar—enhance 25°C–40°C Yes Yes Yes Yes Yes No No No
biodegradation
TPH/creosote/coal tar—stringent soil 100°C–250°C No Yes Yes Yes Yes Yes Yes Yes
standards Up to Up to Up to Up to
100°C 100°C 100°C 100°C

9.3.5.1  Target Treatment Temperature
For most CVOCs, except those that degrade readily by hydro-
lysis such as methylene chloride (MeCl2), 1,2-dichloroethane
(1,2-DCA), and 1,1,1-trichloroethane (1,1,1-TCA), the target
treatment temperature should be the boiling point of the pore
water or groundwater. Heating to 100°C or slightly lower where
vacuum is applied ensures that all DNAPL is vaporized and
removed and that steam stripping will reduce dissolved and
adsorbed concentrations.23 One mistake is to rely on the psy-
chrometric effect (air mixing with steam and lowering the boil-
ing point), since typical heterogeneity makes it impossible to
distinguish whether a zone heated to 85°C is being cleaned due
to air flow or whether it is stagnant and bypassed by the heat-
ing (Heron et al., 2005). Ultimately, this reduces the certainty
Soil Treatment 483

TABLE 9.7
Applicability of Thermal Remediation Technologies for Various Geologic Settings
Low Temp. TCH TCH/ERH
Geology Thermal Electric TCH Gas ERH ET-DSP SEE with SEE STAR
Sand and gravels—vadose zone Yes Yes Yes No Maybe Maybe Maybe Yes
Sand and gravels—saturated zone Yes Yes Yes Yes Yes Yes Yes Yes
Silt and clay Yes Yes Yes Yes Yes No Yes No
Heterogeneous mixtures Yes Yes Yes Yes Yes No Yes Maybe
Interbedded/layered systems Yes Yes Yes Yes Yes Maybe Yes Maybe
Saprolite Yes Yes Yes Yes Yes No Maybe No
Sedimentary rock Yes Yes Yes Maybe Maybe Maybe Maybe No
Fractured metamorphic/igneous rock Yes Yes Yes Maybe Maybe Maybe Maybe No
Competent rock Yes Yes Yes No No No Maybe No

TABLE 9.8
Applicability of Thermal Remediation Technologies for Various Groundwater Flow Conditions
TCH/ERH
Groundwater Flux Low Temp. Thermal TCH Electric TCH Gas ERH ET-DSP SEE with SEE STAR
Low: <1–2 ft/day Yes Yes Yes Yes Yes Yes Yes Maybe
High: >2 ft/day No Maybe Maybe Maybe Maybe Yes Yes Yes
Depth
0–50 ft Yes Yes Yes Yes Yes Yes Yes Yes
50–100 ft Maybe Yes Maybe Yes Yes Yes Yes Yes
100–500 ft No Yes No Maybe Yes Yes Yes Maybe

of reaching cleanup goals in a timely manner. Below the water
table, the target temperature increases with depth due to the
increased pressure. At a depth of 10 m below the water table,
the groundwater boils at approximately 120°C. Target tempera-
tures must be the boiling temperature to ensure steam stripping.
For sites with SVOCs, PAHs, PCBs, or other high boiling
point compounds, the target temperature will be higher than
100°C (e.g., 150°C–350°C). For these sites, the target temper-
ature should be selected based on lab treatability tests and/or
past experience for similar COCs in similar soils.
During operation, subsurface temperature monitoring is
essential. For heterogeneous sites, thermocouples should be
placed no more than 1.5 m apart vertically, and a network of
monitoring wells should cover the target area and the zones
around it.
9.3.5.2  Mass and Energy Balance
A key to a good thermal project design and execution is care-
ful energy management and monitoring of the progress in
different ways—an example of the use of a detailed energy
balance for finding problems is presented in Figure 9.18. At
this site, the energy balance indicated that a cool zone was
present (average site temperature was 80°C–90°C, but the
thermocouples showed 100°C–110°C) and subsequent drill-
ing revealed a recalcitrant zone, which was then targeted for
more intense treatment. The results were encouraging, show-
ing the importance of complete heating and the value of care-
ful monitoring and engineering checks.
9.3.5.3  Hydraulic and Pneumatic Control
Before heating, inward flow of fluids (vapor and water) must
be ensured. During SEE and DUS, inward flow of ground-
water and vapor must also be ensured. Detailed calculation
of necessary rates must be performed (steam can rapidly
displace large quantities of fluids). During ERH and ISTD,
vapor capture must be ensured by a robust vacuum extraction
system that allows a flow pathway for the steam and CVOC
vapors to extraction points. One cannot rely on steam bubbles
migrating upward to the vadose zone or on clay drying to
create permeability—the generated vapor must flow readily
to extraction wells screened in the right zones. During ERH
and ISTD, hydraulic control must be maintained, either by
boiling sufficient amounts of groundwater to create capture,
pumping, or through use of a hydraulic barrier.
9.3.5.4  Design Considerations
The following provides a summary of the key design consid-
erations for the primary thermal remediation technologies
(ERH, TCH, and SEE):
• Vapor cover: Typically required to prevent short cir-
cuiting of vapor flow around vapor extraction wells
and ensure to sufficient sweeping of the vadose zone
for pneumatic control.
• Insulated vapor cover: Substantial heat losses
occur at the ground surface due to the significant
484 Remediation Engineering

12,000 150
Steam energy
Electrical energy
10,000 Total injected 125
Total energy extracted

Calculated average temperature (°C)

Cumulative energy (million BTU)
Net energy addition
8,000 Average temperature (calculated) 100

6,000 75

4,000 50

2,000 25

0 0
10/1 10/16 10/31 11/15 11/30 12/15 12/30 1/14 1/29 2/13 2/28

FIGURE 9.18  Cumulative energy balance for a SEE project highlighting energy deficit between 11/15 and 12/30. (From Heron, G. et al.,
Thermally enhanced remediation at DNAPL sites: The competition between downward mobilization and upward volatilization, in Gavaskar,
A. et al., eds., Proceedings of the First International Conference on Remediation of Chlorinated and Recalcitrant Compounds, Monterey,
CA, May 18–21, 1998, Battelle Press, Columbus, OH, 1998, Vol. 1(2), pp. 193–198.)

temperature gradients. An insulated vapor cover is • Volume or mass of water to be boiled off to
necessary if heating and treating to the ground sur- reach treatment objectives (typically between
face and/or high vapor concentrations are expected, 15% and 30% of water present in the treatment
such as at high-mass/DNAPL sites. zone)
• Vapor extraction—pneumatic control: A separate • Heat losses to surface, bottom, and sides
network of vertical and/or horizontal vapor extrac- • Flux of groundwater through treatment zone
tion wells provides the best approach for ensuring • Heat extracted along with vapor and ground­water
adequate pneumatic control. Co-locating vapor The duration of heating is calculated by dividing the
extraction with the electrodes is counterproductive total energy requirement by the average assumed
as this will lead to preferential drying of the elec- power input rate.
trodes and removal of heat. • Presence of subsurface utilities: The best approach
• Extraction of groundwater—hydraulic control: If is to identify and remove and/or close in place sub-
water is added to the electrodes and/or the treat- surface utilities running through or within 10–20
ment zone extends below the water table and has a of the treatment zone. This is especially true of
moderate to high permeability, a separate network buried conductive metal objects, as these could
of dedicated groundwater extraction wells needs to interfere with the uniform flow of current and
be incorporated into the design to ensure hydraulic heating and possibly lead to stray currents outside
control of contaminants mobilized during heating. of the well field. Some utilities can be electrically
This is of special importance at SEE sites where isolated or grounded and left in place during heat-
water may be added to the treatment zone in substan- ing, such as concrete or fiberglass sewer or water
tial rates as steam. It is typical for most SEE sites to lines. PVC or plastic piping, including monitor-
incorporate an aggressive hydraulic control system ing wells, are typically removed and closed due
that is capable of extracting and treating twice the to temperature and material failure concerns. In
maximum steam injection rate as water. A combined some cases, utilities can be insulated and actively
vapor and groundwater extraction well system can be cooled to protect them from high temperatures
used, such as a multi- or dual-phase extraction well: during heating.
• Energy required for uniformly heating the treat- • Availability of necessary utilities
ment zone: Total energy required for heating must • Suitable electrical service
account for: • Access to sewer discharge
• Heat capacity of soil and water within treatment • Natural gas
zone (i.e., raise temperatures to 100°C) • Potable/makeup water
Soil Treatment
• Permitting
• Drilling
• Electrical
• Building/piping/general construction
• SW control
• Liquid treatment and discharge
• Vapor treatment and discharge
• UCI permit for injection of water and/or saline
• Third-party (UL) certification
9.3.6 Thermal Remediation-Performance
Monitoring
A flexible approach to sampling and data collection can not only
enhance the operation of a thermal system but also shorten the
time to reach remedial goals and lower overall costs. Although
extraction wells and manifolds are typically hot, steam rich,
and under vacuum and standard EPA methods do not exist for
collection and sample analysis, screening-level sampling can
reveal areas where problematic compounds persist and reveal
area where treatment is complete (diminishing returns). The
following sections provide an overview of the various types of
performance monitoring that can be conducted during imple-
mentation of a thermal remedy to verify: rates and uniformity
of heat-up, pneumatic and hydraulic control maintained, mass
removal, achievement of mass reductions and soil and ground-
water remedial goals, compliance with vapor and liquid dis-
charge standards, and health and safety of site workers.
9.3.6.1  Thermal Well Field Monitoring
Subsurface thermocouples are typically located in dedicated
monitoring borings to provide suitable data for evaluating
the heating progress. These data are used to monitor heat-
ing progress and identify potential problematic areas and may
also be used to determine the locations of unanticipated heat
loss or water infiltration and/or for deciding where and if it is
necessary to enhance the heating.
Subsurface temperatures are typically measured at 3–5 ft
depth intervals from the ground surface or top of the treatment
interval to the bottom of the treatment interval or just below.
Normally, the temperature monitoring system is logged auto-
matically and records temperature data to document heating
progress.
At some sites, subsurface pressure can also be monitored
using simple screened air piezometers installed to the desired
depth within the vadose zone and equipped with differential
pressure gauges or with a sampling port for manual pressure
measurement. Daily readings can be taken to ensure that the
treatment zone is under negative pressure and that pneumatic
control is maintained.
9.3.6.2  Remote Monitoring
Most thermal remediation systems incorporate a program-
mable logic controller (PLC) or series of PLCs to monitor and
record selected system operating data including relevant tem-
peratures, pressures, and flows through the aboveground vapor
485
treatment equipment, as well as the position of safety sen-
sors and controls (e.g., pressure switches, level switches, and
motor operated valves). The PLC(s) can be accessible remotely
through a wireless Internet connection, allowing the engineers
to remotely access the PLC and observe the operating infor-
mation. The PLC will also include the alarms and shutdown
conditions and notification system so that the engineers and
field operations staff are promptly notified of system problems.
9.3.6.3  Process Monitoring
Because the extracted COCs flow through the liquid and
vapor extraction manifold pipes to the treatment system and
the COCs are recovered as a vapor and to a lesser degree,
as a liquid, tracking the mass removed from the reme-
diation area is straightforward. Samples and process data
from numerous locations are normally used to optimize
the operation of the system and to provide estimates of the
following:
• Mass removed in the vapor state (measured in the
vapor conveyance manifold pipe and/or in the treat-
ment system pre/post vacuum blower)
• Mass removed in dissolved state (measured in
influent liquid extraction line from the extrac-
­
tion wells and in condensate from the moisture
separator)
• NAPL (if present) recovered from the oil–water sep-
arator (e.g., in LNAPL and DNAPL collection tanks)
• Mass load on the water treatment system
• Destruction/removal efficiency of the vapor treat-
ment system (determined by comparing the results of
vapor influent samples, with post treatment system
concentrations)
9.3.6.3.1  Screening-Level Sampling
A handheld photoionization detector (PID) or flame ioniza-
tion detector (FID) is typically be used to screen the vapor
concentrations at numerous locations by collecting a sample
using a sampling pump and a tedlar bag:
• At the wellheads from the individual extraction wells
• At the combined influent to the treatment system
• At the effluent from the effluent from the treatment
system (the final discharge point)
The PID and/or FID can also be used to screen the breath-
ing space within the well field and extraction and treatment
system compounds and locations around the perimeter of the
site to verify that ambient air quality conforms to site-specific
criteria.
9.3.6.3.1.1  Grab Samples of Process Vapor Streams for
Laboratory Analysis  Grab samples for laboratory analysis
are normally collected for verification and accurate determi-
nation of the COC load in the extracted and discharged water
and vapor streams. The methods and sampling frequency
486
depends on the COCs, treatment system design, and discharge
permit conditions.
9.3.6.3.2  Energy Balance Calculations
It is important to periodically calculate an energy balance for
the site using the following data:
• Energy delivered to the subsurface
• Energy removed in the form of hot groundwater
(estimated based on pumping rates and liquid line
temperatures)
• Energy removed in the form of steam (estimated
based on the vapor extraction manifold tempera-
ture and estimated flow rate based on pitot tube flow
readings in the manifold lines)
• Energy removed in noncondensable air (estimated
from total treatment system vapor flow rate)
• Estimated heat losses
The energy balance provides a way of estimating the aver-
age heating rate (in degrees per day) and an average treat-
ment zone temperature for the site. These numbers can be
compared to the design numbers (energy delivery, average
temperature) and the observed subsurface temperatures (from
the temperature monitoring measurements). The periodic cal-
culation of the energy balance for a site can be used to verify
that the thermocouples are providing accurate representation
of conditions throughout the treatment zone and to assess the
progress of heating.
The energy and mass balances are integral to optimizing
the performance of the remedial system. If the energy balance
matches the measured temperatures, it provides an additional
assurance that the entire treatment zone has been heated suf-
ficiently and evenly.
9.3.6.3.3  Soil and Groundwater Sampling
It is common to collect interim soil and groundwater samples
while the site is being heated and is hot (e.g., 100°C). These
data can be compared with baseline, pretreatment data to
evaluate changes in soil and groundwater concentrations
and progress toward the remedial goals. Methodologies
have been developed for collection of soil and groundwa-
ter samples from hot thermal remediation sites that mini-
mize losses of VOCS or CVOCs and ensure the data are
representative of actual subsurface conditions at the time
of sampling.
After the site has achieved the temperature performance
criteria and the interim soil and/or groundwater sampling
indicate achievement of the cleanup criteria, it is expected
that asymptotic COC removal levels will be reached.
Multiple lines of evidence, including subsurface tempera-
tures, extracted COC concentrations, and interim soil and
groundwater sampling results, will be used to determine
when extracted COC concentrations have dropped to a
level that indicates the site is ready for final confirmatory
sampling.
Remediation Engineering
Confirmatory soil samples are typically collected from a
combination of biased and randomly selected locations within
the treatment area.
Drilling for collection of interim and confirmation sam-
ples during thermal remediation can be performed safely
when not drilling into significant steam zones.25 The data
can be used to document remedial progress and final per-
formance before operation is completed. It is useful for
gathering information in zones where contaminant extrac-
tion continues despite a sense that heating is complete. Soil
and sediment sampling is particularly useful since potential
rebound after cooling would be the result of partitioning
of contaminants from the sediments to groundwater. Since
the sampling represents the potential source for rebound, it
is preferred over waiting for cooling and then performing
groundwater sampling.
9.4  IN SITU SOIL MIXING
In situ soil mixing was first used in the United States for geo-
technical and earth retention applications in the late 1950s
and early 1960s. It really became an environmental reme-
diation technology only in the 1980s, starting primarily with
inorganic compounds such as metals and then emerging as
a viable remedial alternative for organic compounds such as
MGP residuals and chlorinated solvents in the 2000s. Soil
mixing for remediation has also gained increased regula-
tory support, both on the state and federal levels over the last
few years.
Soil mixing can be defined as any technique used to
mechanically mix soils with or without additives and can be
performed ex situ or in situ. For the purposes of this discus-
sion, the focus will be on in  situ methods and applications;
however, the same principles apply to both. More commonly,
the term refers to processes by which reagents are injected and
mixed with the soil. Implementation methods vary depending
on a number of site-specific factors (e.g., type and depth of
waste, soil types, site access), including mixing reagents (wet
and dry) using crane or drill mounted augers (deep soil mix-
ing) or excavators with traditional buckets or specialized mix-
ing attachments (shallow soil mixing).
9.4.1 Introduction
In  situ soil mixing methods can be classified in two major
categories: in situ solidification/stabilization (ISS) and IST.
• ISS: Contaminants are not purposefully changed
chemically to less harmful forms, but reagents are
used to encapsulate waste material, such as NAPL,
in low permeability matrices that restricts the con-
taminants, mobility, provides long-term control of
mass discharge by reducing the surface area exposed
to groundwater leaching, and enhances geotechnical
properties (e.g., strength, permeability), eliminating
the contaminants impact on surrounding soils and/
or groundwater.
Soil Treatment
• IST: Where ISS encapsulates soil in place, IST utilizes
reagents to actively promote a chemical environment
where contaminants are purposefully destroyed or
changed to less harmful constituents via mechanisms
such as reduction or oxidation. IST achieves remedial
objectives through reduction of contaminant mobil-
ity, toxicity, and solubility. For inorganics such as
heavy metals, IST transforms the inorganics to less
soluble/toxic form and their mobility in groundwater
is reduced. For organic COCs such as hydrocarbons,
chemical processes during IST degrade the contami-
nants to less toxic and/or mobile substances.
ISS and IST of hazardous wastes have been common prac-
tice for decades. The methods described in this section could
be applied to contaminated soil, sediment, or sludge. ISS and
IST have been used to treat both organic and inorganic con-
taminants. Inorganic contaminants include metals such as
arsenic, cadmium, chromium, copper, lead, mercury, nickel,
selenium, antimony, uranium, and zinc. Organic compounds
include chlorinated solvents, coal tar wastes, pesticides, her-
bicides, petroleum constituents, PAHs, VOCs, PCBs, and
dioxins/furans.26
Some advantages (and challenges) for soil mixing as com-
pared to other types of traditional soil remediation methods
(i.e., excavation) include the following:
• Constructability: Being able to rapidly implement
and minimize excavation activities and associated
dewatering, excavation support, material handling,
transportation, and disposal activities can provide
schedule and cost advantages. Some constructability
challenges include material handling associated with
bulking/excavation of overburden obstructions.
• Deep mixing: Advancements in equipment and tech-
niques are constantly improving, which results in
faster and more effective implementation and leads
to more cost-effective solutions. A good example
of an improvement is the fact that just a few years
ago when completing IST, the reagents or mix being
used in the process typically was the same from the
start of mixing down to the target zone. Now there
are contractors that have the ability to use one drill-
ing fluid to get down to the target zone and before
reaching it change the drilling fluid and add the
required reagents needed for treatment.
• Long term control of mass flux: Encapsulation or
treatment of contaminants mitigates continued
leaching into surrounding groundwater by minimiz-
ing contact and flux through the monolith. Certain
contaminants, such as some specific metals, may
become more soluble (leachable) in certain pH
ranges associated with typical ISS reagents.
• Low sensitivity to many soil types and conditions:
ISS and to a lesser extent IST have a low sensitiv-
ity to soil types and settings and can be performed
above and below the groundwater table or even on
487
sediments below a surface water body in certain
conditions. Some exceptions include high plasticity
clays, which may experience excessive bulking and
organic rich materials, which may inhibit strength
development needed to encapsulate the waste.
• Regulatory acceptance: As mentioned earlier, there
has been an increased acceptance of ISS and IST
remedies among both state agencies and the EPA,
and increased awareness and experience is leading to
more sites being selected for ISS and IST remedies.
However, these technologies are still relatively new
in many states and countries, and regulatory chal-
lenges still exist, for example, leaching performance
testing methods and goals, and postremediation veri-
fication and monitoring still may present feasibility
challenges.
9.4.2 Planning for Implementation
Given the reliance on meeting performance requirements to
meet remedial objectives and the difficultly of reworking an
in situ soil remedy, it is typical for the appropriate reagents
and their proportions in the ISS mixture to be determined
through laboratory bench-scale treatability testing prior
to design and construction. Bench testing is performed  to
verify feasibility, determine the appropriate admixture
to meet the remedial objectives, and develop operational
parameters (e.g., construction quality assurance require-
ments) to be used during construction. A critical goal of
testing at the bench scale is mimicking field-scale imple-
mentation during the testing, and results from the labo-
ratory tests will enhance the knowledge on the choice of
binders and amounts. It should be noted that there are times
when, because of soil types or other challenges, it may not
be possible to imitate the mixing process in the laboratory,
and on those occasions, the correct reagent dosing needs
to be determined, and the actual field implementation and
confirmation that the mix design is adequate can only be
determined by field pilot testing.
Prior to starting bench-scale testing, investigation and field
sampling is performed to select and obtain samples of soil,
waste, and groundwater for testing. Accurate characteriza-
tion of soils is important to simulate field conditions during
laboratory testing and ensure successful transition to full-
scale implementation. Soil sampling is typically performed in
potential treatment areas based on historical remedial inves-
tigations, and approach may be dependent on the site specif-
ics. Depending on a number of factors, typically samples of
both source (high impacts) and fringe/perimeter samples (low
impacts) are targeted and tested. Depending on size of the
project and soil or contaminant variability, one or multiple
soil homogenates may need to be tested in the laboratory.
Due to the volume of material required for treatability testing
(approximately 5–10 gal per treatability sample/homogenate),
sample collection is typically performed using sonic or tra-
ditional auger/casing style drill rigs due to ability to collect
larger volume of samples. If in situ mixing depths are shallow
488
(a)
FIGURE 9.19  Importance of treatability testing for getting the best results in field implementation. (a) Laboratory testing. (b) Field
implementation.
enough, samples may also be collected from test pits or other
bulk soil sampling techniques. Soil samples collected for test-
ing are typically homogenized vertically but kept segregated
by location to simulate mixing techniques and provide the
necessary volume for testing. Care is to be taken during col-
lection and containerizing to preserve in situ water and con-
tamination for inclusion in bench-scale testing.
Once soil samples have been collected, ISS treatability
testing is performed. The objectives of the ISS treatability test
are as follows (Figure 9.19):
1. Evaluate the ability of selected reagents to achieve
performance requirements such as target strength
gain and reduction in permeability across the site.
2. Optimize the dosage of reagents to mitigate costs
and constructability challenges associated with over-
dosing, including excessive bulking and workability,
while still meeting site-specific criteria for strength
and permeability reduction.
3. Investigate performance of solidification between
various locations within the solidified mono-
lith. For example, testing an area where soils are
expected to be more heavily impacted with hydro-
carbon products (i.e., worst case) versus a location
at the perimeter of the monolith, where soils may
be less impacted but may be in constant contact
with groundwater.
4. (Optional) Demonstrate successful encapsulation
of COCs within the solidified monolith through
visual observation and reduction in leachable COCs
through monolith leachability testing.
9.4.2.1  Reagent Selection
The admixtures used in ISS and IST can be classified into the
following categories (Tables 9.9 and 9.10):
• Binders work to solidify the waste, with some also
engendering a degree of treatment. Binding reagents
may include Portland cement, slag cement, lime and
cement kiln dust, and fly ash.
Remediation Engineering
(b)
• Fillers work to increase the geotechnical perfor-
mance of the end product, by diminishing the inhi-
bition that some of the organics can have on the
binding reagents (e.g., free phase NAPL). Fillers
are typically inert granular fill materials such as
sands, silts, and fine gravels. Bentonite clay is also
used in certain circumstances to help reduce per-
meability for ISS applications or help maintain
impacted groundwater-reagent contact in certain
IST applications such as zerovalent iron (ZVI)-
clay mixing.
• Sorbents work to sequester organics, helping to
further reduce leaching potential and include
granulated activated carbon (GAC) and organoclay
materials and are most effective on organic COCs.
Other reagents such as bentonite clay absorb organ-
ics and attapulgite clay can absorb acid waste and
metals.
• Other reactive agents for IST can be added to main-
tain a desired geochemical condition (such as buffers
like limestone) or actually participate in destruction
of contaminant mass. Some common reactive agents
used in IST applications include oxidants including
potassium permanganate and sodium persulfate,
reductants such as ZVI and precipitants like phos-
phates. Each targets and is effective for treating cer-
tain COCs.
TABLE 9.9
Examples of Different Types of Admixtures Used
in In Situ Solidification/Stabilization
Binders Fillers Sorbents Other
• Cement • Sand • Organic clay • Buffer
• Kiln Dust • Slag • Bentonite • ZVI
• Fly Ash • Clean Soil • Iron Rich Solids • Oxidants
• Lime • Reductants
Soil Treatment 489

TABLE 9.10
Key Mechanisms and Applicability of Some Admixtures
Media Key Mechanisms Target COCs
ZVI Dihaloelimination (mostly) CVOCs
Abiotic reduction Redox-sensitive metals (U, Cr)
Sorption Arsenic (metals)
Compost/mulch Sulfate reduction–metal sulfide precipitation Metals
Anaerobic degradation/dechlorination CVOCs
Anaerobic degradation (enzymatic) Perchlorate, energetics
Microbial reduction Sulfate, nitrate
Phosphates Cation exchange Radionuclides
Precipitation of metal phosphates Lead, radionuclides
Substitution for calcium Strontium
Precipitation of calcium minerals Arsenic (at high pH)
Zeolites Cation exchange, adsorption Radionuclides, ammonium
Slag Adsorption, formation of hydroxyapatite Phosphate
Adsorption, precipitation with Ca, Fe phases Arsenic
Precipitation of metal hydroxides Metals
Dihaloelimination (unconfirmed) TCE
Limestone pH buffering, precipitation of hydroxides, Carbonates Metals
GAC Adsorption Organics

9.4.2.2  Design Goals regulatory agency, and surrounding groundwater

As discussed earlier for soil mixing, treatability testing is per- cleanup standards. Traditional soil-based leaching
formed to test impacted materials mixed with reagents against methods such as SPLP, TCLP, and DI WET do not
set performance objectives. Where the goal of IST is to add effectively represent field-scale leaching of ISS due
reagents to directly reduce the levels of soil or groundwater to the amount of surface area that is exposed to leach-
COCs to below some objective level (typically a state or feder- ing using these methods. Instead, dynamic (mono-
ally mandated concentration limits), for ISS, performance is lithic) leaching methods such as ANS 16.1 (nuclear
measured by several factors, typically including the following: waste), ASTM C1308-08 (cemented mine tailings),
and EPA LEAF method 1305 should be utilized.
• Permeability: Typically the permeability requirement
for an ISS monolith is a maximum of 1E−6  cm/s. While monolithic leaching methods are more representa-
This hydraulic conductivity is considered low enough tive than traditional methods, there are still some questions as
to prevent significant groundwater contact through to how well laboratory leaching results reflect full-scale per-
the ISS monolith. Alternatively, based on the hydrau- formance. For example, during a treatability sample for a for-
lic conductivity of the untreated aquifer, a design goal mer MGP site, the total mass of naphthalene and mass leached
of 2 orders of magnitude reduction in permeability is out of the treatability sample cylinder was measured for three
also a typical performance standard. Permeability is samples (Table 9.11). Initial results showed a significant per-
the most important factor in measuring ISS perfor- centage of mass leached from the small monoliths. Based on
mance and controlling leaching of impacted materi- the geometry of the sample and % mass leached, a penetra-
als into the groundwater. tion depth for leaching was able to be calculated. What can
• Compressive strength: Typically a minimum of
28 days of unconfined compressive strength (UCS)
of 30–50 pounds per square inch (psi) is required.
Compressive strength promotes durability of the ISS TABLE 9.11
monolith, which along with a lowered permeability Results from a Leaching Treatability Test
contributes to successful encapsulation of the COCs. Average Total Average
Site-specific goals, such as a minimum required UCS Naphthalene Mass of Naphthalene Percentage
for geotechnical stability, or a maximum UCS due to Triplicate Monolith Mass in of Mass
future usage may likely be required and should be Location Samples (μg) Leachate (μg) Leached (%)
evaluated on a site-specific basis. Sample 1 5,424 747 14
• Leachability: Leaching methods and requirements Sample 2 2,792 28 1
are not yet standardized and will vary from project Sample 3 24,445 1424 6
to project, dependent on COC types, location and
490 Remediation Engineering

(a) (b)

FIGURE 9.20  Results of groundwater modeling showing groundwater flux reductions after the implementation of ISS.

be determined is that on the treatability scale, the penetration

depths are significant on a small (~1 in.) monolith due to the TABLE 9.12
amount of surface area exposed per volume of the sample. Treatability Test Results Showing the Impacts
However, for a full-scale monolith, the penetration depth is of Organic Content on Leachability after
insignificant due to the much smaller surface-area-to-volume
In Situ Solidification/Stabilization
ratio of a typical full-scale ISS monolith. In addition, in field
scale, typically the lowest concentrations are located on the UCS (psi)
perimeter of the monolith, in the penetration area exposed to Site ID CoC Level 7-Day 28-Day Perm (cm/s)
leaching.
Site 1 Low 75 128.3 1.00E−07
As mentioned earlier, permeability is the most important High 23.2 45.8 2.20E−06
factor controlling ISS performance, including leaching. This Site 2 Low 76 136.0 4.80E−08
is also shown during groundwater modeling simulations that High 22 55.0 4.80E−07
are performed at sites to estimate groundwater flux. An exam-
ple is shown in Figure 9.20.
Modeling was performed on an untreated soil aquifer,
where the soil had a measured permeability of 1E−4  cm/s,
As shown earlier, both sites show the effects of binder inhi-
and the ISS treated material on the right was measured with
bition due to high levels of organics, with reductions in UCSs
a permeability between 1E−6 and 1E−7  cm/s. The ground-
of between 60% and 71% and up to one order of magnitude
water model showed groundwater flux reductions through the
increase in permeability between the highly impacted and
monolith between 97% and 99.6% over baseline conditions.
lesser impacted materials.
In this case, the groundwater modeling was used in conjunc-
Controlling trace metal leaching, for example, in ISS of ash
tion with permeability and compressive strength results in
materials, is also something that needs consideration during
lieu of requiring treatability samples to meet certain leaching
treatability testing. ISS using Portland cement results in a pH
requirements during bench-scale testing.
increase, and the surface charge of soil (or ash) becomes more
9.4.2.3  ISS Treatability Challenges negatively charged at elevated pH. In this condition, anionic
trace metals such as As, Sb, B, Cr, Mo, and Se may become
Several notable challenges associated with ISS feasibility that
more soluble at a high pH. Control of leaching in these cases
are focused on during treatability include binder inhibition
may be improved through additional treatment amendments
from organic compounds and trace metals leaching. Organic
such as ferric iron. Ferric iron addition promotes the forma-
compounds have a strong effect on the microstructure of the
tion of freshly precipitated iron oxyhydroxide and will help
cement paste. Almost all organic compounds are retarders in
sorb and retain the oxyanions.
cement setting, and many organic acids that strongly chelate
calcium also have strong retarding effect. Organic compounds
retard the cement setting process by forming a protective layer
9.4.3 Implementation Methods
around the cement grain.
Treatability results for two former MGP sites with VOC and Traditionally, there are two main methods implementing for
SVOC soil and groundwater impacts are shown in the follow- in situ soil mixing, deep soil mixing via augers mounted on
ing. For each site, two homogenates were created from a highly large cranes or excavators and shallow soil mixing typically
impacted area and lesser impacted area, and the same ISS mix performed via excavators either using traditional or modified
design was applied to both homogenates in each case. The UCS buckets or specialized attachments such as rotary or tiller
and permeability results for each site are provided (Table 9.12). styles.
Soil Treatment
(a)
FIGURE 9.21  Implementation of deep soil mixing for ISSS.
9.4.3.1  Deep Soil Mixing
The deep mixing method involves the mixing of soils at
large depths, typically up to 60–80 ft bgs, depending on soil
types and equipment used, it is possible to mix up to 100 ft
bgs (Figure 9.21). Deep soil mixing technology is a process in
which reagents are mixed with water in an on-site batch plant
and injected into the ground and blended with in  situ soils
using single or multiple augers between four and twelve feet in
diameter. Deep auger mixing is usually performed using augers
mounted either on a crane (e.g., Manitowac) or track mounted
drill rig (e.g., Delmag). Treatment reagents are pumped in and
are precisely measured to allow the correct proportions to be
mixed with the untreated waste soils or sludge. The augers mix
through the total depth of the impacted material in an up and
down motion to homogenize the in  situ materials and grout.
Drilling fluid is required for auger mixing (not compatible with
dry reagent mixing), which is implemented in overlapping col-
umns using multiple configurations: single patterns, block pat-
terns, panel pattern, or stabilized grid pattern.
During deep soil mixing via augers, visual confirmation of
mixing is difficult to achieve, and reliance on discreet sampling
of ISS and equipment readings is required to verify ISS mixing
is performed to the limits and homogenized effectively.
Costs for ISS using deep soil mixing techniques can vary
greatly depending on site conditions, reagent types and per-
centages, auger size, expected productivity, and depth but
generally can be expected to cost approximately $60–$100/cy
and production is typically between 250 and 500 cy/day. If
IST is the goal, the cost per cy typically increases and the ulti-
mate cost will be driven by the amount of reagent needed to
allow the chemical reaction to occur to the desired end point.
9.4.3.2  Shallow Soil Mixing Methods
Shallow soil mixing is generally considered soil mixing to
depths up to approximately 20–30 ft bgs and is generally
defined as anything accessible using traditional excavator
equipment. Shallow mixing is typically completed via excava-
tors with buckets or specialized attachments (e.g., drum mixer,
tillers). Reagents can be added via drilling fluid (grout) or dry,
potentially helping with excessively wet materials. Shallow soil
mixing is usually done in cells typically 200–600 ft2 in area.
491
(b)
Visual confirmation is also easier to achieve compared to deep
soil mixing as excavators can bring mixed material up within
the mixing bucket for visual observation. Use of common equip-
ment, access requirements, and production is also an advantage
of excavator bucket mixing (Figure 9.22).
Costs for ISS using shallow soil mixing techniques can also
vary similarly to deep mixing but generally can be expected
to cost approximately $50–$80/cy and production is typically
between 300 and 750 cy/day.
9.4.3.3  Other Soil Mixing Methods
Jet mixing or jet grouting generally involves hydraulically
mixing soils with a drilling fluid that carries the stabilizing
reagents. A significant advantage of jet mixing over other
in situ mixing methods is the smaller size of the equipment.
The jet mixing drill can be about the size of a compact auto-
mobile and thus can maneuver inside buildings and under
obstacles. The jet pump can be located some distance away
from the actual location to minimize noise levels.
The first step in the method is to position a jetting pipe at
the bottom of the treatment zone. The pipe can be the drill pipe
itself, but in hard or rock-bearing soils, holes may need to be
drilled first and the jetting pipe placed in a separate step. Next,
the jetting pipe is rotated slowly and pressurized with a grout
made of cement or slag, additives, and water. The high pressure
forces the grout out laterally through special jet parts located
in the sides of the pipe and near its bottom. The grout exits the
jet ports at very high velocity, impinges on the soil, shattering
and penetrating it for several inches or feet away from the jets.
The rotating jets destroy soil formations and intimately
and uniformly mix the native soil with cement. Finally, the
rotating pipe is drawn slowly upward at a carefully con-
trolled rate so that the jets create a nearly cylindrical column
of treated soil. Typical column diameters can be from 2 to
5 ft. Jet mixing conditions vary with design requirements, but
typical pressures are 4000–6000 psi, lift rates about 1 ft/min,
and cement/water ratios about 1 to 1. Column diameters and
properties achieved depend greatly on the native soil.
Jet grouting costs are significant compared to both deep
soil mixing and shallow soil mixing. Costs generally are on
the order of $300–$500/cy of treatment.
492
(a) (b)
FIGURE 9.22  Two examples of shallow soil mixing for ISS.
9.4.3.4  Implementation Challenges
Fluid injection and mixing creates an increase in soil vol-
ume known as swell. The amount of swell is a function of
soil type, injection volume, reagent type, and operating condi-
tions. Typical swell return is typically 15%–25% of the treated
volume, depending on the type of soil and amount of reagent
injected. However, certain soil types such as highly plastic
clays can produce swell percentages in excess of 100%. Soil
(a)
(c)
FIGURE 9.23  Typical obstructions to be anticipated during the implementation of ISS: (a) rocks; (b) buried tanks; (c) and (d) underground
structures.
Remediation Engineering
swell can have significant impacts on schedule and costs due
to material handling and disposal if not properly evaluated
during treatability.
Obstructions encountered during mixing can also cause
issues with schedule and costs during full-scale implemen-
tation (Figure 9.23). Obstructions can be either naturally
occurring (e.g., boulders) or man-made (e.g., gasholder foun-
dations). Effective characterization during planning is needed.
(b)
(b)
Soil Treatment
Shallow obstructions can be removed from the mixing zone,
but deeper obstructions that cannot be removed may have to
be left in place and mixed around using methods such as jet
grouting at a higher unit cost, as described earlier. Typical ISS
equipment cannot drill/mix through obstructions like rocks
or significant construction debris.
Additional factors that may limit the applicability and
effectiveness of the ISS include the following:
• Depth of contaminants may limit some types of
application processes.
• Future usage of the site may “weather” the materi-
als and affect ability to maintain immobilization of
contaminants.
• Some processes result in a significant increase in
volume (up to double the original volume).
• Certain wastes are incompatible with variations
of this process. Treatability studies are generally
required.
• Reagent delivery and effective mixing are more dif-
ficult than for ex situ applications.
• Like all ISTs, confirmatory sampling can be more
difficult than for ex situ treatments.
• The solidified material may hinder future site use.
9.4.4 ISS Case Studies
9.4.4.1  Case Study 1: Former MGP Site (New York)
The MGP site is located in an industrial/commercial area in
upstate New York. Environmental conditions at the former
MGP site were assessed by a series of investigations conducted
between 1971 and 2010. Site investigations involved sampling
surface and subsurface soil, groundwater, soil vapor, sedi-
ment, and surface water. Samples were analyzed for a vari-
ety of compounds, including the MGP signature compounds,
benzene, toluene, ethylbenzene, and xylenes (BTEX), PAHs,
and cyanide.
To overcome many logistical and technical challenges for
the final soil remedial action, the implementation team coor-
dinated closely with the site owner and responsible party to
develop the approach and details. The ISS remedy was suc-
cessfully implemented between February and May 2012 and
included treatment of approximately 10,000 yd3 of impacted
soil within an approximately 0.5 acre area to depths extending
24 ft below grade (Figure 9.24).
Unique site conditions were a significant factor in the
design and implementation of the site remedy. Geology
beneath the site includes a historical waste material (low-
strength, high pH), and the amount and type of coal tar var-
ied depending on area and depth. A treatability study was
performed to evaluate and optimize potential grout mix
designs that used locally sourced materials, where possible,
to achieve established narrow performance requirements.
The mix needed to meet minimum regulatory UCS and
permeability requirements but not exceed a project-spe-
cific upper bound strength limit (to allow for future exca-
vation using conventional equipment for potential facility
493
FIGURE 9.24  Implementation at a former MGP Site in New York
(Case Study 1).
expansion). For efficiencies in the field, one final grout mix
design was selected that achieved objectives across the range
of conditions. It included 1.5% Portland cement, 5% ground-
granulated blast furnace slag, and 0.5% bentonite.
From the review of a compilation of historic site draw-
ings and utility maps, it was understood that there was the
potential to encounter foundations of former MGP struc-
tures and a vast array of subsurface utilities—several that
are critical to facility operations and many from the former
MGP and subsequent facility uses that had been abandoned
in place. Therefore, the team used a variety of conventional
and innovative methods to map and assess the utilities in
the field, from utility one-call and private locators to elec-
tromagnetic and ground-penetrating radar surveys, test pit
excavations, and vacuum boring. This extra ordinary level
of precaution was exercised to prevent accidental utility
strikes/damage during remedy implementation. Once the
utility locations were understood and other key data were
collected, the remedial design was geared toward accom-
plishing the ISS work via a bucket mixing approach (as
opposed to conventional auger mixing), which ultimately
streamlined efforts and minimized mixing downtime that
would have otherwise occurred due to auger refusal associ-
ated with subsurface obstructions. The quality control (QC)
requirements of the remedial design set the stage for con-
tractor selection and implementation of the following inno-
vative approaches:
• Using excavator-mounted GPS sensors and equip-
ment to document ISS mixing locations and depths
• Using a highly automated, computer-controlled
grout plant with electronic weigh scales and elec-
tronically actuated valves to efficiently batch-
produce homogenous grout meeting the design mix
specifications
• Cutting a series of holes at strategic locations in the
excavator bucket to provide more uniform and effi-
cient mixing of the ISS grout into the impacted soil
494
All key design and performance criteria were achieved on
this project. Quality control samples demonstrated that all
soil treated by ISS met UCS and permeability requirements
without a need to remix any ISS cells.
The ISS remedial construction project incorporated sev-
eral green remediation components that benefited the com-
munity, including
• Recycling 350 tons of asphalt and more than 40 tons
of metal piping
• Pretreating and discharging greater than 4600 gal of
contaminated water to the wastewater treatment plant
• Reusing nearly 550 tons of soil/stone subbase as
backfill
• Disposing 99% of material transported off-site for
use as landfill daily cover
• Solidifying 10,000 yd3 of soil in place, as opposed
to transporting more than 500 truckloads of material
nearly 60 miles for disposal
• Reducing the amount of backfill that needed to be
imported to the site by truck by performing ISS as
opposed to excavation
• Reducing the amount of water to be managed
• Replacing a formerly leaking water line that pro-
vides the secondary water supply (potable water) to
the wastewater treatment plant with a new wrapped
cast iron water line that does not leak and provides
approximately 20 psi additional pressure
The remedial activities also resulted in certain improve-
ments to the site for the property owner, including improved
surface water runoff from an area that was historically wet,
new asphalt pavement that replaced deteriorating pavement,
improved soil conditions (increased bearing capacity) for
future facility construction, and expanded parking. The
remedial activities addressed the most heavily impacted
material at the site and achieved the design and performance
criteria.
9.4.4.2 Case Study 2: Former Creosote
Facility (Idaho)
This project at a former creosote facility on the banks of a
navigable river in northern Idaho included installation of a
750 linear feet slurry wall to 65 ft below ground surface (bgs)
for groundwater cutoff. The project also required excavation,
and thermal desorption of creosote impacted soil from ground
surface to approximately 10 ft bgs and ISS of soils from 10 to
60 ft bgs.
Predesign testing was conducted to determine appropri-
ate ISS mixes that would meet the following performance
criteria:
• UCS - 30 psi or greater.
• Hydraulic conductivity - 1 × 10 –6 cm/s or less. Con­
ductivity was measured following ASTM Inter­
national test method D5084.
Remediation Engineering
Three phases of treatability testing were performed as part
of the predesign activities, plus an additional phase during
design to further refine the successful ISS mix design. The
treatability studies for the proposed ISS mixture were per-
formed using soil collected during pre-design investigation
(PDI) activities.
Durability testing was also performed along with the per-
formance testing. The purpose of the durability testing was to
evaluate the potential degradation of the solidified material
due to reaction with site groundwater.
The results of the durability testing on ISS samples showed
that there was no mass loss after being submerged in ground-
water for 30 days and that ISS will continue to improve its per-
formance after 28 days of curing (compared to the bench-scale
results of similar mix), as the submerged groundwater con-
dition provided a good curing environment for the ISS. UCS
testing was performed on samples for durability to confirm
geotechnical performance as well. Based on the final treat-
ability and durability testing results, it was determined that an
ISS mix design consisting of 10% blast furnace slag and 5%
Portland cement met the treatability performance objectives.
In addition to the treatability testing, a site groundwater
flow model was used to analyze the effects of the upland
remedy on natural groundwater flow patterns. The model
simulations demonstrate that the ISS perimeter wall and ISS
monolith are of sufficiently low permeability to inhibit flow
from entering or flowing through the remediated area, which
was used to help convince the regulatory agencies of the suc-
cess of the ISS remedy to prevent leaching of creosote impacts
into the adjacent river.
The design components included a perimeter ISS slurry
wall, constructed using the same ISS mix design for the upland
soils, and was installed using a long-reach excavator to 65 ft
bgs. The slurry wall was installed to cutoff flow into excava-
tion and ISS areas due to the extreme amount of dewatering
that was estimated to be required (over 1900 gpm). Once the
perimeter slurry wall was installed, preexcavation activities
to remove approximately 11,500 cy of near-surface impacted
soils and allow for ISS material bulking was performed
within the ISS perimeter wall area, which was also designed
to support earth and hydrostatic pressures during excavation
activities. ISS technology was then used to solidify the soil
underlying the excavation within the ISS perimeter wall. The
volume of soil treated with ISS was approximately 26,500 cy
of subsurface materials using admixtures (e.g., blast furnace
slag cement, Portland cement, and water) to fixate/immobilize
subsurface impacted materials (Figure 9.25).
The full-scale mixing was initially carried out using both
excavator bucket mixing for cells reaching less than 20 ft bgs,
and deeper ISS cells were constructed using large diameter
auger (LDA) mixing. Shallow soil mixing with excavators
was selected due to several advantages including immediate
removal of any obstructions, homogenization of soils across
a larger area, and increased production and efficiencies.
Shallow soil mixing was performed using a PC400 excavator
with traditional excavator bucket attachment. For the deeper
areas, purpose-built mixing tools including LDAs were used
Soil Treatment
(a)
FIGURE 9.25  Implementation of ISS at a former creosote site in Idaho (Case Study 2).
to inject the ISS reagents directly into the soil. An 8.5 ft diam-
eter auger mixing tool was utilized attached to a rotary drill
head. The drilling rig used was a Delmag RH34 to achieve the
best possible production and quality for the project.
During the full-scale implementation, a real-time verifi-
cation of the mix design was carried out for each individual
daily production cell to account for the effects of soil hetero-
geneities and moisture changes. ISS samples were collected
for each daily production cell and, on the basis of the result
of visual observations and laboratory tests to define the soil
characteristics, the mix design was adjusted, if necessary.
Both the PC400 excavator and Delmag RH34 drill rig
were equipped with GPS allowing the operator to know real-
time X, Y, and Z location of the bucket/auger throughout the
mixing process. In order to avoid problems associated with
sampling of brittle soils resulting from the ISS treatment, QC
testing was based on a wet sampling approach. Samples of
freshly mixed ISS materials were sampled every 500 cy of ISS
treatment, using a hydraulic sampling device that allowed for
sampling of discreet samples anywhere in the treated soil col-
umn. Samples were poured into 3″ × 6″ plastic cylinder molds
for curing and laboratory testing for UCS and permeability.
Construction challenges associated with this site included
encountering wetter than expected materials, due to both
the soil types, which consisted of SM or ML materials and
weather, which was exceptionally wet for the season (ISS had
been scheduled to occur during the normally seasonal dry
months). Adjustments to the ISS design were made during
construction, including reducing the amount of water used in
the grout mixture added to the soils, and additional reagent
added in several areas were utilized to adjust for field condi-
tions based on visual inspection of ISS materials and early
ISS performance testing done at 7 days. These adjustments,
along with construction quality assurance procedures estab-
lished in the remedial design allowed successful completion
of the ISS remedy for the site without significant delays or
remixing being required.
Excessive and variable bulking of ISS was also a con-
struction challenge due to the soil issues discussed earlier as
well as variable thickness of ISS over the footprint. During
design, an estimated swell of approximately 25% was
495
(b)
expected, however during implementation, actual swell-
ing occurred at over 30%–35% in certain areas. Allowing
for additional capacity during excavation activities miti-
gated the effects of this and resulted in less backfill being
required than anticipated. Additionally, sequencing of the
ISS was crucial to managing swell materials, as deeper
areas of ISS generated excess swell, while shallower areas
allowed for additional capacity to accommodate swell.
Sequencing was worked concurrently with the contractor
to minimize double handling of swell materials during con-
struction, increasing construction efficiency and minimiz-
ing the project schedule, which was critical to keeping the
overall project on track.
9.4.5 In Situ Treatment (IST)
As discussed earlier, IST, unlike traditional ISS, includes a
degree of treatment by including a reactive material in addi-
tion to sorbents and binders discussed earlier. Reactive mate-
rials either participate in destruction of contaminant mass or
alter geochemical conditions and include ZVI, chemical oxi-
dants (such as persulfate), gypsum, and buffers. Of these reac-
tive materials, oxidants and ZVI will be discussed in detail in
the following sections, as they are the most common of the
reactive materials used.
The true challenge of IST of source mass is achieving
adequate contact of reactive material within highly heteroge-
neous and anisotropic aquifers. As contaminants leach from
their release point into natural aquifers, they can diffuse into
the nonmobile fraction of the aquifer via concentration gradi-
ents and groundwater migration. Subtle variations in lithology
(i.e., grain size, permeability, conductivity) over a contami-
nated thickness can result in storage of these contaminants.
The effectiveness of any reactive material to treat a contami-
nant is contingent upon contact with the targeted contami-
nants. When slugs of DNAPL contamination have been stored
within the natural soil structure, in situ mixing provides an
aggressive technique for liberating this mass and making it
available for treatment.
In situ mixing homogenizes the mixed soil and reduces the
overall hydraulic conductivity of the monolith. Contaminant
496
flux through heterogeneous and anisotropic porous media
is characteristically limited to preferential pathways vary-
ing in grain size, permeability, hydraulic conductivity, etc.
In most instances, these preferential pathways may account
for a small percentage of the vertical thickness contribut-
ing to contaminant transport. By homogenizing the entire
vertical interval of contamination, the resultant flux through
the mixed interval is dramatically reduced. Therefore, the
homogenized lithology especially with the addition of a clay,
such as bentonite, will reduce groundwater flux through the
monolith by disrupting preferential pathways, diverting flow
around the monolith.
9.4.5.1  Chemical Oxidants
The same aqueous chemical oxidation reactions discussed in
Chapter 6 can be applied as a soil remedy, as reactions will
occur within the injected slurry and within the soil moisture and
groundwater present in the soil treatment area. The effective-
ness of chemical oxidation strategies depends on several vari-
ables that describe the oxidant, target compounds, nontarget
compounds, and aquifer or vadose zone matrix. Among these
are the following:
• Kinetics of the oxidant-target contaminant reaction,
as the reaction rate will likely decrease due to con-
tact efficiency as the treated area cures
• Nontarget chemical oxidant demand that may be
present in the formation, which must be overcome
with excess oxidant application
• Oxidizable compounds sequestered in nonaqueous
phases, such as natural soil organic matter or resid-
ual petroleum hydrocarbons associated with con-
taminant releases that are “shielded” from oxidant
reactions
These variables are highly site dependent and determine the
potential rates of reaction, the mass of oxidant that must be
injected to achieve remedial objectives, and the potential
amount of contaminant that will remain when oxidation reac-
tions have reached their completion.
There are four basic oxidants available for in situ applica-
tion: hydrogen peroxide, ozone, permanganate, and persulfate.
Activated persulfate is a radical-based chemical oxidation sys-
tem that offers a slower (and more controllable) reaction but
employs a highly reactive sulfate radical that can effectively
oxidize a wide variety of organic compounds. Therefore, per-
sulfate has multiple advantages for safe, controlled, and effec-
tive oxidation of contaminants, when compared to the other
oxidation systems, including the following:
• A variety of activation strategies that can be engi-
neered to generate sulfate radicals from the persul-
fate anion precursor.
• Persulfate has a relatively slow activation and sub-
sequent oxidation kinetics, which limits the rate at
which heat and gas are generated and allows the for-
mation to buffer liberated heat and gas.
Remediation Engineering
Often, persulfate is mixed with Portland cement, to create a
low permeability and high strength monolith following treat-
ment. Another benefit of Portland cement is that the hydrox-
ide that is created during the hydration reactions activate
the persulfate through the same mechanisms discussed in
Chapter 6.
9.4.5.2 In Situ Soil Mixing with
Zerovalent Iron and Clay
This technology was developed by Colorado State University
and is primarily used to treat source areas with organic con-
taminants. The abiotic reaction of ZVI with organic wastes,
particularly chlorinated solvents (DNAPL), does not produce
the same intermediates as reductive biological reactions. ZVI
is used in a number of different ways to remediate chlorinated
solvents including as a solid in PRBs (see Chapter 10) or
injected at the nanoscale. However, injection approaches are
limited in their ability to distribute a solid substrate homoge-
neously or to meaningful distances.
The incorporation of clay (normally bentonite), in addition
to reducing the permeability of the treated area, also serves
other purposes, such as maintaining the ZVI as a slurry (pre-
venting settling of ZVI to the bottom of the mixed area) and
reducing the soil friction for the LDAs in order to ease mix-
ing. A traditional dosing rate for ZVI is between 0.5% and 5%
(on a dry soil weight basis) using a fine-grained ZVI material;
the resulting spacing between ZVI particles in treated soils
may be on the order of 1 mm, which ensures contact of the
contaminants with the reactive ZVI.27
The implementation of this technology at Lake City Army
Ammunition Plant (LCAAP), where bentonite and ZVI com-
prised a source area DNAPL treatment remedy, is shown in
Figure 9.26. By mixing 4% by weight ZVI with clay decreased
TCE concentrations in soil from approximately 200 to
0.8 mg/kg in less than 30 days.
The primary components of this multifaceted source area
remedy include ZVI and clay soil mixing, enhanced reductive
FIGURE 9.26  ZVI/clay mixing with a crane and 8 ft auger at the
Lake City Army Ammunition Plant.
Soil Treatment
dechlorination, and monitored natural attenuation. DNAPL,
saturated soil, and groundwater remediation utilizing a ZVI
and clay soil mixing approach were conducted within three
separate locations with a total area of 4500 ft2. A 7 ft, LDA,
drilling shroud for vapor capture and control crane were used
to advance mixing columns downward to a total depth rang-
ing between 32 and 47.5 ft below land surface or consistent
with the encountered bedrock surface. During advancement,
the ZVI–clay slurry was injected into the drilling augers to
facilitate mixing of ZVI and clay. The clay material served
to reduce the overall hydraulic conductivity of the soils such
that the ZVI material could facilitate both abiotic and biotic
destruction of the target contaminants.
9.5 PHYTOTECHNOLOGIES
By the year 2000, achieving ever-diminishing cleanup stan-
dards for site closure was rare for the growing list and vari-
ety of contaminants in soil and groundwater. The utilization of
standard remediation technologies in many cases required too
much time and too much money. The market demanded alterna-
tives. New classes of remediation technologies were developed
and researched and began to achieve success and acceptance.
USEPA’s Introduction to Phytoremediation was published in
2000 and in many ways was the introduction of the technology
to remediation practitioners, regulators, and site managers. As
referenced, phytoremediation is an “emerging technology” that
“uses various plants to degrade, extract, contain, or immobilize
contaminants from soil and water.” At that time, the technology
was receiving attention as an “innovative, cost-effective alter-
native to the more established treatment methods used at haz-
ardous waste sites.” Despite its promise, the results of the last
20 years of application of phytoremediation for site remediation
have produced an uneven track record.
The application of phytoremediation has undergone many
changes since the term was first used in 1989.28 Even the name
of the technology has changed. The term phytotechnology is
now preferred by both USEPA and the Interstate Technology
and Regulatory Council.29,30 Phytotechnology is understood
to be a more inclusive term of both destructive processes and
removal/containment processes. To state it bluntly, the term
phytotechnology de-emphasizes the destructive aspects of the
technology whose success has been primarily limited to treat-
ability studies and research facilities.
Why have containment and removal been the most suc-
cessful aspects of the application of phytotechnologies? The
simple answer is water. Water comprises between 75% and
90% of a plants’ mass, and approximately 10% of the mois-
ture in the atmosphere is the direct result of plant transpira-
tion (evaporation of water from plant leaves).28 Plants transfer
a tremendous amount of groundwater and soil moisture to the
atmosphere. For example, an acre of corn transpires about
3,000–4,000 gal of water each day and a large oak tree can
transpire 40,000 gal/year.31 The most successful field appli-
cations of phytotechnologies for site remediation rely on
transpiration for their effectiveness. Examples of success-
ful application include tree/grass covers to limit infiltration
497
through contaminated soil or landfill waste, tree barriers to
withdraw groundwater and control groundwater plume migra-
tion to receptors, and tree covers for the purpose of with-
drawing contaminated groundwater and transpiring it to the
atmosphere to be photodegraded, among others.
The scientific understanding of the transpiration process
and its relationship to groundwater was significantly enhanced
in the American West of the early 1900s. O.E. Meinzer was
a hydrogeologist with the USGS and is known as the “father
of modern groundwater hydrology.”32 He observed that the
apparent location of the water table in reference to land sur-
face had a direct effect on plant occurrence and distribution
in southern California and Nevada. Meinzer’s observations of
plant and groundwater interaction helped establish some of
the first principles of the remediation of groundwater using
plants.28 Meinzer coined the term phreatophyte, commonly
found in phytoremediation/phytotechnology literature, as a
plant “that habitually obtains its water supply from the zone of
saturation, either directly or through the capillary fringe.”32,33
W.N. White made similar observations of groundwater
withdrawal by plants in the American West. He observed a
daily fluctuation in the water table noted in automatic water-
level recorders during the growing season. During the daylight
hours, the water table would decline steadily until evening
when the water table would begin to increase until the fol-
lowing morning when the process would repeat (Figure 9.27).
White observed this phenomenon to be greatest in areas of
“groundwater plants” and nearly nonexistent in cleared fields.
White also noted the diurnal pattern to be affected by sea-
son, humidity, temperature, wind, and plant health.28 White’s
observations were so complete that he used them to develop an
equation to calculate the volume of groundwater transpired.
The equation is known as White’s equation. He published his
observations and equation in a 1932 USGS publication titled
A Method of Estimating Ground-Water Supplies Based on
Discharge by Plants and Evaporation from Soil.33
The successful application of phytotechnologies can take
a variety of forms that will be discussed in this chapter.
However, the most consistently successful field applications
of phytotechnologies have utilized the interaction of ground-
water and plants first described and studied by O.E. Meinzer
and W.N. White and others in the early 1900s. The goal of
using plants to remediate contaminants directly within the
root zone (rhizodegradation) or within the plant itself (phy-
todegradation), in many cases, remains an unattained goal.
After all this time, a recent publication assessed the tech-
nology in this way, “the outlook of phytoremediation is still
in the research and development phase, and there are many
technical barriers that need to be explored.”34 These processes
have been demonstrated too often to only take a site a short
distance toward a numerical cleanup goal resulting in lost
time for the overall project.
While some aspects of phytotechnologies have matured
and been utilized to great effectiveness in the last 15 years,
many aspects are still in their infancy requiring additional
research and testing before being considered a practical reme-
dial solution. As with all remedial technologies, the ultimate
498
3.40
3.50
Depth to water (ft)
3.60
3.65
3.70
Aug. 20 21
3.80
FIGURE 9.27  Daily fluctuations of the water table in a salt-grass meadow before and after the salt grass was cut, August 20-27, 1927.
(From White, W.N., A method of estimating ground-water supplies based on discharge by plants and evaporation from soil—Results of
investigations in Escalante Valley, Utah, Water Supply Paper 659-A, USGS, Washington, DC, 1932.)
fate of phytotechnologies is one of effectiveness and econom-
ics. Phytotechnologies must be proven to be the most cost-
effective and reliable solution to achieving a site’s remedial
goals for it to be used. Unfortunately, the last 15 years have
seen too many examples of phytotechnologies being selected
for its intangible benefits (“green” technology, sustainable,
good for the environment, low maintenance) instead of dem-
onstrated remedial effectiveness.
Practitioners of phytotechnologies need to greatly increase
the publication of verified full-scale successes (and failures)
that document the important processes and mechanisms
for overall improvement and acceptance of this technology
within our industry. Otherwise, the technology will never
achieve anything more than niche or novel status.
9.5.1  Chemicals in the Soil–Plant System
Using plants to facilitate remediation of contaminants in soil
and water is essentially taking advantage of the plant’s natural
processes. Plants synthesize their food by converting inorganic
materials, such as carbon dioxide and water, into organic mat-
ter. Plants obtain carbon dioxide from the atmosphere. All other
materials are facilitated by water obtained from the root system.
Water’s importance is emphasized by the fact that it comprises
between 75% and 90% of a plants’ mass.28 Inorganic macro-
nutrients (N, P, K, Ca, Mg, and S) and inorganic micronutri-
ents (Fe, Cl, Mn) are all obtained through the root membrane.
Once inside the plant, the dissolved nutrients are transported
throughout the plant via the vascular system. A contaminant’s
pathway into the plant is also facilitated by water.
9.5.1.1 Metals
Metallic elements are present in the soil in a variety of forms
more or less available for uptake by plants. Many of the COCs
at waste sites are metals or metalloids. Availability of metals
is determined by their characteristics, such as behavior of the
Remediation Engineering
Salt grass cut at
midday Aug. 25
22 23 24 25 26 27
ion as a Lewis acid and the type and strength of the bond cre-
ated (ionic or covalent) and, therefore, the mobility of the metal
in the soil environment. Soil characteristics (e.g., pH, clay and
organic matter content and type, and moisture content) also
determine availability to plants by controlling speciation of
the element, temporary immobilization by particle surfaces
(adsorption–desorption processes), precipitation reactions, and
availability in soil solution. The most general sinks for metals
are iron and manganese oxides and organic matter. Although
particulate soil organic matter serves to immobilize metals,
soluble organic matter may act to keep metals in solution in a
form absorbed and translocated by plants.
Metal fractionation or sequential extraction schemes—
such as TCLP—sometimes are used to describe metal behav-
ior in soils. Most metals interact with the inorganic and
organic matter that is present in the root–soil environment.
Potential forms of metals include those dissolved in the soil
solution, adsorbed to the vegetation’s root system, adsorbed
to insoluble organic matter, bonded to ion exchange sites on
inorganic soil constituents, precipitated or coprecipitated as
solids, and attached to or inside the soil biomass.
The final control on availability of metals and metalloids
present in the soil to plants is the selective absorption from soil
solution by the root. Metals may be bound to exterior exchange
sites on the root and not actually taken up. They may enter
the root passively in organic or inorganic complexes with the
mass flow of water or actively by way of metabolically con-
trolled membrane transport systems often meant to take up
a nutrient that the “contaminant” metal mimics. At different
soil solute concentrations, metals may be absorbed by both
processes. Absorption mechanisms and quantity absorbed are
influenced by plant species (and cultivar), growth stage, physi-
ological state, and the presence of other elements.
Once in the plant, a metal can be sequestered in the roots
in vacuoles or in association with cell walls and organelles
or translocated to aboveground parts in xylem as organic or
Soil Treatment
inorganic complexes. Location and forms of metals in plants,
as well as their toxic effects, depend on plant species, growth
stage, physiological state, and presence of other metals.
Mechanisms of toxicity of metals tend to be dependent on
the nature of the reactivity of the metal itself and its avail-
ability in the soil and soil solution media. They may alter
or inhibit enzyme activity, interfere with deoxyribonucleic
acid synthesis or electron transport or block uptake of essen-
tial elements.35 Response to toxic levels of metals by differ-
ent plants is due to a number of defense mechanisms. These
include exclusion from the root, translocation in nontoxic
form, sequestering in nontoxic form, sequestering in non-
toxic form in the root or other plant parts, and formation of
unusable complexes containing metals that may otherwise be
inserted into biomolecules instead of the proper element (e.g.,
arsenic [As] replacing phosphorus [P]).
9.5.1.2 Organics
Organic compounds of environmental concern include non-
ionic compounds (such as PAHs, chlorinated benzenes,
PCBs, BTEX compounds, and many pesticides), ionizable
compounds (chlorophenols, carboxylic acids, surfactants,
and amines), and weakly hydrophobic VOCs (TCE). For the
nonionic compounds, sorption in soil is mainly a function of
degree of hydrophobicity and amount of sorbent hydrophobic
phase (i.e., soil organic matter). Sorption of the compound by
soil organic matter is reversible. The activities of these com-
pounds in soil can be predicted by the organic matter–water
coefficient, Kom, as estimated by the octanol–water coeffi-
cient, Kow.48 Absorption onto colloidal organic matter in solu-
tion may alter the availability of these nonionic compounds.
Ionizable compounds contain anionic or cationic moieties or
both within their structure. These charged structures interact
with organic and inorganic charged surfaces in the soil in a
variety of reversible reactions. The extent and nature of the
associations with charged surfaces depends on characteristics
of the organic compound, solution pH and ionic strength, and
mineral composition of the soil particulates. Organic com-
pounds may be degraded by microorganisms in the soil to
metabolites with greater or lesser toxicity. Very stable com-
pounds, like highly chlorinated PCBs, may persist in essen-
tially unaltered form for many years.
Plant roots are not discriminating in uptake of small
organic molecules (molecular weight less than 500) except
on the basis of polarity.43 More water-soluble molecules pass
through the root epidermis and translocate throughout the
plant. The less soluble compounds (like many PAHs) seem
to have limited entry into the plant and minimal transloca-
tion once inside. Highly lipophilic compounds, such as PCBs,
move into the plant root via the symplastic route (from cell to
cell, as opposed to between cells) and are translocated within
the plant. Within a plant, the contaminant may be adsorbed on
a cell surface or accumulated in the cell. Many contaminants
become bound on the root surface and are not translocated.
Not all organic compounds are equally accessible to
plant roots in the soil environment. The inherent ability of
the roots to take up organic compounds can be described by
499
the hydrophobicity (or lipophilicity) of the target compounds.
This parameter is often expressed as the log of the octanol–
water partitioning coefficient, Kow. Direct uptake of organics
by plants is a surprisingly efficient removal mechanism for
moderately hydrophobic organic compounds. There are some
differences between the roots of different plants and under
different soil conditions, but, generally, the higher a com-
pound’s log Kow, the greater the root uptake.
Hydrophobicity also implies an equal propensity to par-
tition into soil organic matter and onto soil surfaces. Root
absorption may become difficult with heavily textured soils
and soils with high native organic matter. There are several
reported values available in the literature regarding the opti-
mum log Kow value for a compound to be a good candidate for
phytotechnologies. In general, compounds with log Kow values
<3.5 and >1.0 are good candidates for uptake by plants.29,36
Hydrophobic chemicals (log Kow > 3.5) are not sufficiently
soluble or are bound so strongly to the surface of the roots that
they are unable to be translocated into the plant. It has also
been reported that compounds that are quite water soluble (log
Kow < 1.0) are not sufficiently sorbed to the roots or actively
transported through plant membranes.29 Contaminants such
as BTEX, chlorinated solvents, and short-chain aliphatic
chemicals fall within the log Kow range that allow them to be
susceptible to translocation into the plant.29
From an engineering point of view, a tree could be thought
of as a shell of living tissue encasing an elaborate and massive
chromatography column of twigs, branches, trunk, and roots.
The analogous resin in this system is wood, the vascular tis-
sue of the tree, and this “resin” is replenished each year by
normal growth. Wood is composed of thousands of hollow
tubes, like the bed of a hollow fiber chromatography column,
with transpirational water serving as the moving phase. The
hollow tubes are actually dead cells, whose death is carefully
programmed by the tree to produce a water conducting tis-
sue, which also functions in mechanical support. A complex,
cross-linked, polymeric matrix of cellulose, pectins, and pro-
teins embedded in lignin forms the walls of the tubes. The cell
wall matrix is chemically inert, insoluble in the majority of
solvents, and stable across a wide range of pH.
Once an organic chemical is taken up, a plant can store
(sequestration) the chemical and its fragments in new plant
structures via lignification or it can volatilize, metabolize, or
mineralize the chemical all the way to carbon dioxide, water,
and chlorides. Detoxification mechanisms may transform the
parent chemical to nonphytotoxic metabolites, including lig-
nin, which are stored in various places in plant cells. Many
of these metabolic capacities tend to be enzymatically and
chemically similar to those processes that occur in mamma-
lian livers; one report has equated plants to “green livers” due
to similarities of detoxification processes.
Different plants exhibit different metabolic capacities.
This is evident during the application of herbicides to weeds
and crops alike. The vast majority of herbicidal compounds
have been selected so that the crop species are capable of
metabolizing the pesticide to nontoxic compounds, whereas
the weed species either lack this capacity or perform it at too
500
Levels Mechanisms
Phytoextraction
Uptake of contaminants into
the plant and their subsequent
sequestration within the plant
tissues
Whole plant
Phytodegradation
Uptake and breakdown of
contaminants within plant
tissues through internal
enzymatic activity
Leaves
Phytohydraulics
Uptake and transpiration of
water
Shoot
Phytovolatilization
Uptake and translocation, and
Leaves and
subsequent volatilization of
stems
contaminants in the
transpiration stream
Phytosequestration
Sequestration of certain
contaminants into the
rhizosphere through release of
phytochemicals and sequestration
of contaminants
on/into the plant roots and
Root stems through transport
proteins and cellular processes
Rhizodegradation
Released root-phytochemicals
to enhance microbial
biodegradation of contaminants
in the rhizosphere
FIGURE 9.28  Schematic representation of major phytotechnology mechanisms and their significance for varied contaminants’ cleanup.
(From Anjum, A.A. et al., Introduction, in Anjum, N.A. et al., eds., Phytotechnologies, CRC Press, Boca Raton, FL, 2013, pp. 1–4.)
slow a rate. The result is the death of the weed species without
the metabolic capacity to rid itself of the toxin. lows based on current understanding of the technology29
The sheer volume and porous structure of a tree’s wood (Figure 9.28):
provide an enormous surface area for exchange or biochemi-
cal reactions. Some researchers are attempting to augment the
inherent metabolic capacity of plants by incorporating bacte-
rial, fungal, insect, and even mammalian genes into the plant
genome.
9.5.2 Types of Phytotechnologies
A review of where phytotechnologies fit into the scheme of
hazardous waste remediation enables us to differentiate the
various types and mechanisms of phytotechnologies. The sci-
entific understanding of plant, soil, and rhizosphere biochem-
istry, and contaminant fate and transport must be contrasted
with field and pilot studies that represent the current proof of
concepts. The technology is summarized in the following as
those approaches ready for application, promising treatments
expected to be tested soon, and concepts of phytotechnolo-
gies requiring intensive development. Finally, the intrinsic
strengths of phytotechnologies as a remediation approach
and the future potential of this technology must be reviewed
for regulatory acceptance in the context of hazardous waste
remediation.29
Remediation Engineering
Significant for
Organic compounds (such as PCBs) and
inorganics (such as As, Cd, Cr, Cu, Ni, Se,
radionuclides)
Organic compounds (such as BTEX,
chlorinated solvents, munitions, petroleum
products)
Organic compounds (such as BTEX,
chlorinated solvents, PCBs, pesticides) and
inorganics (such as As)
Organic compounds (such as PCBs, pesticides)
and inorganics (such as Cd, Cr, Se,
radionuclides)
Organic compounds (such as PCBs, pesticides)
and inorganics (such as Cd, Cr, Se,
radionuclides)
Organic compounds (such as BTEX,
chlorinated solvent, PCBs, munitions,
petroleum products) and inorganics (such as
radionuclides)
Phytotechnology approaches can be summarized as fol-
• Phytosequestration: The ability of plants to sequester
certain contaminants in the rhizosphere through exu-
dation of phytochemicals and on the root through trans-
port proteins and cellular processes (containment).
• Rhizodegradation: Exuded phytochemicals can
enhance microbial biodegradation of contaminants
in the rhizosphere (destruction).
• Phytohydraulics: The ability of plants to capture and
evaporate water off the plant and take up and tran-
spire water through the plant (containment).
• Phytoextraction: The ability of plants to take up
contaminants into the plant with the transpiration
stream (removal by plant).
• Phytodegradation: The ability of plants to take up
and break down contaminants in the transpiration
stream through internal enzymatic activity and pho-
tosynthetic oxidation/reduction (destruction).
• Phytovolatilization: The ability of plants to take up,
translocate, and subsequently transpire volatile con-
taminants in the transpiration stream (removal by
plant).
Soil Treatment
Optimal performance of the technology is an important key
to its ability to regain trust and acceptance as a presumptive
remediation technique. With the possible exception of some
of the mechanisms mentioned earlier that are already widely
studied and understood, all of phytotechnologies’ major appli-
cations require further basic and applied research in order to
establish optimal field performance. Research and develop-
ment should continue to be carried out to (1) obtain a bet-
ter understanding of mechanisms of uptake, transport, and
accumulation of contaminants; (2) improve collection and
genetic evaluation of hyperaccumulating plants; (3) obtain a
better understanding of interactions in the rhizosphere among
plant roots, microbes, and other biota; and (4) demonstrate
verifiable full-scale field success from design and installation
through long-term operation and monitoring data.
Phytotechnologies’ ability to make further inroads depends
on its ability to regularly achieve site remediation goals in a
verifiable manner. Applications of this technology in the past
have often been done without collecting the appropriate data
to understand the key mechanisms over the lifetime of the
project. For those sites that have achieved success, the suc-
cess is poorly understood. Unfortunately, phytotechnology
applications too often have been conceived poorly and were
destined to fail before a single plant went in the ground.
Federal, state, and local regulators have generally been
more than willing to give the technology a try at remediation
sites. One has to wonder whether the time to take advantage
of optimism in a truly “green” technology has passed with
the number of poorly executed projects. While not involved
in every decision-making process, the public is sometimes a
key constituency as well. However, phytotechnologies have
been well received and even popular with neighbors and other
interested parties at field remediation sites.
9.5.2.1 Phytosequestration
Phytosequestration is the use of certain plant species to
immobilize contaminants in the soil and groundwater through
Enhanced rhizosphere biodegradation
– Supply of nutrients, cometabolites
– Transport and retention of water
– Aeration
Root respiration
Sloughing
Enzymes
dehalogenase
nitroductase
FIGURE 9.29  Rhizodegradation and associated processes in the root zone.
501
absorption and accumulation by roots, adsorption onto roots,
or precipitation within the root zone. This mechanism may
reduce the fraction of the contaminant that is bioavailable.
Another element of phytosequestration is to supplement
the system with a variety of alkalizing agents, phosphates,
organic matter, and biosolids to render the metals insoluble
and unavailable to leaching. Materials with a calcareous char-
acter or a high pH, such as lime and gypsum, can be added
to influence the acidity. Specific binding conditions can be
influenced by adding concentrated Fe, Mn, or Al compounds.
To maintain or raise the organic matter content in the soils,
various materials such as humus or peat materials, manure, or
mulch can be added.
This chemical alteration should be quickly followed by
establishing a plant cover and maximizing plant growth. The
amendments sequester the metals into the soil matrix and
plants keep the stabilized matrix in place, minimizing wind
and water erosion.
9.5.2.2 Rhizodegradation
Rhizodegradation (also called phytostimulation, rhizosphere
biodegradation, enhanced rhizosphere biodegradation, or
plant-assisted bioremediation/degradation) is the break-
down of contaminants in the soil through microbial activity
enhanced by the presence of the rhizosphere (Figure 9.29).
Microorganisms (yeast, fungi, and/or bacteria) consume and
degrade or transform organic substances for use as nutrient
substances. Certain microorganisms can degrade organic
substances such as fuels or solvents that are hazardous to
humans and ecoreceptors and convert them into harmless
end products through biodegradation. Natural substances
released by plant roots—such as sugars, alcohols, and
acids—contain organic carbons that act as nutrient sources
for soil microorganisms; these additional nutrients stimulate
their activity. Rhizodegradation is aided by the way plants
loosen the soil and transport oxygen and water to the area.
Plants also enhance biodegradation by other mechanisms
Soil dessication
Root intrusion
Uptake
502
such as breaking apart clods and transporting atmospheric
oxygen to the root zone.
Soil adjacent to the root contains increased microbial
numbers and populations.38 It is common knowledge that the
number of bacteria in the rhizosphere is as much as 20 times
that normally found in nonrhizosphere soil. Short gram-
negative rods (specifically Pseudomonas, Flavobacterium,
and Alcaligenes) are most commonly found in the rhizo-
sphere.38 The increased microbial numbers are primarily due
to the presence of plant exudates and sloughed tissue that
serve as sources of energy, carbon, and other growth factors.
The products excreted by plants include amino acids, carbox-
ylic acids, carbohydrates, nucleic acid derivatives, growth fac-
tors, and enzymes. The activity of microorganisms in the root
zone stimulates root exudation further stimulating microbial
activity.39
Several studies have evaluated the effect of plants and the
associated rhizosphere on the fate of petroleum contami-
nants.29,38,40 For the most part, the presence of plants enhanced
the degradation of contaminants. Also, in studies using
14C-labeled contaminants in closed plant chambers, mineral-
ization was greater in rhizosphere soils than in unvegetated
soils, indicating that the bioavailability of the contaminant
was higher in the rhizosphere.38
Studies using deep rooted prairie grasses to remediate soils
contaminated with polyaromatic hydrocarbons (PAHs) sug-
gest that the roots of these perennial grasses may be more
effective at stimulating the rhizosphere microflora due to their
fibrous nature. Fibrous roots offer more root surface area for
microbial colonization than other roots and result in a larger
microbial population in the contaminated soil. Big bluestem
(Andropogon gerardii), Indian grass (Sorghastrum nutans),
switchgrass (Panicum virgatum), Canada wild rye (Elymus
canadensis), little bluestem (Schizachyrium scoparium),
side oats grama (Bouteloua curtipendula), western wheat-
grass (Agropyron smithii), and blue grama (Bouteloua graci-
lis) are some of the species known to enhance degradation
of petroleum compounds. Crested wheatgrass (Agropyron
desertorum) is known to degrade PCP contaminated soils.38
Alfalfa 4–6 ft
Grasses 2 ft
FIGURE 9.30  Examples of different root depths.
Remediation Engineering
Alfalfa (Medicago sativa), fescue (Festuca arundinacea), big
bluestem (A. gerardii), and Sudan grass (Sorghum vulgare
sudanense) are known to enhance the degradation of PAH
compounds in the rhizosphere. The degradation rates among
various PAHs studied correlated with the water solubility of
the compound with the more soluble compound, showing the
highest degradation.
Cometabolic transformation of chlorinated solvents and
other compounds also has been reported in the literature.35
Wherever significant cometabolic transformations took place,
the following enzyme systems were present: dehalogenase,
nitroreductase, peroxidase, laccase, nitrilase, and oxygenase.
The rhizosphere is often divided into two general areas: the
inner rhizosphere at the very root surface and the outer rhizo-
sphere embracing the immediately adjacent soil. The micro-
bial population is larger in the inner zone where biochemical
interactions are most pronounced and root exudates are con-
centrated. In addition to plant exudates, the rapid decay of
fine-root biomass can also become an important addition of
organic carbon to soils. A recent report considers some strate-
gies for engineering plants to improve bioremediation in the
root zone. One of the simpler approaches is to make use of the
organism Agrobacterium rhizogenes to induce a state called
“hairy root disease.” Depending on virulence of the strain
used, the extent of root production is variable. But generally,
infection leads to a significant enhancement of rooting with-
out obvious detrimental effects on the host plant. Increased
root mass has the apparent advantage of increasing the sur-
face area available for microbial colonization. Root exuda-
tion may be increased in proportion to increase in root area.
Such rhizosphere enhancements could improve bioremedia-
tion potential of the plant–microbial system. It is suggested
that when water is not freely available in unlimited quanti-
ties, increased root mass could lead to greater water uptake
and hence greater contaminant mobilization and potential
degradation.
Different plant species often establish somewhat different
subterranean floras (Figure 9.30). The differences are attrib-
uted to variations in rooting habits, tissue composition, and
Poplar trees 15 ft
Indian
mustard 1 ft
Soil Treatment
excretion products of the plant. The primary root population
is determined by the habitat created by the plant; the second-
ary flora, however, depends upon the activities of the initial
population. The age of the plant also alters the microbial
population in the rhizosphere. Roots also harbor mycorrhizae
fungi, which metabolize organic contaminants. These fungi,
growing in symbiotic association with the plant, have unique
enzymatic pathways, similar to white rot fungus enzymes that
help to degrade organics that could not be transformed solely
by bacteria.
In summary, plants provide exudates that offer an excellent
habitat for increased microbial populations and pump oxygen
to roots, a process ensuring aerobic transformations near the
root that otherwise may not occur in bulk soil. Due to the
presence of certain primary substrates in the exudate system,
anaerobic cometabolic transformations may also take place
in the rhizosphere. Typical microbial population in the rhizo-
sphere comprises 5 × 106 bacteria, 9 × 105 actinomycetes, and
2 × 103 fungi per gram of air-dried soil.
The state of science in rhizodegradation can be summa-
rized as follows:
• Contaminant degradation can be achieved in  situ,
which is the biggest advantage.
• Translocation of the contaminant to the plant or
atmosphere is less likely than with other phytoreme-
diation techniques since degradation takes place at
the source of contamination.
• Installation and maintenance costs are low since no
harvesting and disposal are required.
• Various microorganism species and enzymes have
been isolated that degrade different contaminants.
• Analytical methods to better quantify treatment effi-
ciency and success are improving.
• Field management techniques for nutrients, water,
and plant selection are advancing.
• TPH and PAHs up to hundreds of ppm have been
studied in the field with varying success.35
• Degradation of various pesticides (atrazine, metola-
chlor, parathion, diazinon, and 2,4-D, 2,4,5-T herbi-
cides) has been studied, again with mixed results.35
• TCE, PCP, and PCB degradation have also been
investigated—again with varying success.
• More research needs to be done to further elucidate
microbial metabolism in the rhizosphere, toxicity
toward plants, biodiversity in the rhizosphere, bio-
geochemical optimization in the rhizosphere, and
interrelation between biological, chemical, and phys-
ical characteristics of the rhizosphere.
The following plants, in addition to the ones discussed pre-
viously, have been used for successful implementation of
phytodegradation at field sites35: (1) red mulberry, crabapple,
spearmint, and Osage orange that are capable of stimulating
PCB degradation; (2) alfalfa, loblolly pine, and soybean for
TCE degradation; (3) alfalfa for TCA degradation; and (4) rye,
St. Augustine, and white clover for TPH.
503
9.5.2.3 Phytohydraulics
Phytotechnologies can be applied for containment of con-
taminated groundwater under the right hydrogeologic con-
ditions such as sites with shallow groundwater depths. In
general, favorable economics is one factor in the technology’s
favor, particularly in contrast to the high cost of operation and
maintenance of conventional groundwater treatment systems.
Furthermore, the high transpiration rates of many deep rooted
trees may make them more efficient at removing water at low
permeability sites.
Phreatophytes (like willows, cottonwood, and hybrid pop-
lar), which take up and “process” large volumes of soil water,
are good candidates for applications specifically for ground-
water containment (Figure 9.31). Peak transpiration rates for
mature phreatophytes can be as high as 100–200 gal per day
per tree. An acre of a variety of species of grasses can tran-
spire more than 5000 gal per day per acre.29
The application of phytohydraulics for groundwater plumes
is preferred when the contaminants are water soluble, leach-
able organics, and inorganics present at concentrations that
are not phytotoxic. Hydraulic control by plants can occur only
within the root zone or within a depth influenced by roots; the
placement depth of roots during planting can be varied. Root
depth, early tree growth, and nutrient uptake were enhanced
by placing poplar tree root balls closer to shallow groundwa-
ter during planting.
The primary considerations for selecting phytotechnology
for hydraulic control as the method of choice are the depth
to groundwater and concentration of contaminants that affect
plant growth. Soil texture, degree of saturation, and soil per-
meability are also influential factors. Planting technique and
materials can extend the influence of plants through nonsatu-
rated zones to water-bearing layers. However, any designer or
installer should carefully consider the selection of phytotech-
nologies if its applications require elaborate methods to force
a plant to grow in a manner it would not do on its own.
As mentioned earlier, phreatophytes such as poplars are
capable of extending their roots into aerobic water tables.
FIGURE 9.31  Five-year old hybrid poplar tree stand (>40 ft tall)
used to control migration of groundwater contaminants at a site in
Missouri.
504 Remediation Engineering

Above
capillary
fringe At capillary
fringe

In capillary fringe
and groundwater table

FIGURE 9.32  Placement of root ball with time due to maturation of the tree.

31.0

Groundwater Zone of tree plantation

flow

28.0
30.5
29.0
30.0

30.0

Groundwater table elevation contours

FIGURE 9.33  Measured groundwater flow conditions at maturation of tree growth.

For example, the roots of poplars growing alongside streams
can easily be observed intertwined in the stream bottom.
The degree to which poplar roots would penetrate the satu-
rated zone cannot be easily estimated. If their access to soil
moisture from precipitation is limited, poplars will draw
large amounts of water from the top of a saturated aquifer.
Evapotranspiration will draw down the water table below
the trees similar to a pump and treat system (Figures 9.32
and 9.33). Simulations of a proposed design can be carried
out based on extent of contamination, hydrogeological data,
past precipitation and infiltration records, and evapotrans-
piration data.
A big advantage of phytoremediation over conventional
pump and treat systems is the ability of the roots to penetrate
the microscopic scale pores in the soil matrix. Contaminants
adsorbed or trapped in these micropores are impacted mini-
mally or not at all by the pump and treat system. In the case
of phytoremediation, the roots can penetrate these micropores
for contaminant removal.
9.5.2.4 Phytoextraction
Phytoextraction, also called phytoaccumulation, refers to the
ability of plants to take up contaminants into the roots and
translocate them to the aboveground shoots or leaves. Once
a chemical is taken up, the plant may store the chemical,
sequester the chemical into its cells, metabolize it through
phytodegradation mechanisms, and/or phytovolatilize the
chemical from the transpiration stream exiting the plant.29
The mechanisms and processes involved in extracting met-
als and organic chemicals from the subsurface by plants have
attracted a great deal of interest for more than three decades.
Regarding metals, certain plants, called hyperaccumulators,
absorb unusually large amounts of metals in comparison to
other plants and the ambient metals concentration.
Soil Treatment
Phytoaccumulators or phytoextractors must have a high
accumulation factor, that is, a high uptake of metals from the
soil. The uptake should be metal specific, which diminishes
the risk of impoverishing the soil of nutrient elements. The
property of having a high specific uptake must be genetically
stable. Since the removal of metals from the soil is actually
achieved through the harvest, it is necessary that the plant
have a high transport of the metal(s) from the roots to the
shoots to be effective during remediation applications. In
addition, a high biomass production of the phytoaccumulator
is needed for high removal of metals per unit area. It is also
an advantage if biomass production is of economic interest.
Hyperaccumulators have been preferred during phytoextrac-
tion applications because they take up very large amounts of a
specific metal. They are often endemic and of a specific popu-
lation (genotypes/clones) of a species.41 However, these plants
seldom have high biomass production and may also have low
competitive ability in less polluted areas, probably because the
plant uses its energy to tolerate such high levels of metals in the
tissue instead of growth. Hyperaccumulators can accumulate
≥0.01% of Cd, ≥0.1% of Cu, or ≥1.0% Zn in leaf dry mass and
may have the metal evenly distributed throughout the plant.42
There are also high accumulators that accumulate some-
what lower metal concentrations than hyperaccumulators but
much more than “normal” plants. They usually have high bio-
mass production. In these plants, there is no uniform distribu-
tion of metal throughout the plant, and thus the plant might
have high accumulation either in the roots or in the shoots.
These plants are selected and planted at a site based on the
type of metals present and other site conditions. After they
have been allowed to grow for several weeks or months, they
are harvested.
Landfilling, incineration, and composting are options to
dispose of or recycle the metals, although this depends upon
the results of TCLP testing and cost. Planting and harvesting
of plants may be repeated as necessary to bring soil contami-
nant levels down to allowable limits. A plan may be required
to deal with the plant biomass waste. Testing of plant tissue,
leaves, roots, etc., will determine if the plant tissue is a haz-
ardous waste. Regulators will play a role in determining the
testing method and requirements for the ultimate disposal of
the plant waste.
The state of science in phytoextraction is as follows43:
• Botanical prospecting dating to the 1950s in the
former USSR and United States is available to
practitioners.
• More than 400 species of hyperaccumulators world-
wide have been catalogued.
• Field test kits for metal hyperaccumulation have
been developed.
• Uptake and segregation processes using cation
pumps, ion transporters, Ca blocks, metal chelating
exudates and transporters, phytochelatin peptides,
and metallothioneins have been evaluated and con-
tinuous research is being performed to develop fur-
ther understanding.
505
Hyperaccumulators have metal accumulating characteristics
that are desirable but lack the biomass production, adaptation
to current agronomic techniques, and physiological adapta-
tions to climatic conditions required at many contaminated
sites. Harvesting at different seasons in a year had pronounced
differences in accumulation levels. In the future, genetic
manipulation techniques may provide better hyperaccumula-
tor species. The success of phytoextraction depends on the
use of an integrated approach to soil and plant management:
the disciplines of soil chemistry, soil fertility, agronomy,
plant physiology, and plant genetic engineering are currently
being used to increase the rate and efficiency of heavy metal
phytoextraction.
The schematic of the process involved in heavy metal
phytoextraction is shown in Figure 9.34. Translocation
from the root to the shoot must occur efficiently for ease
of harvesting. After harvesting, a proper, acceptable bio-
mass processing step or disposal methods should be
implemented.
9.5.2.5 Phytodegradation
Phytodegradation, also called phytotransformation, is the
breakdown of contaminants taken up by plants through
metabolic processes within the plant, or the breakdown of
contaminants external to the plant through the effect of com-
pounds (such as enzymes) produced by the plants. Pollutants
are degraded, used as nutrients, and incorporated into the
plant tissues. In some cases metabolic intermediate or end
products are re-released to the environment depending on
the contaminant and plant species (phytovolatilization)
(Figure 9.35).
Plants synthesize a large number of enzymes as a result of
primary and secondary metabolism and can quickly uptake
and metabolize organic contaminants to less toxic compounds.
Plant enzyme systems can be constitutive or induced and can
play a role in solar driven transformations and plant adapta-
tion and/or tolerance to adverse growth conditions resulting
from contamination of the soils. Plant-formed enzymes that
are useful for phytodegradation are nitroreductases (for muni-
tions and pesticides), dehalogenases (for chlorinated solvents
and pesticides), phosphatases (for pesticides), peroxidases
(for  phenols), laccases (for aromatic amines), cytochrome
P450 (for pesticides and chlorinated solvents), and nitrilase
(for herbicides).
Plant transformation pathways can be of many differ-
ent types and obviously depend on plant species and tissue
type. In simplistic terms, these pathways can be categorized
as reduction, oxidation, conjugation, and sequestration. The
“green liver model” has been proposed to describe the meta-
bolic pathways of herbicides, pesticides, explosives, and other
nitroaromatic compounds. Contaminant degradation by plant-
formed enzymes can occur in an environment free of micro-
organisms (e.g., an environment in which the microorganisms
have been killed by high contaminant levels). Thus,  phyto-
degradation potentially could occur in soils where biodegra-
dation cannot.
506 Remediation Engineering

Disposal or
Me Harvest reclamation
of metals

Me
Me Me
Me
Me Plant transpiration results
Me
in metal contaminants being
concentrated in the plant
Me

Me Me

Translocation to leaf
and stalk biomass

Contaminant
root uptake

Contaminant
uptake

FIGURE 9.34  Process schematic describing the various processes during phytoaccumulation of heavy metals.

Photosynthesis
H2O transpiration and
O2
volatilization of VOCs
CO2
Phloem
photosynthates Xylem Dark respiration
+O2 H2O, nutrients
CO2, H O
Phytodegradation O2
– Metabolism within the plant
– Production of enzymes that
help to catalyze degradation

Lignification,
metabolites
sequestration

H2O, nutients, O2
Root respiration transpiration
CO2, H O
O2

Contaminent
uptake
Exudation
O2, CH3COOH, C4H5OH CO2, H2O, Cl
cometabolism Contaminant mineralization

FIGURE 9.35  Phytodegradation and phytovolatilization mechanisms associated with some other mechanisms essential for plant life.
Soil Treatment
The current state of science in phytodegradation (phyto-
transformation) is summarized as follows29:
• Plant-formed enzymes that degrade organic contam-
inants have been isolated and metabolic pathways
can be predicted.
• Phytodegradation can be used for the treatment of
soil, sediments, sludges, and groundwater depending
on contaminant type and concentrations.
• Mass balance and pathway analyses studies have
been conducted to prove complete degradation;
potential toxicity of intermediate compounds also
can be predicted.
• Differentiation between degradation by plant
enzymes, rhizosphere microorganisms, and other
breakdown processes is being performed.
• Development of engineered solutions based on the
use of monocultures versus multicultures found in
wetlands and terrestrial communities is being fur-
ther investigated.
• Organic contaminants are the main category of con-
taminants with the highest potential of phytodegrada-
tion. Inorganic nutrients are also consumed through
plant uptake and metabolism. Phytodegradation out-
side the plant does not depend on log Kow and plant
uptake.
• Axenic plant tissue cultures of the aquatic plant
Myriophyllum and the periwinkle Catharanthus
are being used for elucidating plant transformation
pathways.
The aquatic plant parrot feather (Myriophyllum aquaticum)
and the algae Nitella have been used for the degradation of
TNT. The nitroreductase enzyme has also been identified in
other algae, ferns, monocots, dicots, and trees.
Degradation of TCE has been detected in hybrid poplars
and in poplar cell cultures, resulting in production of metab-
olites and in complete mineralization of a small portion
of the applied TCE.44,45 Poplars have been used to remove
atrazine and inorganic nutrients.30 Black willow (Salix
nigra), yellow poplar (Liriodendron tulipifera), bald cypress
(Taxodium distichum), river birch (Betula nigra), cherrybark
oak (Quercus falcata), and live oak (Quercus virginiana)
have been known to support degradation of herbicides.36
One recent study demonstrated that poplar trees, which
possess cytochrome P-450s analogous to the oxygenases
responsible for transformation of compounds such as TCE
in the mammalian liver, exposed to 100 mg/L of TCE did
uptake and chemically alter this contaminant. TCE and its
metabolites were found in the roots and tissue of the study
trees but not in control trees or in the soil used for potting
the trees. In a subsequent study, poplar seedlings exposed to
14 C-labeled TCE were found to generate 14 C-labeled carbon
dioxide. Intermediate compounds generated during oxida-
tion are thought to be 2,2,2-trichloroethanol and di- and
507
trichloroacetic acid. Similar studies have shown positive
results for toluene and benzene.
A recent study using parrot feather showed positive
results for phytotransformation of perchlorate at concen-
trations of up to 20 ppm.46 Based on the results of these
experiments and ecological knowledge of parrot feather,
this species is an excellent candidate for future research
on in situ phytoremediation of contaminated water bodies.
Parrot feather also is a good candidate for phytoremediation
of contaminated groundwater temporarily held in artificial
ponds.
9.5.2.6 Phytovolatilization
Phytovolatilization is the uptake and transpiration of a con-
taminant by a plant, with release of the contaminant or a
modified form of the contaminant to the atmosphere from the
plant. Phytovolatilization occurs as growing trees and other
plants take up water and organic and inorganic contaminants.
Some of these contaminants can pass through the plants to
the leaves and volatilize into the atmosphere at comparatively
low concentrations. Many organic compounds transpired by a
plant are subject to phytodegradation.
Thus far, phytovolatilization has mainly been applied to
groundwater contamination. However, the potential exists
for application to soil, sediments, and other contamination
and needs some careful applications. The state of science
with respect to phytovolatilization can be summarized as
follows35,47:
• Contaminants could be transformed to less toxic
forms (e.g., elemental Hg and dimethyl selenite
gas).
• The contaminant or a hazardous metabolite might
accumulate in vegetation.
• Significant reductions of TCE, TCA, and carbon
tetrachloride have been achieved in experimental
studies.
• Poplars, willow, alfalfa (M. sativa), and black
locust species have been studied to evaluate
phytovolatilization.
• Indian mustard and canola have been used in phyto-
volatilization studies of Se.
• Selenium (as selenate) was converted to less toxic
dimethyl selenite gas and released to the atmosphere.
Kenaf and tall fescue have also been used to take up
Se but to a lesser degree than canola.
• A weed from the mustard family (Arabidopsis
thaliana), genetically modified to include a
gene for mercuric reductase, converted mercuric
salts to metallic mercury and released it to the
atmosphere.
• Groundwater must be within the influence of plant
(usually a tree) roots and soil must be able to transmit
sufficient water to the plant.
508
• Climatic factors such as temperature, precipita-
tion, humidity, solar radiation, and wind velocity
can affect transpiration rates and thus the rate of
phytovolatilization.
• Improved methods for measuring phytovolatiliza-
tion, diurnal and seasonal variations, and precipita-
tion versus groundwater use need to be developed.
• Significant research needs to be focused on mod-
eling impacts of vegetation such as transpiration
stream concentration factors, canopy effects, and
root concentration factors.
9.5.3 Phytoremediation Design
The design of a phytotechnology system varies according
to the contaminants, conditions at the site, level of cleanup
required, and plants used. A thorough site characterization
should provide the needed data to design any type of reme-
diation system. Clearly, phytoextraction has different design
requirements from phytostabilization or rhizodegradation.
Nevertheless, it is possible to specify a few design consider-
ations that are part of most phytotechnology efforts. Site char-
acterization data will provide the information required for the
designer to develop a properly functioning system. The design
considerations include contaminant levels; plant selection;
treatability; irrigation, agronomic inputs (P, N, K, salinity,
zinc, etc.), and maintenance; groundwater capture zone and
transpiration rate; and contaminant uptake rate and cleanup
time required.
Other factors to be considered during the evaluation,
design, and implementation phases of phytoremediation at a
contaminated site are the following:
• Soil water: The most crucial factor in a plant’s life is
water, which links it to the soil via roots and serves
as a vehicle for nutrient transport. Water also con-
trols the exchange of gases and moderates soil tem-
perature changes. Plant available water is held in
the soil between the field capacity and permanent
wilting point. Plant roots can extract water at lower
potentials, depending upon the plant type and arable
environment. Root growth rates are controlled by
the presence of continuing supplies of water to main-
tain hydrostatic pressure in the elongating cells of
the root and metabolites for cell wall construction.
Water flows radially into elongating root cells only
when the cell’s total water potential is lower than
the combined osmotic and matric potentials of the
soil. Soil water content will influence plant biomass
growth.
• Soil air: Plants need molecular oxygen to respire
and convert carbohydrates to carbon dioxide and
water. This is an exothermic reaction and releases
respiratory energy utilized for many plant processes.
The disappearance of oxygen triggers a sequence
of changes in the biogeochemical properties of the
soil; the absence of oxygen alone is sufficient to alter
Remediation Engineering
plant metabolism profoundly. Suboptimal concentra-
tions of oxygen in the soil occur because of interac-
tions among soil properties such as porosity, water
content, temperature, surface water infiltration, and
continuity of air-filled pores with biotic activity.
• Soil temperature: Temperature influences plant pro-
cesses at the cellular level, such as osmotic potential,
hydration of ions, stomatal activity and transpira-
tion, Gibbs free energy available for work, mem-
brane permeability, solute solubilities, diffusion,
and enzymatic activities. Temperature and cultivar
strongly influence the establishment of plants. Low
temperatures also decrease metabolic activity and
root growth.
• Physical impedance: Physical impedance, some-
times called mechanical impedance or excessive soil
strength, can severely affect normal root growth pat-
terns. Such impedances result from increased soil
bulk density, increased cohesion and friction between
soil particles, reduction in soil water content, frost
heave action of soil, and the presence of permafrost
within the root zone. Under an excessive soil strength
environment, roots enter the soil volume where pore
sizes are larger than the root tip. Conversely, if pore
sizes are too small for entry of the main root but not
for the laterals, then laterals proliferate and produce
a highly branched root system.
• Topography: Topography is a critical factor because
it is a key factor in determining runoff velocity
and erosion. In general, the amount of soil ero-
sion increases manifold with increasing degree
and length of slope. Contaminated sites with slopes
greater than 10% are often not suitable for phytore-
mediation without surface modification because of
excessive erosion.
• Soil pH: Plant roots are damaged at pH lower than
4.0. The roots are shortened, thickened, fewer in
number, and dull brown or gray in color. Salinity
is another challenge to phytotechnology applica-
tions in the field. Soluble salts reduce the total water
potential of the soil solution, thus tending to reduce
the potential difference between soil water and the
atmosphere. Excessive soil salinity reduces root
elongation and upsets hormonal balance, as well
as altering soil structure that, in turn, affects plant
growth.
9.5.3.1  Contaminant Levels
During the site characterization phase, the concentration level
of the COCs will be established. High levels of contamina-
tion may eliminate phytoremediation as a treatment option.
Plants are not able to treat all contaminants. The composition
of organic compounds (structure, log Kow, degree of weath-
ering and boiling point range) and degree of adsorption are
important factors in the application of phytotechnologies. It
is important to understand the range of contaminants that can
be treated using phytotechnologies. In addition to knowing
Soil Treatment
contaminants and their concentrations, the depth of the con-
taminants must be known. The primary consideration in this
area is that the contaminant concentrations cannot be phyto-
toxic or cause unacceptable impacts on plant health or yield.
Higher concentrations of contaminants might be tolerated
more readily by plants than by soil microorganisms.
9.5.3.2  Plant Selection
The goal of the plant selection process is to choose a plant
species with suitable characteristics for growth under site
conditions that meet the objectives of phytotechnologies.
Native, crop, forage, and other types of plants that can grow
under regional and climatic conditions should be preferred.
Plants are selected according to the application and the
COCs. For phytotransformation of organic compounds, the
design requirements are that vegetation is fast growing and
hardy and easy to plant and maintain, utilizes a large quan-
tity of water by evapotranspiration, and transforms the COCs
to nontoxic or less toxic products. In temperate climates,
phreatophytes (e.g., hybrid poplar, willow, cottonwood, and
aspen) are often selected because of fast growth, a deep root-
ing ability down to the level of groundwater, large transpira-
tion rates, and the fact that they are native throughout most
of the country.48 A screening test or knowledge from the
literature of plant attributes will aid the design engineer in
selection of plants.
Plants used in phytoextraction include sunflowers and
Indian mustard for lead; Thlaspi spp. (pennycress) for zinc,
cadmium, and nickel; and sunflowers and aquatic plants for
radionuclides. Aquatic plants are used in constructed wetlands
applications. The two categories of aquatic plants used are
emergent and submerged species. Emergent vegetation tran-
spires water and is easier to harvest if required. Submerged
species do not transpire water but provide more biomass for
the uptake and sorption of contaminants.
9.5.3.3 Treatability
Treatability or plant screening studies are recommended prior
to designing a phytotechnology system. If the decision tree
flowcharts indicate phytotechnology is an applicable technol-
ogy for a site, a plant scientist should assist in the treatability
studies that assure concerned parties that the phytotechnol-
ogy system will achieve desired results. Treatability studies
provide toxicity and transformation and assess the fate of the
contaminants in plant system. Different concentrations of
contaminant are tested with proposed plant species. VOCs are
often transpired to the atmosphere by plants; calculations will
predict the amount and type of material transpired.
9.5.3.4 Irrigation, Agronomic Inputs,
and Maintenance
Irrigation of plants ensures a vigorous start to the system even
in drought. Hydrologic modeling may be required to estimate
the rate of percolation to groundwater during irrigation condi-
tions. Irrigation should be withdrawn if the area receives suf-
ficient rainfall to sustain the plants. Agronomic inputs include
the nutrients necessary for vigorous growth of vegetation and
509
rhizosphere microbes. The soil must be analyzed and then
items such as nitrogen, potassium, phosphorous, aged manure,
sewage sludge compost, straw, and/or mulch are added as
required to ensure the success of the plants. Maintenance of
the phytotechnology system may include adding fertilizer,
agents to bind metals to the soil, or chelates to assure plant
uptake of the contaminants. Replanting may be required due
to drought, disease, insects, or animals killing plants.
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4. Nunnally, S.W. (1977). Managing Construction Equipment.
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(1998). Thermally enhanced remediation at DNAPL sites:
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viscopedia.com/basics/factors-affecting-viscometry/#c85.
13. Suthersan, S., Horst, J., Klemmer, M., and Malone, D. (2012).
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under-utilized in  situ remediation solution, Ground Water
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Association, 32(3), 34–40.
14. Washington, J. (1995). Hydrolysis rates of dissolved volatile
organic compounds: Principles, temperature effects, and lit-
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tion heating for in-situ thermal desorption of soils, Chapter
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18, 1990. Assignee: Battelle Memorial Institute.
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17. Jeffers, T.H., Bennett, P.G., and Corwin, R.R. (1993).
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mass: Field studies, Report of investigations 9461. Bureau of
Mines, U.S. Department of the Interior.
18. Heron, G., Christensen, T.H., and Enfield, C.G. (1998). Henry’s
law constant for trichloroethylene between 10 and 95°C,
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19. Francis, J. and Wolf, J. (2004). In  situ remediation of chlo-
rinated VOCs and BTEX using electrical resistance heat-
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(eds.), Remediation of Chlorinated and Recalcitrant
Compounds—2004. Columbus, OH: Battelle Press.
20. U.S. EPA. (2004). Cost and performance report, electric
resistive heating at the ICN Pharmaceutical Site, Portland,
OR, February 2004. In-situ thermal treatment of chlori-
nated solvents: Fundamentals and field applications. EPA
542-R-04-010, March. Office of Solid Waste and Emergency
Response, Office of Superfund Remediation and Technology
Innovation.
21. McGee, B.C.W. (2003). Electro-thermal dynamic stripping
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File date March 22, 2001.
22. Major, D. and Savron. (2016). Personal communication.
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underground toxic wastes. In Tien, C.-L. (ed.), Annual
Reviews of Heat Transfer. New York: Begell House Inc., Vol.
7, pp. 333–405.
24. Beyke, G. and Fleming, D. (2005). In situ thermal remediation
of DNAPL and LNAPL using electrical resistance heating,
Journal of Remediation, 15(3), 5–22.
25. Gaberell, M et  al. (2002). Soil core characterization strat-
egy at DNAPL sites subjected to strong thermal and chemi-
cal remediation. In Proceedings of Battelle Conference on
Remediation of Chlorinated and Recalcitrant Compounds,
Monterey, CA.
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stabilization, July 2011.
27. Sale, T. (2012). Colorado State University. Personal
communication.
28. Landmeyer, J.E. (2012). Introduction to Phytoremediation of
Contaminated Groundwater. New York: Springer.
29. ITRC. (2009). Phytotechnology Technical and Regulatory
Guidance and Decision Trees, Revised. Washington, DC:
Interstate Technology and Regulatory Council.
30. USEPA. (February 26, 2016). Phytotechnologies over-
view. Retrieved from Clu-In contaminated site clean-up
information: https://clu-in.org/techfocus/default.focus/sec/
Phytotechnologies/cat/overview.
31. USGS. (February 26, 2016). The water cycle—USGS water
science school, evapotranspiration. Retrieved from United
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cleevapotranspiration.html.
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(eds.), Phytotechnologies: Remediation of Environmental
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36. Conger, R.M. and Portier, R. (1997). Phytoremediation
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and Pereira, M.E. (2013). Introduction. In Anjum, N.A., Pereira,
M.E., Ahmad, I., Duarte, A.C., Umar, S., and Khan, N.A. (eds.),
Phytotechnologies. Boca Raton, FL: CRC Press, pp. 1–4.
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United States with a discussion of principles. Water-Supply
Paper 489. Washington, DC: USGS.
 10 Reactive Walls
10.1  REACTIVE BARRIERS
A permeable reactive barrier (PRB) is a remediation industry
standard term that defines an in situ treatment zone designed to
intercept and remediate a contaminant groundwater plume.1 The
concept of a PRB is the installation of a permeable or imper-
meable wall perpendicular and downgradient of a contaminated
groundwater plume. Permeable barriers are continuous walls
that encourage contaminated groundwater to flow throughout
the entire length of the barrier. Impermeable barriers direct the
flow of impacted groundwater to specially designed perme-
able reactive gates installed along the impermeable barriers.
Engineered treatment reactions that destroy or immobilize tar-
geted contaminants in the groundwater occur either through-
out the continuous PRB or within the reactive gates. Treated
groundwater then follows its natural course after exiting the
barrier. The flow through the barrier is passive and is driven
by the natural groundwater gradient. If a groundwater plume is
relatively narrow, a continuous PRB can be installed across the
full width of the plume and thus preclude the necessity for the
installation of impermeable barriers with reactive gates.
The PRB strategy has been proven successful at many
sites, and the installation process has evolved since the earliest
implementations. As of 2011, there were more than 200 field-
scale PRBs in operation throughout the world,1 with the first
field-scale pilot PRB dating back to 1991 by the University of
Waterloo.2–4 At first, PRBs were typically trenches or sheet pile
walls with reactive gates (impermeable barriers). However, as
the regulatory view of the technology developed since the first
implementation in the early 1990s, the PRB concept may range
from a physically constructed trench to a transect of injection
wells to a series of overlapping soil-mixed columns.1 The effec-
tiveness of the PRB is influenced by many design components,
and the selected construction of a PRB should provide the most
effective approach for the lowest cost. PRBs reduce long-term
operation and maintenance (O&M) costs and, therefore, life
cycle costs, which are typically appreciable for most remedia-
tion projects. The popularity of PRBs has resulted in numerous
guidance documents from government and state research agen-
cies, and the amount of published information supporting PRB
installation and operation is abundant.1,5–10 This chapter aims
to succinctly summarize the key points of design, installation,
operation, and monitoring.
PRBs may be conceptualized as in situ reactors designed
to achieve the same treatment reactions that are utilized in a
groundwater extraction and treatment system (GETS). A PRB
has a distinct advantage over a GETS due to the greater
contaminant treatment reagent contact time (i.e., residence
time [ϑ]) available in situ. Typical groundwater flow veloci-
ties will provide residence times (ϑ) of days, if not weeks,
in comparison to minutes or hours available in aboveground
reactors. As a result, mass removal efficiencies could be
expected to reach close to 100% in a properly designed PRB.
Additionally, PRBs are considered a more sustainable in situ
remedial strategy, if designed to last for an extended duration.
A recent sustainability life cycle assessment between PRBs
and GETS found that it takes 10 years in the minimum thresh-
old for a PRB to outcompete GETS.11
Proper design and construction are important because once
a PRB is installed, little can be done to rectify any issues.12
Of the currently operating PRBs, some are failing to meet
design objectives13 as a result of neglecting shifts in hydraulic
gradient, incorrect treatment interval thickness, passivation of
treatment reagent, diminished reactivity over time, and less
permeability across the PRB than ambient aquifer.14 Of the
reported poor performance of PRBs, the most common cause
is a poor understanding of the site-specific hydrogeology.15
This chapter explores the concepts and design of PRBs and
provides case study examples with which the authors have
design, implementation, and evaluation experience.
10.2  TECHNOLOGY OVERVIEW
A PRB may be considered as an alternative to a GETS.
Depending on the anticipated future use of the contaminated
aquifer and the acceptable remediation time frame, PRBs
may eliminate the need for active in situ treatment. PRBs can
be installed at the downgradient edge of a groundwater con-
taminant plume as a containment strategy and/or immediately
downgradient of the source area to prevent further transport
of contaminant mass. Physical, chemical, or biological mech-
anisms can be implemented within the PRB. In this section,
the conventional configurations for a PRB are discussed.
10.2.1  Configurations
The configuration of a PRB to the contaminated groundwater
flow direction will influence the geometry (dimensions and
arrangement) of the treatment component. For impermeable
reactive barriers with reactive gates (referred to as “funnel
and gate” configurations), the design is complex. For example,
suppose existing site infrastructure constrains the construc-
tion of the funnel and gate PRB such that groundwater flow is
anticipated to increase within the reactive gate. The increased
groundwater velocity may result in an insufficient residence
time (ϑ), and as a result the design may fail to meet the targeted
objectives. Potential solutions may be numerous reactive gates
in parallel or series, widening the reactive gates, or switching the
configuration (i.e., continuous PRB or caissons PRB). Selection
511
512
of the optimal geometry for a continuous PRB is simpler than
for a funnel and gate PRB. A continuous PRB is constructed
with permeable treatment media across its entire length, and
there are less hydrogeologic concerns for achieving complete
capture of the groundwater contaminant plume. The feasibility
and cost of constructing a continuous PRB will determine the
depths to which this configuration can be installed.
The PRB configuration is a critical parameter that requires
an engineering cost-benefit analysis. It is obvious that the dif-
ferent options present pros and cons and have variable cost
implications. The reactive gates and treatment interval usually
dictate the cost associated with the installation of the PRB.
Thus, the optimum design will minimize the number and
thickness of the reactive gates/treatment interval while still
accommodating groundwater flow from the entire contami-
nated plume and providing adequate residence time (ϑ) within
the treatment reagent. Typical PRB configurations available
from which to choose include continuous PRBs, funnel and
gate PRBs, and in situ reactive vessels. If the groundwater flow
and contaminant plume orientation are well understood with
minimal construction constraints, the continuous PRB is the
best design choice.8 The two selected for discussion in this
chapter are continuous and funnel and gate PRBs. In situ reac-
tive vessels are similar in construction to funnel and gate PRBs,
except the reactive gates is replaced by a reaction vessel, which
essentially is a residence tank emplaced below ground surface.
10.2.1.1  Continuous Permeable Reactive Barrier
The simplest configuration is a continuous PRB that extends
across the entire width of the plume (Figure 10.1). This PRB can
Continuous reactive
media intercepts entire
plume
(a)
Reactive gate
Funnel and gate PRB
Funnel
Contaminant plume
GW flow
(b)
FIGURE 10.1  Cross-sectional views of (a) continuous and (b) funnel and gate permeable reactive barriers.
Remediation Engineering
be installed by excavating a trench in the aquifer matrix and
backfilling with a combination of inert, highly porous material
(e.g., coarse sand) and treatment reagent (e.g., zerovalent iron
[ZVI]). This mixture facilitates groundwater flow and contami-
nant treatment simultaneously. For sites at which the targeted
treatment interval is below the reach of excavating equipment,
reagent injections may be used to create the continuous PRB.
As the contaminant plume moves through the continuous PRB,
contaminants are removed by various physical, chemical, and
biological mechanisms (i.e., air stripping, biodegradation,
adsorption, chemical oxidation, abiotic degradation, metals
precipitation), depending on the treatment reagent selected. The
potential treatment reactions for various contaminants that could
be implemented within a PRB are summarized in Table 10.1.
Suitability of this PRB configuration will depend upon the site-
specific geologic and hydrogeologic conditions and the nature
and extent of contamination. The preferred treatment processes
are those that are easily implemented in a cost-effective man-
ner and require minimal O&M. The most common treatment
processes are anaerobic, driven by reaction products from the
corrosion of ZVI metal embedded in the PRB.
The construction process must avoid excessive mixing of
aquifer matrix material (usually low-permeability soils) with
the porous fill so that maximum hydraulic conductivity can be
maintained in the PRB. If this separation is not maintained, it
is possible to construct a relatively low-permeability barrier
that blocks groundwater flow. It is also important to main-
tain a consistent placement of fill, because variations in per-
meability will channel groundwater flow to some areas and
bypass others, shortening the treatment reagent lifespan.16
Continuous PRB
Contaminant plume
GW flow
Funnel and gate:
Physical barriers direct
groundwater to a smaller
reactive gate
Reactive Walls 513

TABLE 10.1
Relevant Reaction Mechanisms for Example Constituents of Concern in Permeable
Reactive Barriers
Physical Chemical Biological
COC Air Sparging Adsorption Precipitation Abiotic Reduction Oxidation Aerobic Anaerobic
CE X a X X X X
CA X X X X X
CP X X X X X
Freon X X X
NB X X X X X
BTEX X X X X
PAH X X X X
EN X X X X
ClO4− X X X
NAPL X
Creo X
+Me X X X X
As X X
Cr(6+) X X X X
UO22+ X X X X
Sr-90 X X
Se X X
PO43− X
NO3− X X X
NH4+ X X
SO42− X X X
MTBE X X X
1,4-D X X

Sources: ITRC, Permeable reactive barrier: Technology update, The Interstate Technology and Regulatory Council PRB:
Technology Update Team, Washington, DC, 2011, http://www.itrcweb.org/Guidance/GetDocument?documentID=69;
Suthersan, S.S. and Payne, F.C., In Situ Remediation Engineering, CRC Press, Boca Raton, FL, 2005.
a X mark indicates a recommended treatment mechanism.

CE, chloroethenes; CA, chloroethanes; CP, chlorinated pesticides; NB, nitrobenzene; BTEX, benzene, toluene, ethylbenzene,
and xylenes; PAH, polyaromatic hydrocarbons; EN, energetics; ClO4−, perchlorate; NAPL, nonaqueous phase liquid; Creo,
creosote; +Me, cationic metals; As, arsenic; Cr(6+), hexavalent chromium; UO22+, uranyl uranium; Sr-90, strontium; Se, sele-
nium; PO43−, phosphate; nitrate, NO3−; ammonium, NH4+; sulfate, SO42−; MTBE, methyl tert-butyl ether; 1,4-D, 1,4-dioxane.

10.2.1.2  Funnel and Gate Permeable Reactive Barrier
Funnel and gate PRBs comprise a groundwater flow barrier
(the funnel) constructed perpendicular to the axis of ground-
water flow that directs groundwater flow through a reactive
chamber (reactive gate) and discharges the treated groundwa-
ter to the downgradient side of the PRB. A general descrip-
tion of the funnel and gate concept, showing low-permeability
barriers in several configurations, is presented in Starr and
Cherry.17 Because the impermeable funnel section blocks the
flow, groundwater mounds on the upgradient side of PRB.
The diagrams in Starr and Cherry17 represent relatively simple
systems. In practice, it is desirable to prevent the buildup of
groundwater on the upgradient side of the PRB, opting instead
to provide collection trenches upgradient of the barrier to
channel groundwater flow through the reactive gate.
Funnel and gate PRBs can be constructed across the entire
vertical thickness of a contaminated aquifer. At a site with
dense nonaqueous phase liquid (DNAPL) present, the funnel
and gate PRB may be needed to extend over a considerable
vertical thickness given the propensity of DNAPL to transport
contamination vertically. When the groundwater contaminant
plume is shallow, a condition most likely associated with the
presence of light nonaqueous phase liquid (LNAPL), penetra-
tion of the aquifer may be required only to the depth of mea-
sureable contamination. The two configurations mentioned
earlier are known as a “fully penetrating gate PRB” and a
“hanging gate PRB,”17 respectively (Figure 10.2).
The main advantage of a funnel and gate PRB over a con-
tinuous PRB is that a smaller-scale reactive gate is used for
treating a given plume, usually at a lower cost. Groundwater
flow through an aquifer is heterogeneous and typically fol-
lows discretized intervals of higher permeability. Treatment
reagent in a PRB is a cost driver, and a continuous PRB treat-
ment reagent is required across the entire length of the PRB.
514
Contaminant-
Contaminant plume free water
Bedrock
Contaminant source
in the saturated zone
(a)
Contaminant-
free water
Contaminant
plume
Bedrock
Source of
contaminant
(b)
FIGURE 10.2  Cross-sectional views of (a) fully penetrating gate
and (b) hanging gate funnel and gate permeable reactive barriers.
Because groundwater flow is variable across the length of the
PRB, it is possible that some treatment reagent may never be
used. In a funnel and gate PRB, groundwater flow is brought to
the reactive gate, ensuring that all treatment reagent is utilized.
Additionally, if a PRB requires periodic treatment reagent
replacement (such as a granular activated carbon [GAC] or ion
exchange media) or flushing out precipitated minerals, it will
be easier to accomplish this in a smaller reactive gate. Similar
to the continuous PRB configuration, various physical, chemi-
cal, and biological mechanisms are applicable (i.e., air strip-
ping, biodegradation, adsorption, chemical oxidation, abiotic
degradation, and metals precipitation [Table 10.1]). In addition,
physical recovery techniques for LNAPL and DNAPL recov-
ery can also be implemented within the reactive gate.
The funnel and gate PRB geometry required to direct all
the contaminated groundwater through the reactive gate and
the ease of installation will determine the applicability in
most cases. The simplest geometry of a funnel and gate PRB
is a single reactive gate with cutoff walls extending on both
sides of the reactive gate (Figure 10.3). This configuration is
more suitable for a narrow, elongated plume. Selected treat-
ment reactions to address the specific contaminants and the
ease of implementation will also influence the applicability of
a funnel and gate PRB.
When dealing with a groundwater plume that contains
multiple contaminants, two or more reactive gates in series
may be required to implement different treatment reactions.
For example, a plume containing trichloroethylene (TCE)
and acetone may require a reactive gate with an air injection
Remediation Engineering
Gate
Funnel
(a)
Gate
Funnel
(b)
FIGURE 10.3  Possible configurations of (a) single gate funnel and
(b) gate permeable reactive barriers.
and extraction system (for removing TCE) to be followed by a
fixed film bioreactor gate (for degrading acetone). If the same
plume has pentachlorophenol (PCP) in it, a third reactive gate
with GAC may be required for PCP removal. Reactive gates
in series are shown on Figure 10.4.
When the contaminant plume is relatively wide, multiple
reactive gates may be required in parallel to direct contami-
nated groundwater to flow through the reactive gates (Figure
10.4). Multiple reactive gate PRBs can be installed as fully
penetrating or hanging gates as dictated by the depth of con-
tamination. When designing a multiple reactive gate PRB, a
balance between maximizing the size of the capture zone and
the retention time (ϑ) in the reactive gate should be achieved.
In general, capture zone size and retention time (ϑ) are
inversely related.17
The treatment reactions summarized in Table 10.1 can also
be implemented in multiple reactive gate geometries. The
width and depth of the funnel, the required number of reactive
gates, and the total thickness of the reactive gates all play sig-
nificant roles in deciding whether this technique is the most
cost-effective alternative to address the subject groundwater
contaminant plume.
10.2.1.2.1  Funnel Width and Angle
Increased funnel widths provide a larger capture zone, and
thus the required groundwater flow capacity through the
Reactive Walls 515

reactive gates is increased accordingly. Beyond the localized

Reactive Pea
gravel influence around the funnels, the width of the capture zone is
cell
generally proportional to the groundwater flow through the
Caisson
reactive gate for a given site. The required capture zone will
gate 1 determine the optimum funnel width and the number of reac-
Plume tive gates.
It has been shown that the maximum discharge and capture
Caisson occurs when the funnel is perpendicular to the groundwater
gate 2 flow direction17 (Figure 10.5). The effective width of the funnel
decreases when the funnel is not straight and has an apex angle.
U-shaped funnels provide a smaller capture zone in compari-
Funnel son to a straight funnel of the same length (Figure 10.5).

(a) 10.2.1.2.2  Reactive Gate Length

As the total length of the reactive gate(s) increases, relative to
Reactive Pea the total funnel width, the absolute and relative flow and the
Funnel medium 1 gravel
width of the capture zone increase. The absolute flow (Qabs) is
defined as the flow through the reactive gate(s) at a given time.
The relative flow (Qrel) is the fraction of flow intersected by
Plume the funnel width, which flows through the reactive gate(s). It
Gate is calculated by dividing the flow through the reactive gate(s)
(Qabs) by the natural groundwater flow (Q) through a section
of the aquifer equal to the width and depth of the funnel at an
Reactive
upgradient location in the absence of the funnel and gate PRB
medium 2 according to the following equation:
(b)
Qabs
Qrel = (10.1)
FIGURE 10.4  Illustration of reactive gates in both (a) series and (b) Q
parallel orientation. (From Gavaskar, A.R. et al., Permeable Reactive
Barriers for Groundwater Remediation Design, Construction, and A reactive gate that is as wide as possible is desirable from
Monitoring, Battelle Press, Columbus, OH, 1998.) a treatment perspective; however, economic considerations
limit the length of the reactive gate.

10.2.1.2.3  Reactive Gate Permeability

It is easy to understand that when the permeability of the reac-
tive gate is higher, the absolute flow (Qabs) also will be higher.
However, it has been reported that there is relatively little
increase in absolute flow (Qabs) through the reactive gate when
Gate Gate the reactive gate permeability is greater than 10 times that of
native soils of the aquifer.17 This is due to the fact that flow
is limited by the transmissivity of the aquifer upgradient and
downgradient of the reactive gate. While there is a general ten-
Funnel Funnel dency among designers of funnel and gate PRBs to make the
(a) (b) reactive gate permeability as high as possible, high values are
not required for proper functioning of the PRB and may not
be desirable due to the potentially shortened residence times
(ϑ). However, consideration should be given to the potential
Gate Gate
fouling of the reactive gate treatment reagent due to microbial
growth and/or inorganic mineral precipitation and the eventual
Funnel
decrease in reactive gate permeability. In addition, treatment
Funnel reactions such as adsorption or biodegradation via immobi-
(c) (d) lized biomass may require increased surface area within the
reactive gate. Under these circumstances, the porosity of the
FIGURE 10.5  Illustration of effective width of a funnel and treatment reagent that will provide a higher permeability will
impact on capture zone by the funnel configuration. Comparison have to be balanced with the need to have a higher available
between (a) straight and (b) apex-angled funnels and (c) straight and surface area. Media with higher available surface area will be
(d) U-shaped funnels. finer particles and thus will have a lower mobile porosity.
516 Remediation Engineering

10.2.2  Constructability Considerations
In addition to being cost-effective over an extended duration,
PRB typically remains functional for years with little or no
O&M requirements (aside from performance monitoring).
PRBs may require a high initial capital investment in some
cases, but comparatively lower long-term life cycle costs as a
result of greatly reduced O&M costs justify the capital invest-
ment. A summary of various installation techniques for PRB
construction for both continuous PRBs and funnel and gate
PRBs is presented in Table 10.2.
10.2.2.1 Components
The required components of a PRB are dependent on the
configuration. Continuous PRBs require treatment reagent
and structural backfill spanning the vertical interval tar-
geted for treatment. They also require careful compac-
tion to maintain a higher permeability than ambient soil to
promote rather than discourage flux through the treatment
interval. Deep continuous PRBs will settle and consolidate
over time under the overburden pressure of the backfill, and
this should be considered during construction. Continuous
PRBs (depending on the selected reagent mechanism;
Section 10.2.1) may benefit from injection/extraction wells
installed along the length of the PRB to facilitate recharge or
regeneration of the treatment reagent. Funnel and gate PRBs
require impermeable funnels to direct groundwater through
reactive gates. The funnels need to be keyed into an aquitard
at the base or sufficiently deeper than the deepest vertical
contaminant impact to ensure groundwater doesn’t short cir-
cuit beneath the PRB. The reactive gates are designed such
that the treatment reagent may be recharged or regenerated
easily, if necessary.
10.2.2.1.1  Continuous Permeable Reactive Barriers
Construction of a PRB will be influenced by the installation
depth. Deeper PRB installation depths require larger trench
thicknesses to facilitate the installation. Various backfill
materials can be used as the treatment reagent within the
PRB depending on the targeted treatment process. A sum-
mary of various treatment reagents used in PRBs is presented
in Table 10.3, but this is not a comprehensive list. Given the
inherent flexibility of the PRB concept (i.e., a vertical barrier
intercepting a groundwater contaminant plume), the selected
treatment reagent and PRB configuration is limited only by
the creativity and innovation of the designer.
There are various methods to install a trench-based PRB.
Backhoes, or trenchers (also known as ditchers), can be used

TABLE 10.2
A Summary of Various Installation Methods for Permeable Reactive Barrier Construction
Installation Method Maximum Depth (ft) Approximate Cost Comments
Slurry wall and sheet pile installation

Soil–bentonite slurry wall

Standard backhoe excavation 30 $2–10/ft2 Requires a large working area to allow for mixing of backfill.
Modified backhoe excavation 80 $2–10/ft2 Generates some trench spoil. Relatively inexpensive when a
Clamshell excavation 150 $6–17/ft2 backhoe is used.
Cement–bentonite slurry wall
Standard backhoe excavation 30 $4–22/ft2 Generates large quantities of trench spoil. More expensive than
Modified backhoe excavation 80 $4–22/ft2 other slurry walls.
Clamshell excavation 200 $16–55/ft2
Composite slurry wall 100+ NA Multiple-barrier wall.
Geomembrane barrier 40–50 $38/ft2 Permeability less than 1 × 10–7.
Steel sheet piles 60 $15–30/ft2 No spoils produced.
Sealable-joint piles 60 $15–30/ft2 Groutable joints.
PRB installation
Caisson-based construction 50+ $50–300/vertical ft Relatively inexpensive.
Mandrel-based construction 40–50 $10–25/ft2 Relatively inexpensive and fast production rate. A 3–5 in. thick zone
can be installed in a single pass.
Continuous trenching 25 $5–12/ft2 High production rate.
High mobilization cost.
Jetting 200 $40–200/ft2 Ability to install barrier around existing buried utilities.
Deep soil mixing 150 $80–200/yd3 May not be cost-effective for PRBs. Columns are 3–5 ft in diameter.
Hydraulic fracturing 80–120 $2,300/fracture Can be installed at deep sites. Fractures are only up to 3 in. thick.
Vibrating beam 100 $8/ft2 Driven beam is only 6 in. wide.

Source: Gavaskar, A. et  al., Design guidance for application of permeable reactive barriers for groundwater remediation, Strategic Environmental
Research and Development Program, March 2000.
Reactive Walls
TABLE 10.3
Potential Sources of Treatment Reagent and the
Associated Relevance to In Situ Remediation with
a Permeable Reactive Barrier
Treatment
Reagent Applicability to In Situ Remediation
Pea gravel Structural integrity and porosity; works well with air
sparing PRBs, but also applicable wherever natural
permeability is more coarse-grained.
Coarse sand Structural integrity and porosity; works well with
most treatment reagents and provides a reasonable
hydraulic gradient across the PRB.
ZVI Abiotic reductive dechlorination, iron-mediated
metals precipitation.
Crushed sea shells Excellent media for adsorption of biomass (aerobic
and anaerobic); structural integrity and porosity.
Limestone Structural integrity and porosity; acidity
neutralization facilitating metal hydroxide and metal
carbonate precipitation.
GAC Adsorption of organic compounds; surface area for
biomass growth.
Zeolites Cation exchange and adsorption of metals.
Organophilic clays NAPL adsorption.
Apatite Metals precipitation; complexation to immobilize
inorganics.
Gypsum Anaerobic biological oxidation.
Oxidant canisters Most borehole releasing oxidants are ineffective for
in situ remediation that requires large volume to
distribution relationships. In a PRB, oxygen and
ozone diffusers, paraffin wax cylinders, oxygen
releasing compounds, oxidant-impregnated GAC,
etc., may be more relevant within the
treatment interval.
Organic carbon Anaerobic biological reduction (most importantly not
only metals precipitation and reductive
dechlorination but also anion reduction as necessary
[perchlorate, nitrate, sulfate]).
ZVI–carbon Abiotic and biological reductive dechlorination,
combo metals precipitation, anion reduction.
Emulsified ZVI Similar to ZVI–carbon.
Sparged air Enhanced volatilization of organic compounds,
requires vapor recovery.
to excavate the trenches. Depending on the depths of excava-
tion and location of the trenches, shoring techniques may have
to be implemented to prevent the trench from collapsing. If
the trench has to be excavated near a building, shoring may
be required to ensure the safety of the building foundations.
Application of a biodegradable slurry has been used in the
recent past to minimize the cost of shoring. The slurry helps
to stabilize the slopes until the backfill material is placed in
the trench. The slurry will be completely biodegraded within
a short time frame and the trench will, thus, function as a
permeable trench. Trench boxes may also be used to install a
trench for a PRB.
517
10.2.2.1.2  Types of Funnel Walls
There are various types of impermeable or less permeable
subsurface barriers that can be used as funnels in a funnel and
gate PRB. The purpose of the funnel is to direct the flow of
contaminated groundwater through the reactive gates where
the targeted treatment processes occur. Slurry walls and sheet
pile walls are commonly used techniques, and they are dis-
cussed here, but several other techniques are presented in
Table 10.2.
10.2.2.1.3  Slurry Walls
Recall from Chapter 9 that in situ soil stabilization (ISS) is
a soil treatment technique that destroys the natural structure
of soil by mixing solidification agents or treatment reagents
into a treated monolith. In an ISS application the main focus
of the technology is solidification or stabilization to reduce
contaminant mass flux or destroy contamination; however,
as a result of mixing the soil and removing heterogeneities
and anisotropies, the bulk permeability of the treated mono-
lith is reduced. It has been well established that groundwater
flow in aquifers is highly discretized within intervals of high
hydraulic conductivity,16 and by blending the collection of
hydraulic conductivities within a particular aquifer thickness,
the resultant hydraulic conductivity is less than the discrete
intervals driving groundwater flow. This is the same concept
as a slurry wall, except instead of encapsulating an area, here
the slurry wall is installed within a vertical trench over the
aquifer thickness targeted for a funnel and gate PRB.
Slurry walls are a means of placing a low-permeability, sub-
surface funnel. They consist of vertically excavated trenches
(or deep soil mixing techniques) and are described by the
material used as backfill. Slurry walls installed through deep
soil mixing techniques are installed using large overlapping
augers equipped with mixing paddles. As the group of augers
is advanced into the ground, additives such as bentonite or
cement are injected and mixed with the soil.
Soil–bentonite slurry walls are composed of soil materi-
als (often the excavated soil) mixed with bentonite clay (ben-
tonite) slurry. Cement–bentonite walls are constructed using
a slurry of Portland cement and bentonite and set to form a
permanent, low-permeability wall. Diaphragm walls are
installed of precast or cast-in-place reinforced concrete panels
(diaphragms) installed during slurry trenching. Each of these,
as well as hybrids of the three, have different characteristics
and applications. In general, soil–bentonite slurry walls are
less permeable and are more resistant to chemical degrada-
tion than cement–bentonite walls. Slurry walls can be con-
structed to significant depths (150–200 ft). A structural cap
may have to be installed to maintain the strength and integrity
of the slurry walls. At a site with significant vehicular traffic,
a structural cap on the wall will likely be required.
Due to the subsurface nature of construction, the potential
exists for construction and post-construction defects associ-
ated with slurry walls. These defects may include discontinu-
ous resistance to groundwater flow across the targeted length
(i.e., gaps in the low-permeability wall), poorly mixed backfill,
518
TABLE 10.4
Permeability of Permeable Reactive Barrier Materials
for Impermeable Barriers (e.g., Funnels)
Permeability Permeability
Material (Lab) cm/s × 10–8 (Field) cm/s × 10–8
Bentonite slurry 5 50
Cement–bentonite 3 100
Compacted soil–bentonite 0.1 10
Soil–cement 0.5 50
Cement–grout 0.1 1,000
Concrete 0.1 —
Silicate grout 47 10,000
Natural Silt: (no lab) 6,000 × 10−8 cm/s (field)*
Source: Boscardin, M.D. and Ostendorf, D.W., Cutoff walls to contain
petroleum contaminated soils, in Petroleum Contaminated
Soils, Calabrese, E.J. and Kostecki, P.T., eds., Lewis Publishers,
Boca Raton, FL, 1989.
* Natural silt is representative of fine-grained natural stratigraphy for
comparative purposes.
and trapped pockets of slurry. Post-construction defects may
include cracking due to change in moisture, temperature, con-
solidation, and stress as well as increased permeability due to
chemically aggressive contaminants. It is known that some
contaminants can react with slurry wall construction materi-
als and potentially cause increases in permeability over time.
When selecting the construction materials for the slurry wall,
chemical compatibility with the contaminants is typically
considered; however, the duration of contact for a PRB can
exceed 10 years, and durability over that length of time is dif-
ficult to predict. Bentonite-based slurry walls are adversely
impacted by some organic contaminants.18 However, propri-
etary mixes of treated bentonite may provide satisfactory per-
formance under appropriate conditions.
The estimated resultant permeability of various slurry
walls using several construction materials is presented in
Table 10.4. Note that laboratory results performed under con-
trolled conditions exhibit lower permeabilities than field con-
ditions. This is intuitive as the degree of distribution of the
low-permeability material is achieved at a higher certainty
with aggressive mixing at the bench scale.
10.2.2.1.4  Sheet Pile Walls
An impermeable or low-permeable funnel can be installed
using closely spaced steel sheet piles in a longitudinal direc-
tion. The sheet pile funnel can be installed using conventional
pile driving techniques. Vibratory or impact pile drivers can
be used depending upon the soil conditions. Vibratory equip-
ment is suitable for most soil conditions, but better results can
be achieved with impact equipment in certain cohesive soils.
A foot plate at the toe of each larger interlock prevents most
of the soil from entering the sealable cavity during driving.
After the pile driving is done, the cavities are water jetted to
remove the loose soil caught up in the interlocks. A number
Remediation Engineering
of clay-based, cementitious polymer and mechanical sealants
are available to meet a variety of site conditions.
The space between adjoining sheet piles may allow leakage
of contaminated groundwater without being deflected toward
the reactive gate for treatment. A technique (i.e., the Waterloo
BarrierTM) was developed to seal the joints between adjacent
sheet piles specifically for the purpose of installing funnel and
gate PRBs.19 This proprietary technique incorporates a sealable
cavity into the sheet pile interlocks (Figure  10.6). Extensive
field-scale tests conducted indicate that bulk hydraulic con-
ductivity values of less than 10 –8 cm/s can be achieved with
this arrangement. Potential leak paths through the barrier are
limited to the sealed joints, and therefore the joints should be
inspected before the sealing operation to confirm that the com-
plete length of the cavity is open and can be sealed. Each joint
should be sealed from bottom to top, facilitating the emplace-
ment of a sealant into the entire length of the joint.
10.2.2.2  Installation Methods
There are two general installation methods for PRBs: excava-
tion-based and injection-based installations. Important physical
characteristics that influence the installation method selection
include geotechnical parameters (i.e., grain size, Atterberg lim-
its, moisture content, cohesion), groundwater elevation, con-
taminated soil classification, and the PRB installation depth.
The geotechnical parameters and groundwater elevation are
important because they dictate the level of sophistication of
an excavation-based installation (i.e., degree of sloping and
shoring, dewatering, and strength considerations). The ground-
water elevation and the PRB installation depth influence the
required injection pressures for an injection-based PRB instal-
lation. The excavated soil contaminant soil classification may
disqualify an excavation-based installation method for a source
area PRB because the waste disposal charge may be excessive.
Typically, shallow PRBs are most cost-effectively installed
through excavation-based installation methods, and deep
PRBs are most cost-effectively installed using an injection-
based installation method. This section briefly identifies and
describes the various excavation- and injection-based installa-
tion methods. For more information on the available installa-
tion methods, the reader is referred to the Interstate Technology
Regulatory Council (ITRC) guidance documents1,5–7 and Naidu
and Birke20 (and associated references therein).
10.2.2.2.1  Excavation-Based Installation Methods
The degree of sidewall stability support for an excavation-
based installation determines the type of excavation-based
installation method. The simplest excavation method is an
unsupported excavation, in which no sidewall stability support
is required. It is intuitive that the applicability of unsupported
excavation is heavily based on the site-specific groundwa-
ter elevation and geotechnical parameters. Benching, or a
successively more narrow excavation, may eliminate the
need for sidewall stability support if the cohesion of the site
soils is sufficient to prevent collapse. The more complicated
­excavation-based installation method is supported excavations
that do require sidewall stability support.
Reactive Walls
Female
joint
Grout
Male
joint
Plan view
FIGURE 10.6  Sealable, interlocking joints for sheet pile walls. (From Gavaskar, A.R. et al., Permeable Reactive Barriers for Groundwater
Remediation Design, Construction, and Monitoring, Battelle Press, Columbus, OH, 1998.)
Five available supported excavation-based installation
methods are continuous trenching, biopolymer/slurry wall
trenching (hydraulic shoring), sheet piling, augured boreholes/
caissons/soil mixing, and clamshell excavators:
• Continuous trenching (Figures 10.7 through 10.9)
is excavation and backfilling of the PRB simultane-
ously and can be completed in 1–3 ft in thickness
to depths of approximately 35 ft.1 There is no open
trench with continuous trenching and therefore slope
stability is intrinsic, but limits the depth of installa-
tion. This is the most popular excavation installation
method assuming the depth of the PRB is less than
35 ft.
• Biopolymer/slurry wall trenching (hydraulic shor-
ing; Figure 10.10) uses a biodegradable guar gum
slurry or bentonite clay/cement/soil slurry, respec-
tively, which occupies the excavated PRB until the
FIGURE 10.7  One-pass trencher preparing to install a permeable
reactive barrier with zerovalent iron as the treatment reagent.
519
Female
joint
Joints
Male
joint
First
sheet pile
Second
sheet pile
Waterloo barrier
sealable joint
sheet pile section
treatment reagent and structural backfill is placed.
Trench thicknesses of greater than 2 ft and up to 70 ft
deep are supported with this approach.1 For biopoly-
mer slurry shoring, an enzymatic solution circulated
throughout the PRB is used to naturally degrade
the biopolymer, which provides total organic car-
bon (TOC) for natural bacteria, after construction is
complete. Slurry walls constructed of soil/benton-
ite, Portland cement/bentonite, and other composite
slurries are commonly used as impermeable funnels
for a funnel and gate PRB.21
• Sheet piling (Figures 10.6 and 10.11) relies on
installing sheet piling around the perimeter of the
PRB excavation, with internal bracing as installa-
tion depth increases (up to approximately 50 ft).20
A vibratory hammer is used to install the sheet pile,
FIGURE 10.8  One-pass trencher installing permeable reactive
barrier with zerovalent iron as the treatment reagent to a 35 ft depth.
520 Remediation Engineering

HDPE panels
are lowered
Rollers feed pipe through a separate
compartment

Dual-laser
guidance system

HDPE
panels in place

Filter media feeds

through hopper

Boot supports
trench sidewalls
Digging
chain Backfill

Gate

FIGURE 10.9  Schematic of continuous trencher in operation. (From Gavaskar, A.R. et al., Permeable Reactive Barriers for Groundwater
Remediation Design, Construction, and Monitoring, Battelle Press, Columbus, OH, 1998; Reprinted from Groundwater Control, Inc., Here’s
how it works…, Groundwater Control Inc., One-pass deep trencher, Soil and Groundwater Cleanup Informational Brochure, Jacksonville,
FL, 1996. With permission of Groundwater Control, Inc.)

FIGURE 10.10  Installation of a continuous permeable reactive

barrier with mulch/walnut shells/emulsified vegetable oil as the
treatment reagent using biopolymer slurry as a hydraulic shoring
solution.

and the University of Waterloo has a patented tech-

nique for sealing adjoining sheet piles that involves
placing grout into the joints (Figure 10.6).22 In a fun-
nel and gate PRB, the sheet piles remain in place
to serve as impermeable funnels. In a continuous FIGURE 10.11  Sheet pile installation. (Reproduced from Naidu, R.
PRB, the sheet piles are removed after the treatment and Birke, V., Permeable Reactive Barrier Sustainable Groundwater
reagent and structural backfill has been placed. The Remediation, CRC Press, Boca Raton, FL, 2015. With permission;
potential for smearing the PRB/aquifer interface Roberton Geo Consultants, Inc., Vancouver, BC, Canada.)
Reactive Walls 521

distribution along the length of the PRB than injection-based

installation methods. An injection-based installation method
must account for the inherent variability in treatment reagent
distribution by increasing the number of injection points and
implementing a high quality assurance/quality control (QA/
QC) protocol to ensure adequate lateral overlap. However,
the advantages of injection-based installation methods
include flexibility in installation (surface access, subsurface
utilities, residential considerations, etc.), the ability to install
PRBs deeper than 100 ft below ground surface (deeper than
all excavation-based installations can practically achieve),
discretization of the treatment interval(s), and less waste
materials. The available injection-based installation methods
include direct injection and pneumatic/hydraulic fracturing
injection:

• Direct injection is simply the addition of treat-

FIGURE 10.12  Excavation of a permeable reactive barrier using a
clamshell excavator. (From Di Molfetta, A. and Sethi, R., Environ.
Geol., 50, 361, 2006.)
exists during sheet pile installation and should be
considered before selecting this installation method.1
• Augured boreholes/caissons/soil mixing is used
to install PRBs when site infrastructure precludes
access. Either hollow stem auger drill rigs or circular
steel caissons are used to install overlapping, adja-
cent columns of treatment reagent and structural fill
to create a PRB. Hollow stem auger borings of up to
30 in. in diameter and steel caissons of up to 15 ft in
diameter have been used to achieve depths of up to
60 ft below ground surface.1 Similar smearing con-
siderations as sheet piling exist with caisson removal.
• Clamshell excavators (Figure 10.12) use a mechani-
cal cable-suspended, crane-operated grabbing tool to
excavate trenches to depths of 200 ft, but reported
PRB installation using this method has been lim-
ited to 45 ft. Biopolymer slurry is used to hydrau-
lically shore the trench. Clamshell excavators have
been used extensively in Europe for PRB installa-
tion. They are efficient for bulk excavation of most
subsurface materials, with the exception of highly
consolidated sediments and bedrock.1
10.2.2.2.2  Injection-Based Installation Methods
It is a fact that excavation-based installation methods for PRBs
have a higher degree of certainty of uniform treatment reagent
ment reagent along the length of the designed PRB
through adjacent injection wells. Sparingly soluble
substances (i.e., oxygen release material, hydrogen
release compound, gypsum, emulsified ZVI) are
typically injected as slurries through closely spaced
direct push injection points (not injection wells). If
the site soils are amenable and the permeability is
sufficient, lateral circulation of the injected reagent
may be appropriate to increase the level of assurance
of distribution. Field response breakthrough data
from an injection-based installation of an anaero-
bic biological PRB in the Western United States
are presented on Figure 10.13. The data presented
on Figure 10.13 shows the field parameter response
(colorimetric dye and turbidity) as well as analytical
results for TOC from a side gradient dose response
well during an emulsified vegetable oil (EVO) and
fluorescent dye injection. The first approximately
17,000 gal injected did not use circulation, and
no evidence of side gradient breakthrough was
observed. After lateral circulation began using adja-
cent injection wells as injection–extraction dipole
couples, a near-immediate response in color and
turbidity (a surrogate for oil droplets) was observed,
and a small increase in TOC was also observed.
This demonstrates that lateral circulation along the
injected-based PRB may increase certainty of treat-
ment reagent distribution.
• Pneumatic and hydraulic fracturing involve pres-
sure addition that exceeds the overburden stress
and cohesion strength of aquifer soil. A detailed
discussion of aquifer fracturing is presented else-
where16 and discussed briefly in Chapters 4 and 6.
Pneumatic fracturing uses air (typically nitrogen)
to create fractures that are then immediately occu-
pied by treatment reagent. Hydraulic fracturing uses
the treatment reagent as a slurry to create the frac-
tures and simultaneously distribute the treatment
reagent. Fracture placement of treatment reagent
accomplishes treatment reagent placement, but does
522 Remediation Engineering

0.1 50

Eosine dye
TOC
0.08 Turbidity 40

Normalized dye and TOC response

Lateral circulation begins

Turbidity (NTUs)
0.06 30

0.04 20

0.02 10

0 0
0 5,000 10,000 15,000 20,000 25,000
Cumulative injected volume

FIGURE 10.13  Influence of lateral circulation along a transect of injection wells comprising an emulsified vegetable oil permeable reactive
barrier for in situ biological reduction of perchlorate (ClO4−). The fluorescent dye and turbidity responses were observed immediately in the
field upon beginning lateral circulation and subsequent laboratory analysis for fluorescent dye and TOC confirmed lateral solution arrival.

so along preferential pathways coincident with fric-
tional angles, typically angling upward. A fracture
placement of treatment reagent for a PRB should
consider conical distribution as a real possibility, and
lateral monitoring should be performed to confirm
treatment reagent distribution.
increases the certainty of treatment reagent distribution. As
the depth increases, the feasibility of ­excavation-based instal-
lation methods decreases and injection-based installation
methods are required. As the depth continues to increase, the
reliability and certainty of lateral treatment reagent distribu-
tion decreases.

10.2.2.3  Limitations of PRB Construction

The paramount design principle of a PRB is that the bar-
rier intersect all of the contaminant flux and provide a suf-
ficient residence time (ϑ) to facilitate complete contaminant
destruction or immobilization. Based on the required com-
ponents and installation methods of a PRB, it is apparent
that some natural limitations of the PRB effectiveness exist.
The PRB design should exploit as many strengths of a given
construction technique while providing for a sufficient safety
factor to account for known weaknesses. For example, if an
­injection-based installation method is to be used, a dense net-
work of injection wells/points is advisable with lateral con-
firmatory borings to establish that uniform distribution has
been achieved. If guar gum is used as a hydraulic shoring
solution in an excavation-based installation method, addi-
tives/preservatives should be added to discourage bacterial
degradation of the biopolymer slurry prior to completion of
the PRB installation to ensure proper placement of treatment
reagent. If ambient geochemical conditions threaten aggres-
sive passivation of reactive media, injection wells should be
installed during PRB installation to facilitate regeneration of
the treatment reagent.
The most critical limitation to a PRB is the depth of installa-
tion. The shallower the PRB, the more likely it can be installed
with an excavation-based installation method, which  greatly
10.2.3 Performance Considerations
The main design objective of a PRB is well documented
throughout all of the guidance documents, and the objective is
to intercept a groundwater contaminant plume and discharge
groundwater below regulatory criteria. This section touches
on the three performance criteria upon which PRBs are evalu-
ated: hydraulic capture, residence time (ϑ), and reactivity.
10.2.3.1  Hydraulic Capture
The most effective PRB hydraulic design does not signifi-
cantly influence the hydraulic gradient (i). The purpose of a
PRB is to facilitate treatment passively as groundwater trans-
ports across the PRB treatment interval, so the permeability
must encourage flow through the barrier. However, the per-
meability should not be so much higher than the surround-
ing aquifer that groundwater potentially preferentially pools
within the PRB. Alternatively, the permeability should not
be equal to or less than the surrounding aquifer. The treat-
ment interval must also cover a sufficient depth to account
for seasonal elevation fluctuation (a concept most important
for hanging gate PRB). Lastly, seasonal variations in ground-
water flow direction should also be captured by the PRB and
may require multiple reactive gates in a funnel and gate PRB
or discontinuous breaks in a continuous PRB.
Reactive Walls
10.2.3.2  Residence Time
The residence time (ϑ) is defined in detail in Section 10.3.2,
but essentially describes the length of time a molecule of
contaminant is in contact with the treatment reagent in the
reactive gate or treatment interval of a PRB. The longer the
residence time (ϑ), the more the certainty of complete con-
taminant removal from groundwater. This is a critical per-
formance criterion because even if the appropriate reaction
mechanism (Section 10.2.1) is selected, if the reaction kinetics
are slow and/or the groundwater flow through the PRB is fast,
the reaction may not occur, reducing the effectiveness of the
PRB. The residence time (ϑ) is expected to change over the
lifetime of a PRB as precipitation and biomass growth passiv-
ate the treatment reagent potentially focused flow through less
porosity (i.e., increasing the velocity through the PRB). Safety
factors are typically applied to the residence time (ϑ), which is
controlled by the installation thickness of the PRB.
10.2.3.3 Reactivity
The reactivity of the treatment reagent is defined as the ability
of the treatment reaction to destroy or immobilize the contam-
inant. In other words, it is a measure of the surface area of the
treatment reagent to establish contact with the contaminants
or the dissolution rate to become bioavailable for biological
metabolisms. The reactivity may be reduced by passivation
of the treatment reagent, which is simply biomass formation
or mineral precipitation that coats the surface area inhibit-
ing the targeted treatment reactions. Decreases in reactivity
are expected, and predictions of decreased reactivity may be
informed by predesign geochemical modeling. A particular
reaction mechanism or the PRB technology may be disquali-
fied if diminished reactivity is anticipated to be appreciable.
10.3  TREATMENT PROCESSES
Clear and transparent design, dutiful construction, and proac-
tive operation of any in situ reactive zone (IRZ) are the keys
to successful implementation of in situ soil and groundwater
remediation. The same is true for PRBs and the several types
of IRZs that can be installed. A PRB is considered to be a
passive IRZ because natural groundwater flow brings the con-
taminants into contact with the stationary treatment reagent
within the PRB. Achieving contact between treatment reagent
and contaminants is a fundamental principle of in situ reme-
diation and dictates success or failure of many remediation
technologies. For example, in situ chemical oxidation (ISCO)
can be highly effective when chemical reagents are adequately
distributed throughout the radius of influence (ROI). However,
outside of the ROI, ISCO is less effective because the highly
reactive treatment reagent has been consumed within the ROI.
With the exception of clean water dilution flux from the ROI,
ISCO is ineffective outside of the ROI. If stakeholder objec-
tives necessitate more expedient remediation, broader distri-
bution of the chemical reagent will be required. For an ISCO
PRB that is designed to intercept a slow moving groundwater
contaminant plume as a management strategy to perpetuity,
if ISCO is effective within the constructed reactive gate of the
523
PRB, downgradient propagation of highly reactive chemical
reagent may not be necessary to achieve treatment objectives.
Briefly, the applicability of a PRB at a site slightly alters dis-
qualifying assumptions for some remedial technologies.
10.3.1 Reaction Mechanisms
In this section, details and applicability of general reaction
mechanisms (i.e., physical, chemical, and biological) are dis-
cussed with respect to a PRB implementation (Table 10.1).
Specific technologies under each general reaction mechanism
are selected to represent the most likely to be implemented
considering cost, applicability, remedial time frame, and reg-
ulatory approval.
10.3.1.1  Physical Reaction Mechanism
The two selected remedial technologies for discussion under
the physical reaction mechanism are air sparging (i.e., removal
via enhanced volatilization) and adsorption (i.e., immobiliz-
ing contamination by encouraging sorption to reactive media).
10.3.1.1.1  Air Sparging
The application of this technology in specially designed reac-
tive gates or treatment intervals should be considered equiva-
lent to operating an in situ air stripper. Most volatile organic
compounds (VOCs) preferentially partition into injected air
bubbles from contaminated groundwater. This partitioning is
referred to as “stripping” the groundwater of volatile chemi-
cals. The details of air sparge optimization and contaminant
partitioning into air bubbles is discussed in Chapter 8. The
volatilized VOCs follow the vertical bubble pathway out of
the groundwater and into the vadose zone or atmosphere. The
stripped contaminants can be easily collected, via a vapor
extraction system, and treated prior to discharge to the atmo-
sphere. Strippability of dissolved contaminants is dictated by
the Henry’s law constants. In general, the higher the Henry’s
law constant, the more readily a compound would partition
to the vapor phase. Injected airflow rates can be optimized to
achieve the required stripping efficiencies. Due to the ground-
water velocities encountered at most of sites, achievable resi-
dence times (ϑ) are likely to be more than sufficient for an air
sparging PRB to achieve the required stripping efficiencies.
Air sparging PRBs can be installed in the form of sparg-
ing trenches (Figure 10.14) or sparging gates/wells. They may
also be installed as a transect of injection wells, commonly
referred to as a sparge curtain. As a physical removal mecha-
nism, air sparging is primarily focused on enhancing vola-
tility and recovering VOCs in the gaseous phase; however,
the dissolved oxygen concentration in groundwater typically
increases as a result of sparging air into the groundwater,
which can facilitate aerobic bioremediation. Air sparging
PRBs require comparatively more routine O&M to inspect
and operate the continuously pulsing system, some sort of
vapor treatment (which could involve biennial vapor phase
GAC change outs), and utility costs to power the air compres-
sor, vacuum blower, and any system automation to assist with
real-time data collection and/or remote operation capabilities.
524 Remediation Engineering

Nutrients
Extracted air

Air extraction

GW flow Air injection

Pea gravel

FIGURE 10.14  Cross-sectional view of a horizontal trench for

air sparging associated with a permeable reactive barrier. Note that
vapor extraction and aboveground vapor treatment are necessary to
capture fugitive contaminant vapors.

10.3.1.1.2 Adsorption
Adsorption mechanisms can be employed in PRBs to remove
a variety of contaminants. Liquid-phase GAC can be used
to remove many organics, especially those not easily remov-
able by air sparging or biodegradation (e.g., PCP [C6HCl5O]
and tetrachlorophenol [C6H2Cl4O]). Ion exchange resins can
be used to remove dissolved heavy metals present in the FIGURE 10.15  Collector line installation for a funnel and gate
groundwater. permeable reactive barrier.

10.3.1.1.2.1  Liquid-Phase Granular Activated Carbon  ​

Dissolved organics can be removed from groundwater in
the presence of GAC by adsorbing onto the extensive inner
surface area of the GAC. Traditionally, the adsorption phe-
nomenon has been categorized as physical adsorption and
chemisorption. Physical adsorption is a rapid process,
caused by nonspecific secondary binding mechanisms,
and is reversible. The adsorbate will desorb into the solu-
tion in response to a decrease in solution concentration.
Chemisorption is more specific because it entails the trans-
fer of electrons between adsorbent and adsorbate and may
or may not be reversible. More general information about
liquid-phase GAC including isotherms and regeneration is
detailed in Chapter 2.
Due to the cost of liquid-phase GAC, the implementation
of this technology is best suited for a funnel and gate PRB. FIGURE 10.16  Constructing the slurry wall component of a fun-
nel and gate permeable reactive barrier.
The virgin carbon can be slurried into the reactive gate, and
the spent carbon can be vacuum slurried out of the reactive
gate. The installation of a funnel and gate PRB with GAC is of natural organic matter such as humic substances and other
showed incrementally on Figures 10.15 through 10.20. micropollutants. Fouling of the GAC may also increase the
Frequency of change outs of the GAC can be estimated resistance to flow through the reactive gate. Design enhance-
by performing a column isotherm study in the laboratory. ments that provide the flexibility for periodic backwashing of
Published information in the literature can also be used for the GAC may overcome this problem.
this purpose. However, it should be noted that the estimated
adsorption capacity of the GAC in situ can be compromised 10.3.1.1.2.2   Ion Exchange Resins  An ion exchange reac-
by the potential fouling caused by growth of microorganisms tion may be defined as the reversible interchange of ions
and deposition of inorganic precipitates. In addition, contami- between a solid phase (the ion exchange media) and solu-
nant adsorptive capacity may be reduced due to the adsorption tion phase. The ion exchange media must be insoluble in the
Reactive Walls
FIGURE 10.17  Overhead view of a funnel and gate permeable
reactive barrier installation.
FIGURE 10.18  Funnel and gate permeable reactive barrier instal-
lation, showing setup of granular activated carbon gate.
FIGURE 10.19  Funnel and gate permeable reactive barrier instal-
lation, showing final connection of collector lines to gate tank.
525
FIGURE 10.20  Funnel and gate permeable reactive barrier instal-
lation, filling gate tank with granular activated carbon.
solution in which the interchange is carried out. The impor-
tant features characterizing ion exchange media are
• A hydrophilic structure of regular and reproducible
form
• A controlled and effective ion exchange capacity
• A rapid rate of exchange
• Chemical stability
• Physical stability in terms of mechanical strength
• A consistent particle size and effective surface area
More general information on ion exchange and design criteria
are summarized in Chapter 2.
Ion exchange reactions take place due to a stronger prefer-
ence of a dissolved ion to sorb onto the ion exchange media
in comparison to an existing sorbed ion. As the dissolved
iron sorbs to the ion exchange media, the existing sorbed ion
desorbs and becomes dissolved in solution or finds another
sorption site on the ion exchange media. Most of the dissolved
heavy metals present in groundwater are divalent (Me2+ ) or
trivalent (Me3+ ) cations, with the exception of hexavalent
chromium (Cr6+ ). These cations heavily favor ion exchange
media, and therefore, ion exchange is suitable for heavy met-
als removal. Depending on the heavy metal(s) to be removed,
a strong acid or a weak acid ion exchange media may have to
be used. Typically, the use of ion exchange media in PRBs
will be specific and under optimum carefully controlled con-
ditions. The presence of other ions and nonideal pH condi-
tions will significantly impact the loading capacity of the ion
exchange media.
The most cost-effective use of the ion exchange method
will be when the dissolved heavy metal concentrations in the
groundwater are at low levels. At high concentrations, media
replacement will be more frequent, and the cost of disposal
or regeneration of the spent media will be prohibitive. The
placement of the fresh ion exchange media in the reactive
gate of a funnel and gate PRB can be carried out in the form
of a wet slurry, and the spent media can be vacuumed out as
a slurry.
526
10.3.1.2  Chemical Reaction Mechanism
Three chemical processes are selected for discussion as the
PRB applicable chemical reaction mechanisms: precipitation,
abiotic reduction, and chemical oxidation. The popularity of
ZVI as a treatment reagent in PRBs has led to an abundance
of peer reviewed literature on the subject.7,13,23–42 In this book,
details pertaining to the ZVI reaction mechanisms are sum-
marized in Chapters 6 and 7. The geochemical cycling of
ZVI, and even of ferrous iron (Fe2+ ), create conditions for
metals precipitation as well as abiotic reductive dechlorina-
tion. Chemical oxidation is discussed in terms of relevance to
emerging contaminants, but generally represents a last resort
from a PRB perspective.
10.3.1.2.1 Precipitation
Precipitation of dissolved heavy metals can be achieved by
manipulating the pH and the oxidation–reduction conditions
of contaminated groundwater as it flows through a PRB.
Heavy metals can be precipitated as hydroxides, carbonates,
or sulfide precipitates (Chapter 7). Precipitation of heavy
metals has been successfully achieved in ex situ wastewater
treatment processes and in situ IRZs. The implementation of
metals precipitation in a PRB is readily implementable, but
special considerations for porosity clogging and passivation of
treatment reagent are required. An advantage of metals pre-
cipitation using a PRB is the comparatively higher residence
times (ϑ) than wastewater treatment systems. A disadvantage
is regenerating treatment reagent or lost treatment reagent
capacity with time as mineral precipitation coats surface area
and/or clogs porosity.40,41 ZVI may be used to remove metals
such as hexavalent chromium (Cr6+) and arsenic (as arsenite:
As3+, AsO33− or arsenate: As5+, AsO43−). Furakawa et al. and
Blowes et al. proposed the following equations to explain why
ZVI interaction with hexavalent chromium (Cr6+) and ground-
water results in acidity generation and/or hydroxide genera-
tion, which typically demonstrates a slight to moderate pH
increase in ZVI PRBs40,41:
2- + 3+ 3+
CrO 4( aq ) + Fe( s ) + 8 H( aq ) ® Fe( aq ) + Cr( aq ) + 4H 2O(l )
0
 (10.2)
2Fe( s )0 + O2( g ) + 2 H2 O(l ) ® 2Fe( aq )2 + + 4OH ( aq ) - (10.3)
Fe( s )0 + 2H 2O(l ) ® Fe( aq )2 + + H 2( g ) + + 2OH ( aq ) - (10.4)
A PRB for metals precipitation is effective as a funnel and gate
configuration because treatment reagent may be regenerated at
a lower cost, and optimum pH and oxidation–reduction condi-
tions can be more carefully controlled in an isolated reactive
gate as compared to a continuous PRB. Depending on the rate
of precipitation, reactive gates in series may be necessary to
filter out the precipitates (or flocculent from acidity neutral-
ization). This filter reactive gate is designed in such a way to
remove the precipitated solids by backwashing. Due to the
constructability considerations, PRBs for metals precipitation
are most appropriate for shallow groundwater elevations.
Remediation Engineering
Metals precipitation can be achieved in a continuous PRB
configuration as well. Limestone and ZVI can be used as the
backfill materials to adjust the pH of the incoming ground-
water and precipitate metals as metal hydroxides (Equations
10.3 and 10.4).
10.3.1.2.2  Abiotic Reduction
Abiotic reduction is simply defined as a chemical reduction
reaction; those reactions that are not facilitated by bacteria
and involve a targeted contaminant gaining electrons. Design
details and a more thorough discussion on abiotic reduction
are provided in Chapter 6. Well-known abiotic reduction reac-
tions include the abiotic conversion of hexavalent chromium
(Cr6+) to trivalent chromium (Cr3+) (one example of this is pre-
sented as Equation 10.2) and the abiotic reductive dechlorina-
tion pathway, both effectively mediated by ZVI (as well as
other reduced forms of metals).
Abiotic reductive dechlorination using ZVI is a major com-
ponent of PRBs and is a driving force behind the popularity of
PRBs. Given the importance of abiotic reductive dechlorina-
tion specifically associated with ZVI, a more detailed discus-
sion is presented here. In order to explore the abiotic reductive
dechlorination pathway a bit more, a few reaction definitions
are necessary. First, a hydrogenation reaction is defined
as a chemical reaction that adds hydrogen to a compound.
Hydrogenation reactions are pertinent to ZVI PRBs because
gaseous hydrogen (H2) can be generated by the corrosion of
ZVI in the presence of water (Equation 10.4) and subsequently
included in compounds.28 Second, elimination reactions
result in a single reactant splitting into two products (typi-
cally in the presence of a strong base). Both alpha-elimination
(α-elimination) and beta-elimination (β-elimination) reactions
are possible with respect to abiotic reductive dechlorination
with ZVI, and the alpha and beta designations refer to the
carbon atoms in the parent compound. The alpha carbon is
attached to the part of the compound that leaves as a result of
the elimination reaction, and the beta carbons are attached to
the alpha carbon. Theorized generation of alkaline conditions
strong enough to facilitate elimination reactions is presented
in Equations 10.3 and 10.4. Third, with respect to reductive
dechlorination, hydrogenolysis is simply replacing a carbon–
chloride bond with a carbon–hydrogen bond. Therefore, in the
abiotic reductive dechlorination pathway, the three reactions
that are relevant include hydrogenation, both α-elimination
and β-elimination, and hydrogenolysis. A summary of the
potential ZVI-facilitated abiotic reductive dechlorination
reactions for tetrachloroethylene was detailed in Arnold and
Roberts43 and is presented on Figure 10.21, which was adapted
from Arnold and Roberts.43 The difference between hydroge-
nation and hydrogenolysis is clearly demonstrated on Figure
10.21 and corresponds to the numbers assigned to the individ-
ual reactions. Note that hydrogenation (adding hydrogen to the
compound) occurs in the following instances: acetylene (C2H2)
to ethene (C2H4), dichloroacetylene (C2Cl2) to dichloroethene
isomers trans and cis (C2H2Cl2), and ethene (C2H4) to ethane
(C2H6). In all of these reactions, the number of carbons and
chlorides do not change, but the number of hydrogens increase.
Reactive Walls 527

Cl Cl
C–C
Cl Cl
PCE
2 1

Cl C C Cl Cl Cl
Dichloroacetylene C C
6
Cl H
TCE
3 5
17 15
16 4

Cl H Cl Cl Cl H
Cl C C H C C C C C C
Chloroacetylene H Cl H H Cl H
8 1,1-DCE
trans-1,2-DCE cis-1,2-DCE
14
10 9
7

H C C H Cl H
Acetylene C C
H H 11
Vinyl chloride
12 13
18
C4 compounds
H H
C C
H H
Ethylene

19

C2 H6
Ethane

FIGURE 10.21  Reaction pathways put forth by Arnold and Roberts46 for chlorinated ethene reduction by zerovalent iron, including inter-
mediates. The numbers highlight different reactions (hydrogenation, hydrogenolysis, or elimination [alpha or beta]). Numbers 1, 3, 4, 5, 7,
9, 14, 17, and 18 correspond with hydrogenolysis reactions (or replacing chloride bonds with hydrogen bonds). Numbers 2, 6, 8, and 10 are
beta-elimination reactions (or compound separation reactions). Number 11 is an alpha-elimination reaction. Numbers 13, 15, 16, and 19 are
hydrogenation reactions (or reactions that result in gaining hydrogen). (From Arnold, W.A. and Roberts, A.L., Environ. Sci. Technol., 34,
1794, 2000.)

In the hydrogenolysis reactions (the sequential dechlorination
reactions), the number of chlorides is reduced as the bonds are
replaced by hydrogen (Figure 10.21).
Abiotic reduction in PRBs is usually implemented with
ZVI and is appropriate in the continuous PRB or funnel and
gate configurations. It is possible to condition an aquifer with
routine sodium dithionite (Na2S2O4) injections (or other chem-
ical reductants such as polysulfides [Sn2−]) in a barrier con-
figuration with the objective of reducing geogenic iron from
ferric iron (Fe3+) to ferrous iron (Fe2+) to facilitate hexavalent
chromium (Cr6+) reduction.44 Typically, ZVI is less expensive
over the life cycle because ZVI has a longer residence time (ϑ)
in  situ, and the O&M of conducting routine injections with
highly reactive chemical reductants can exceed the capital
installation cost of the PRB.
10.3.1.2.3  Chemical Oxidation
ISCO of organic compounds involves converting the com-
pound by means of an oxidizing agent into benign end
products through the removal of electrons from the carbon
atom. A thorough and detailed discussion of design consid-
erations and reactions pertaining to ISCO is summarized in
Chapter 6. For example, benzene (C6H6) can be oxidized to
carbon dioxide (CO2) using the chemical oxidant hydrogen
peroxide (H2O2) by removing 30 electrons per mole of ben-
zene, according to the following equation:
C6H 6 + 15H 2O2 ® 6CO2 + 18H 2O (10.5)
Implementing an ISCO PRB can be cumbersome and can
raise safety concerns. Hence, the use of ISCO in a PRB
should be chosen only when all other reactive processes are
considered not effective to treat a specific contaminant, and
a PRB is still appropriate. Highly soluble groundwater con-
taminants that fall in this category are 1,4-dioxane (C4H8O2)
and perfluorinated alkyl substances (PFAS; such as perfluo-
rinated carboxylic acids [CnF(2n+1)CO2H] and perfluorinated
sulfonate [C8HF17O3S]).
528
The stoichiometric equation for benzene (C6H6) oxida-
tion (or any ISCO stoichiometry) presented in Equation
10.5 has little meaning because the overall natural oxidant
demand (NOD) typically overshadows the contaminant oxi-
dant demand45; implying that for every 1 mol of benzene
(C6H6) some value greater than 15 mol of hydrogen peroxide
(H2O2) would be required. Bench-scale treatability testing can
help inform the  chosen oxidant and strength by empirically
determining the NOD (Chapter 6), and radical cycling may
improve the efficiency of some oxidants. However, this is an
important point if ISCO is to be considered for a PRB. To be
effective, an ISCO PRB must supply chemically active oxi-
dant at the same rate as the in-flux of contaminants and natu-
ral scavengers. Few chemical oxidants offer a low solubility
in groundwater. This means slow release of an oxidant over
a long duration is not yet possible, and radical oxidants are
chemically active in groundwater for an abbreviated period
of time. This requires more O&M to continually add the oxi-
dant to the PRB, and conceptually contradicts the benefit of
a PRB. Sparging ozone gas as an oxidant source in a PRB
may be more desirable than an injection of persulfate (S2O82−)
or hydrogen peroxide (H2O2). Hydrogen peroxide (H2O2) and
ozone (O3) as a combination is a common oxidative process.
There are many proprietary components to the combination
of hydrogen peroxide (H2O2) and ozone (O3), but in general
when implemented in  situ, it is referred to as peroxone45
and when implemented ex situ is referred to as HiPOx.
Similar to the air sparging PRB discussed in Section
10.2.1.1.1, the injection of ozone (O3) could be pulsed from
a maintained system aboveground. Of course, an appropri-
ate engineering cost-benefit analysis would be necessary to
understand the life cycle cost differential between periodic
oxidant additions and continuous pulsed ozone (O3) sparg-
ing. ISCO PRBs are most cost effective when constructed in
the funnel and gate configuration with an underground vault
and hence will be applicable only under shallow-water table
conditions.
It is important to note that the remediation industry is in the
process of developing slow release oxidant cylinders through
ongoing research. The cylinders are made up of variable per-
centages of chemical oxidants and wax. As the wax dissolves,
the oxidant is made available. Since the wax is sparingly solu-
ble, its solubility dictates the availability of the oxidant. These
cylinders in non-PRB in  situ remediation applications have
less value because of the volume-to-distribution relationship
of the oxidant is poor (essentially limited to the borehole of
the cylinder). However, within a funnel and gate PRB where
the permeability of the reactive gate is greater than the ambi-
ent permeability, several cylinders emplaced within a gate
may be appropriate to achieve a longer residence time (ϑ) for
the oxidant. This area of research demonstrates that PRBs are
limited only by creativity and innovation of the remediation
industry.
10.3.1.3  Biological Reactive Mechanism
Biological PRBs are discussed in this section in terms of two
categories: anaerobic and aerobic. Anaerobic biological PRBs
Remediation Engineering
have gained more attention in recent years, and were mainly
delayed by the popularity of ZVI. Aerobic biological PRBs
can be similar in concept to air sparge PRBs, but can also
function completely differently. A common regulatory and
industry perception is that the appropriate bacteria are not
naturally occurring in some instances, and bioaugmentation
(the emplacement of a targeted bacteria in  situ) is required
(Chapter 6). While it is true that bioaugmentation improves
initial rate kinetics of biological reactions, it is the authors’
experience that in most instances bioaugmentation is not a
necessity. Nevertheless, bioaugmentation within a PRB is
feasible and, compared to non-PRB in situ remediation appli-
cations, more effective. Finally, “biowalls,” a common term
with respect to biological PRBs, has implicitly been used to
refer to anaerobic biological PRBs though could refer to aero-
bic biological PRBs as well. In this chapter, organic carbon
PRBs supporting anaerobic biological reactions are the focus
due to popularity throughout the remediation industry.
10.3.1.3.1  Anaerobic Biological PRBs
In Chapters 6 and 7 and Section 10.2.1.2.2, abiotic reduction
reactions using ZVI are presented, and, given the residence
time (ϑ) and effectiveness, it is clear why the preference
for PRBs is ZVI. In the introduction to this chapter, the
evolution of PRBs is discussed, and biological PRBs are a
good example of how the perception of PRBs has changed.
The area of biological PRBs continues to gain popularity
because of the benefits of reduced life cycle O&M and the
availability of solid sources of carbon. In a typical anaerobic
biological remediation IRZ injection (non-PRB), placement
of solid carbon sources (injected as a slurry) is challenging
and may even require fracturing or soil mixing. Even spar-
ingly soluble liquid carbon sources (i.e., soybean oil) may
experience volume to distribution challenges associated with
porosity straining of oil droplets at large ROIs. In a continu-
ous or funnel and gate PRB, distribution of the carbon is
achieved by backfilling the treatment interval or reactive
gate and, under proper construction, ensures homogenous
distribution of the carbon. This enables the use of various
solid carbon sources (e.g., chitin, walnut shells, mulch),
along with injection of soybean oil or more soluble forms
of carbon (e.g., molasses, alcohols, lactate). The installation
of injection wells (and potentially circulation wells) allows
for subsequent carbon recharge when performance monitor-
ing indicates the carbon has been depleted. A more detailed
investigation is recommended prior to recharging carbon in
a PRB that relies on solid carbon sources as groundwater
concentrations of TOC may not fully represent the residual
carbon remaining. Details and design concepts associated
with anaerobic biological remediation are discussed in
Chapter 6. Carbon-amended PRBs are relevant for any con-
taminant that is anaerobically degradable and some metals
that will precipitate under reducing conditions in the pres-
ence of reduced anions such as sulfide (S2−).
A complication that may arise is a reduction in permeability
over time of the reactive gate or treatment interval associated
with anaerobic biomass.46 The treatment residence time  (ϑ)
Reactive Walls
within the reactive gate or treatment interval of a PRB is a
balance between the time it takes for the targeted reaction to
occur (i.e., reaction kinetics) and the groundwater flow veloc-
ity (i.e., flux). Typically, PRBs are designed to allow for treat-
ment across the engineered backfill at an installed compaction
and resultant porosity. If biomass growth becomes apprecia-
ble and reduces permeability significantly, the groundwater
flow velocity through the PRB increases. This accelerates the
mass flux of contaminants through the PRB and may violate
the designed residence time (ϑ) assumption failing to provide
enough reaction time. A benefit to an anaerobic biological
PRB is that the soluble carbon in excess of the contaminant
demand will move downgradient effectively increasing the
influenced treatment thickness of the PRB. This natural prop-
agation of carbon downgradient of the PRB will follow the
most permeable intervals and provide a safety factor against
downgradient contaminant breakthrough.
Lastly, another form of anaerobic biological PRBs may
include supplementing alternative electron acceptors for exist-
ing contamination. Aquifers impacted by petroleum hydro-
carbons (PHs) are typically anaerobic because dissolved
oxygen is energetically favorable and is preferentially con-
sumed by indigenous bacteria during aerobic oxidation (i.e.,
biodegradation) of the PHs. In this instance, the PHs serve
as an electron donor in the bacterial metabolism reactions.
Following the depletion of dissolved oxygen, alternative elec-
tron acceptors (i.e., nitrate [NO3−], ferric iron [Fe3+], manganic
manganese [Mn4+], sulfate [SO42−], and carbon dioxide [CO2])
are utilized in the continued oxidation of PHs. The anaerobic
oxidation of PHs under various dominant electron-accepting
processes (e.g., sulfate reduction, iron reducing, methano-
genesis*) is well-founded in the literature.47–60 Similar to
enhanced aerobic systems, engineered anaerobic biological
oxidation (ABOx) relies on oxidation–reduction couples such
as nitrate reduction (NO3− to N2), ferric iron reduction (Fe3+
to Fe2+), sulfate reduction (SO42− to S2−), and methanogenesis
(generation of methane [CH4]) to facilitate cellular respiration
using the PHs as an electron donor.
Anaerobic processes generally occur at slower kinetic
rates than aerobic processes. Nonoxygen electron acceptors
(i.e., sulfate [SO42−]) can be advantageous to oxygen addition
approaches as they are highly soluble, can be supplied at ele-
vated dissolved concentrations, and have minimal abiotic or
nontarget reactions that typically limit oxygen persistence in
the subsurface. The higher concentrations of sulfate (SO42−)
that can be maintained in a PH-impacted aquifer accompa-
nied by electron acceptor persistence allows for effective PH
degradation. Thus, while the kinetic rates of ABOx may be
slower than under aerobic conditions, if the sulfate (SO42−) is
supplied in a PRB over a relatively long time period, it pres-
ents a cost-effective option compared to long-term operation
of continuous oxygen sparging.
* Methanogenesis is defined as the biological production of methane (CH4)
mediated by methanogens. The production of methane (CH4) is the energy-
yielding metabolism of methanogens.
529
10.3.1.3.2  Aerobic Biological PRBs
When the contaminants present in the groundwater are aer-
obically biodegradable (i.e., oxygen is used as the electron
acceptor), implementation of an aerobic biological PRB pres-
ents an alternative to air sparging and GAC adsorption, which
will reduce the life cycle costs of the PRB by minimizing the
need for treatment of volatilized contaminants in the vapor
phase or the replacement of GAC.
Air injection rates required for the operation of an aero-
bic PRB will be significantly lower than those required for
air sparging (Section 10.2.1.1.1) (i.e., 1–2 standard cubic feet
per minute [scfm] compared to 5–10 scfm). At steady state,
the majority of dissolved contamination will be biodegraded,
eliminating the need to capture fugitive contaminant vapors.
Typically, oxygen-sparging approaches for biological treat-
ment are fundamentally limited by low oxygen solubility
in groundwater and gas transfer inefficiencies that limit the
effective dissolved oxygen concentrations maintained in engi-
neered aerobic reactive zones. In an aerobic biological PRB,
however, the reactive gate of a funnel and gate PRB can be
designed such that oxygen dissolution is maximized, which
improves the overall approach.
If the aerobic biological PRB is to function as a bioreac-
tor, the porous media used in the treatment interval or reac-
tive gate should be able to support the growth of biomass.
Recall from Chapter 6 and elsewhere61–63 that the energetics
associated with aerobic biological reactions supports signifi-
cant biomass growth. The rough surface of oyster shells is
an example, where the enhanced attachment will increase
the biomass per unit volume of the reactor. Similar to Section
10.2.1.3.1 regarding biomass growth in anaerobic biological
PRBs, biomass growth in an aerobic biological PRB will also
increase the resistance to flow through the PRB or channel
flow through the PRB faster than anticipated.
Another option for aerobic biological PRBs is the use of
oxygen releasing materials (ORM). Available in various forms
of peroxides (magnesium and calcium), ORM represents a
low-solubility treatment reagent that dissolves over time to
maintain dissolved oxygen concentrations near the saturation
limit (8–20 mg/L depending on the temperature and depth of
groundwater above the ORM). ORM is typically injected as
slurry under non-PRB active in  situ remediation or used as
a treatment reagent in soil mixing. In a PRB, a high weight
percent may be mixed in with the backfill of a reactive gate in
a funnel and gate PRB to maintain elevated dissolved oxygen
concentrations, potentially for years prior to treatment reagent
recharge.
10.3.2 Reaction Considerations
The selected reaction mechanism will be based on the appli-
cability to immobilize or destroy the targeted contamination
and the relevance to the aquifer hydrogeology and geochem-
istry. For example, while an adsorptive physical reaction
mechanism using ion exchange media may be applicable to
perchlorate (ClO4−) removal, if the aquifer is brackish (i.e.,
saturated with ions), ion exchange may not be the most
530
suitable treatment method due to intensive O&M. The selec-
tion criteria for treatment reagent in PRBs are summarized
in the available literature to include reactivity, availability,
and compatibility.1,12,13 In addition to a thorough review of the
conceptual site model (CSM), supplementing the treatment
reagent selection process with bench-scale treatability test-
ing is recommended. Treatability testing can be conducted in
commercial laboratories for a cost range of $25,000–$45,000
based on the size and complexity of the test. Considering that
most PRB installation costs average an order of magnitude
higher, the upfront treatability testing costs are justified, espe-
cially considering that once the PRB is installed there is little
than can be done to rectify deficiencies.12 Treatability testing
can demonstrate that the considered treatment reagent will
achieve the desired reaction mechanism, empirically deter-
mine the treatment reagent half-life, evaluate the longevity
of treatment reagent, and (if flow through column testing is
employed) empirically determine hydraulic properties. It is
clear that the stakeholder investment in a PRB will be well-
informed by a treatability test.
10.3.2.1 Treatment Reagent Reactivity
(Durability and Stability)
Recall that a principle design paradigm for PRBs is the min-
imal O&M over the lifetime of operation. Therefore, when
selecting a treatment reagent for a PRB, relevance to the tar-
geted contaminant and predicted reactivity over a reason-
able PRB lifetime (i.e., greater than 10 years) are considered
equivalent evaluation criteria. A PRB may not be justifiable
if the O&M associated with the treatment reagent is bur-
densome. The reactivity of the treatment reagent includes
a reaction rate with the contaminant that can occur within
a practical installation thickness of a PRB (approximately
3–5 ft). The definition of a practical installation thickness
for a PRB is a function of site-specific objectives and site-
specific physical constraints (geotechnical concerns and
hydrogeology), but generally, PRB installation that require
numerous passes to achieve a design thickness is imprac-
tical. The relationship between reaction kinetics and resi-
dence time (ϑ) is presented in Section 10.3.2, but briefly,
if the contaminant cannot be immobilized or destroyed in
the amount of time it takes for the contaminant to trans-
port across the thickness of the PRB, the treatment reagent
should be disqualified.
The stability of the treatment reagent, or the ability to
remain reactive with minimal regeneration maintenance over
the planned operation of the PRB, is a function of the site-spe-
cific geochemistry and microbiology. Recall from Chapter 7
and the discussion in Section 10.5.3 that ZVI treatment reagent
was passivated (i.e., coated) with a 30–150  µm thick layer
of mineral precipitate on the upgradient edge of the PRB.32
Fortunately, this passivation has not adversely impacted the
operation of the PRB, but it does demonstrate that geochemi-
cal passivation could be a real concern given a more aggres-
sive ambient geochemistry. Geochemical characterization as
part of baseline data collection to support the design of a PRB
could include field parameters (oxidation–reduction potential,
Remediation Engineering
pH, dissolved oxygen, specific conductivity, and  turbidity)
and inorganic constituents (Ca, Fe, Mg, Mn, Ba, Cl, F, SO42−,
NO3−, silica, carbonate species [alkalinity], etc.).64 These
parameters may be used in a geochemical modeling software
to predict speciation and complexation as discussed in Chapter
7; however, a reminder that the geochemical model is only as
powerful and reliable as the thermodynamic constants used.
The reactivity within a PRB is reasonably assumed to
be first order because the reactivity will decrease to some
degree over the relevant operational time frame of the PRB
and (within the treatment interval or reactive gate) the treat-
ment reagent is assumed to be present at a concentration that
is considerably greater than the influent contaminant. If a
PRB design violates either of these assumptions, the assump-
tion of first-order reaction kinetics should be revisited. The
first-order reaction equation is included in the following equa-
tion for completeness, and the terms, relevant to a PRB, are
defined accordingly:
C = C0e - kt (10.6)
where
C is the concentration of the contaminant leaving the PRB
C0 is the concentration of the contaminant entering the
PRB
k is the reaction constant (specific to the reaction
mechanism)
t is the time for the reaction to take place
10.3.2.2  Treatment Reagent Availability (Cost)
Routine and practical applicable treatment reagent for PRBs
are readily available. For example, the most popular is ZVI,
and it is readily available from numerous vendors at market
pricing. Sorbents like GAC and ion exchange media are also
readily available. The costs of some treatment reagents as of
2009 are summarized in Table 10.5.1 The treatment reagent
cost can be a considerable driver on large continuous PRBs
TABLE 10.5
Examples of Treatment Reagent Costs and Estimate
Longevity Information
Range in Estimated
Treatment Reagent Unit Cost Longevity (Years)
Coarse ZVI (300–2360 µm) $0.30–$0.45/lb >15
Fine/micro ZVI (<300 µm) $0.40–$0.75/lb 5 to >10
ZVI–carbon $1.50–$2.50/lb 3–5
Anaerobic biological PRB carbon $10–$12/yd3 4–6
EVO (biological PRB recharge) $1.25–$2.00/lb 1.5–3
Emulsified ZVI Not available
Organophilic clay $1.10–$1.25/lb >4
Source: ITRC, Permeable reactive barrier: Technology update, The
Interstate Technology and Regulatory Council PRB: Technology
Update Team, Washington, DC, 2011, http://www.itrcweb.org/
Guidance/GetDocument?documentID=69.
Reactive Walls
or even for funnel and gate PRBs if the reactivity lifetime is
low and frequent regeneration is required. A successful PRB
design will minimize the required treatment reagent and the
required regeneration.
10.3.2.3 Treatment Reagent Compatibility
(Hydrogeological, Geochemical,
and Construction)
The final selection criterion for a potential PRB treat-
ment reagent is the compatibility of the natural aquifer and
the treatment reagent. If a treatment reagent meets reactiv-
ity requirements, but will result in considerable geochemi-
cal or microbiological fouling, it should be disqualified. For
example, in an anaerobic biological PRB, if the percentage of
soluble organic carbon will reduce the pH and inhibit the tar-
geted bacterial metabolism, it is incompatible given the natu-
ral buffering capacity of the aquifer. This is also an example
of why treatability testing is so important. Geochemical and
hydrogeological incompatibilities will become apparent dur-
ing treatability testing. Another consideration of treatment
reagent compatibility is the emplacement during construction.
The ideal treatment reagent will be emplaced with the mini-
mum amount of excavated soil.
10.3.3 Treatment Reagent Types
The previous section (Section 10.2.1) identifies and discusses
relevant and practical reaction mechanisms for PRBs. The
purpose of this section is to provide specificity to treatment
reagent types that are relevant and practical for the previously
identified reaction mechanisms. Gaseous treatment reagents
(i.e., air, oxygen-enriched air, ozone) are not discussed here.
10.3.3.1 ZVI
The most popular and prevalent treatment reagent used in
PRBs installed since the 1990s is ZVI. The reaction mecha-
nisms of ZVI are discussed in Section 10.2.1.2.2 and Chapters
6 and 7. The reaction kinetics associated with ZVI are
directly related to its particle size, and reaction rates increase
as ZVI particles size decreases (and surface area increases).1
Target specifications for ZVI used for PRB applications are
greater than 90% iron metal content, less than 3% carbon
content, and no hazardous leachable trace metal impurities.1
It is important to ensure that surface coatings (such as oil and
grease) are not present because sources of ZVI include the
automotive waste and molten iron industries.1 Often times
treatability testing ahead of a PRB implementation will trial
numerous sizes and vendor ZVI products to select the most
cost-conscious, best performing product. Performance can
vary on a site-by-site basis due to subtle changes in the ambi-
ent geochemistry.
10.3.3.2  Mineral Treatment Reagent
The following suite of treatment reagents for use in PRBs are
nonmetallic and inorganic. They represent the following reac-
tion mechanisms: adsorption, precipitation, neutralization,
and ABOx. Due to its popularity throughout the literature and
531
general discussion in Chapter 2, GAC is not specifically dis-
cussed but does represent a common treatment reagent for the
removal of contaminants favoring adsorptive removal from
groundwater.
10.3.3.2.1 Zeolites
Zeolites are natural aluminosilicate minerals that have
high ion exchange capacities (~200 to 400 milliequivalent
weight per 100 g) and large surface areas (up to 145  m 2/g).
Clinoptilolite ([Ca, Mg, Na2, K 2][Al2Si10O24 * 8H2O]) is the
zeolite most commonly researched with respect to poten-
tial PRB applications. Due to the negative surface charge,
zeolites are effective at removing cations from groundwater.
The key reaction mechanisms for metal removal by zeolites
are cation exchange and adsorption.1 Literature demonstra-
tions of cation exchange treatment by zeolites of radionu-
clides (cesium and strontium-90)65–69 and ammonium70 and
adsorption treatment by zeolites of oxyanions (chromate
(CrO42−),71 arsenic (AsO43− and AsO33−),72 and perchlorate
(ClO4 −)73).
10.3.3.2.2  Organophilic Clays
Organophilic clays are a chemically modified form of granu-
lar or powdered clay. Native clay is converted from hydro-
philic, with a potential to swell when exposed to water, to
hydrophobic and oleophilic in nature. Organophilic clay has a
high sorption capacity for oil and creosote, typically >50% by
weight. When oil, creosote, or similar NAPL sorbs to organo-
philic clay, the hydraulic conductivity of the clay decreases.1
In order to maintain appropriate hydraulic capture of a con-
taminant groundwater plume when using organophilic clays,
sand and gravel are necessary to maintain sufficient permea-
bility to support groundwater flux.74,75 Sorption of the oil, cre-
osote, or similar NAPL is the reaction mechanism (through a
partition mechanism) of organophilic clays.
10.3.3.2.3 Apatite
The potential for usage of apatite in PRBs is extensive, and
only a brief discussion is provided here. A thorough review
of apatite chemistry and its use in environmental remedia-
tion is discussed in Magalhaes and Williams.76 The concept
of apatite-facilitating metal complexation for the purposes
of metals precipitation was introduced in Chapter 7. Natural
apatite minerals are composed of calcium and phosphorus,
with variable quantities of hydroxide, fluoride, and chloride.
Some examples include hydroxyapatite (Ca5(PO4)3OH), fluor-
apatite (Ca5(PO4)3F), and chlorapatite (Ca5(PO4)3Cl). A bio-
genically precipitated apatite material that is relevant to the
inclusion as a treatment reagent in a PRB is called Apatite
IITM (Ca10−xNa x(PO4)6−x(CO3)x(OH)2, where x < 1).1 This
form of apatite was developed to increase reactivity.77 The key
treatment mechanisms for metal removal by apatite include
cation exchange, precipitation of metal phosphates, and incor-
poration into the apatite structure.78 Due to the presence of
associated organic materials, apatites may also promote the
precipitation of low-solubility, metal-sulfide phases due bio-
logical activity.77
532
10.3.3.2.4 Limestone
Limestone (CaCO3) can be used in PRBs to facilitate acid-
ity neutralization. Acidity is a common co-contaminant at
sites where groundwater is impacted with metals because
most industrial processes that involve high concentrations of
metals use acidity to keep the metals in solution. Therefore,
when a release or discharge to the aquifer occurs, it is typi-
cally highly acidic. A theoretical and thermodynamically
spontaneous79 acidity neutralization reaction using limestone
(CaCO3) is presented in the following equation:
CaCO3 + H + ® HCO3- + Ca 2 + (10.7)
The resultant cationic calcium is likely to precipitate via ion
exchange or further buffer the groundwater with the forma-
tion of lime (CaO). Limestone (CaCO3) use in PRBs is highly
susceptible to passivation. Depending on the extent of acid-
ity, naturally occurring ferric iron (Fe3+) and aluminum (Al3+)
may be solubilized and will instantaneously precipitate upon
acidity neutralization with voluminous solid precipitates.
Infrastructure for treatment reagent regeneration and sophis-
ticated treatability testing and geochemical modeling should
support a limestone PRB design. The primary reaction mech-
anism for a limestone PRB is acidity neutralization, which
will cause precipitation of heavy metals as metal hydroxides
and metal carbonates (Chapter 7).
10.3.3.2.5 Gypsum
The most relevant and practical form of sulfate (SO42−) for
a PRB to support ABOx is gypsum (CaSO4 * 2H2O), which
has an approximate solubility of 2,000 mg/L (approximately
1,200  mg/L as sulfate [SO42−]) at 20°C. Gypsum may be
emplaced in a PRB as a granular or powdered material, and
the sulfate (SO42−) will naturally dissolve through equilibrium
concentration gradients into the treatment interval or reactive
gate. The primary reaction mechanism for a gypsum PRB is
ABOx of PHs.
10.3.3.3  Organic Treatment Reagent
The categories of available organic treatment reagents include
solid carbon sources (e.g., mulch, compost, sawdust, wheat
straw, chitin, walnut shells, newspaper, raw cotton, alfalfa, jute
pellets, pulp wastes, agricultural waste, products), dissolved
carbon sources that are appropriate for injection using semi-
permanent injection wells (e.g., sodium lactate, molasses, EVO,
various alcohols), and extremely viscous or slurry-based car-
bon sources not appropriate for injection using semi-­permanent
injection wells, but rather require direct push injections for
auger/caisson/soil mixing (hydrogen release compound, cheese
whey, emulsified oil/fibrous carbon, and ZVI mixtures). For
brevity, the focus of this section is on practical carbon sources
routinely considered for inclusion in anaerobic biological PRBs
(various forms of mulch, EVO, and emulsified oil/fibrous
carbon and ZVI mixtures). The reader is referred to relevant
literature on design guidance and considerations for the avail-
able organic treatment reagents, from both injection-based and
PRB-specific aquifer remediation.80–84
Remediation Engineering
Various forms of mulch are ideal as treatment reagent for
anaerobic biological PRBs. Guidance documents generally
recommend targeted anaerobic degradation processes life-
times of 5–10 years, which is an imprecise determination to
make considering the variability of organic content of mulch.
Anaerobic biological PRBs installed thus far do not have
the operational data to predict TOC exhaustion. The authors
were given the opportunity to review the historical monitor-
ing data from an anaerobic biological PRB installed in 2006
at Seneca Army Depot in New York, which was scheduled
(based on a 10-year operational lifetime) to be recharged
with carbon. The Seneca Army Depot anaerobic biological
PRB used mulch and EVO as treatment reagents. Analytical
data available from the performance monitoring well net-
work suggest that recharge is still not required based on
successful performance and residual dissolved-phase TOC
concentrations.
Mulch and compost treatment reagents are typically
mixed with coarse-grained sand or pea gravel (40%–60%
by volume) to provide structural fill and maintain perme-
ability/porosity.1 As the mulch and compost degrade, there
are potential compaction concerns. Wood mulch, a com-
mon mulch source for anaerobic biological PRBs, is a
good source of degradable carbon, with higher percentages
as cellulose (40%–50%) and hemicellulose (20%–30%).
However, lignin (which represents approximately 25%–
30% of the carbon in wood mulch) is resistant to biodegra-
dation.85,86 Mulch treatment reagent is often coupled with
EVO to provide an initially more soluble source of TOC
and the extended duration soy bean oil to supplement recal-
citrant lignin.
EVO is a well-known organic carbon source and is becom-
ing the standard for injection-based in  situ biological reme-
diation. The limitation of EVO injections is challenging
distribution at large ROI due to potential aquifer straining
of the oil droplets, but ongoing research and development is
achieving smaller oil droplet sizes. Notwithstanding ongoing
research, aquifer straining is of less significance within the
treatment interval of a PRB, which is intentionally designed
to have a higher permeability than the surrounding aquifer.
This higher permeability facilitates better lateral distribution.
Typical EVO concentrations in anaerobic biological PRBs
range from 5% to 10% by volume.
Lastly, emulsified oil and fibrous carbon sources have
been combined with ZVI for a powerful biological substrate/
chemical reductant. The product is available as a soluble
powder that may be added as a slurry or as a highly con-
centrated liquid that is mixed with a powder and water in an
attempt to make it more injectable. The synergies of anaero-
bic metabolism and chemical reduction have been well docu-
mented,87–93 and this proprietary product combines the fast
kinetics of abiotic reduction with the supportive sustained
biological conditions. A PRB is an ideal implementation for
this type of sparingly soluble treatment reagent because it
is placed uniformly during construction and has iron-based
cycling potential to facilitate numerous reaction mechanisms
concurrently.
Reactive Walls
10.4  KEY DESIGN PARAMETERS
A successful PRB design includes the following components:
• A suitable PRB configuration (Section 10.1.1)
• An appropriate treatment reagent (Section 10.2.3)
• The correct size (length, thickness, and depth) of the
PRB
• A cost-conscious installation and construction method
(Section 10.1.2.2)
• A comprehensive QA/QC program
In order to evaluate and consider these design components
adequately, a detailed understanding of the site geology and
hydrogeology, nature and extent of the contamination, and
ambient aquifer geochemistry is critical.94 While a PRB
provides a low O&M cost, it cannot be understated that the
installation can be expensive and little can be done to improve
efficiency once it is installed. The design and construction
must incorporate a robust CSM and recognize deviations
from expectations and adapt accordingly.
The number and location of PRBs at a given site is reflective
of the treatment objectives. If site conditions support long-term
in situ remediation management, a single PRB may be placed at
the site boundary with the understanding that site-wide reme-
diation to cleanup goals will take decades. If a more aggressive
time frame is targeted, the selection of a PRB alone should be
questioned. The PRB technology is highly effective, but is a
passive technique that relies on the natural flux of groundwa-
ter. Multiple PRBs may be installed (not unlike injection well
transects) to expedite remediation if the groundwater veloc-
ity and relevant contaminant plume flushing calculations are
supportive, but typically, there are more cost-effective ways to
implement a large-scale IRZ. It is important to understand the
treatment objectives before designing the PRB.
10.4.1 Hydraulics
Understanding the site-specific groundwater flow regime is
essential to designing and constructing a successful PRB.7
Details associated with the groundwater flow regime include
the seasonal variation in direction and elevation, regional
aquifer management (such as pumping or storage), and
groundwater flow velocity. All aquifers are heterogeneous
and anisotropic at every scale,16 and therefore, the ground-
water flow velocity will vary along the length and thick-
ness of the treatment interval or reactive gate. A tracer test16
(Chapters 4 and 6) is recommended in support of a PRB,
though it is recognized that the spatial heterogeneity across
the PRB will vary. Tracer testing presents the most accurate
way of determining the groundwater velocity and evaluating
transport characteristics of the aquifer, such as the relation-
ship between high contaminant flux and stagnant intervals.
Simple single borehole dilution testing can be done at numer-
ous locations across the length of PRB to provide a cross
sectional average of groundwater velocity through a PRB.
Routine single-borehole dilution test over the operational
533
lifetime of the PRB is an inexpensive way to evaluate hydrau-
lic performance and gauge the degree of flow resistance as a
result of passivation.
Groundwater flow and transport models are great tools
to assist in understanding how an aquifer responds or may
respond to a PRB. The groundwater flow and transport models
are only as powerful as the assumed design parameters upon
which they are built. Iterative modeling simulations and con-
taminant particle tracking may be performed to arrive at the
optimum configuration of a PRB, but should be interpreted
logically and not blindly followed. Modeling results that devi-
ate from the anticipated CSM should be met with an open con-
sideration rather than disregarded as anomalous. Groundwater
flow and transport models are informed by site characteriza-
tion, tracer testing, geochemical modeling, and the results
from treatability testing and should be continually updated
as the understanding of the CSM evolves. More information
on groundwater flow and transport modeling is presented in
Chapters 4 and 5.
The factors that are typically evaluated as part of a ground-
water flow and transport model exercise include the following:
• The total thickness and length of the PRB (funnel
walls for a funnel and gate PRB)
• The minimum number of required reactive gates (for
funnel and gate PRBs)
• Particle tracking for the selected configuration to
ensure complete capture of the contaminated plume
• The residence time (ϑ) through the reactive gate or
treatment interval
• Resultant changes in the hydraulic gradient as a
result of permeability differences and the potential
for a dam effect
• Predicted biological or geochemical fouling with
time and increased resistance to flow through the
PRB
• The influence of natural/seasonal groundwater ele-
vation fluctuations and flow directions
• Any geologic/hydrogeologic anomalies that may
lead to preferential flow within the contaminated
plume
• Identifying logical locations for the performance
monitoring wells
• The potential for groundwater flow to miss the
treatment interval or reactive gate (above, below, or
around the PRB)
• Model calibration and sensitivity to the site-specific
hydrogeologic parameters such as hydraulic conduc-
tivity and transmissivity
The ITRC specifies that the thickness of a PRB is calculated
as the seepage velocity (vgw) multiplied by the residence time
(ϑ) to achieve treatment standards.1 The thickness of the PRB
will dictate the following components: the hydraulic flux
across the cross section of the PRB, the degradation kinetics
associated with contaminant treatment, and the constructabil-
ity of the PRB.
534
Darcy flux–specific discharge through the PRB can be
described using the following equation:
Qabs
= Ki (10.8)
A (t) within the treatment interval of the example anaerobic bio-
where
Qabs represents the flow rate of groundwater across PRB
cross sectional area (A)
K represents the average hydraulic conductivity of the
backfill and treatment reagent
i represents the hydraulic gradient across the thickness of
the PRB
The seepage groundwater velocity can be determined by divid-
ing the specific discharge (K*i) by the mobile porosity (θm):
Ki
vgw = (10.9)
qm
The seepage groundwater velocity (vgw) accounts for accelerated
flow through a porous media and, therefore, is more accurate than
using Darcy flux to estimate the residence time (ϑ) of groundwa-
ter within the treatment interval or reactive gate of the PRB.
10.4.2 Treatment Kinetics and Minimum
Residence Time
The most important factor in designing a PRB is the relationship
between the residence time (ϑ) of contaminated groundwater in
the treatment interval or reactive gate and the rate of contami-
nant degradation reactions. In Section 10.2.2.1, reaction kinet-
ics associated with a PRB were defined as following first-order
kinetics per Equation 10.6. If Equation 10.6 is rearranged to
solve for the reaction time (t), the following equation is defined:
ln ( C /C0 )
t= (10.10)
-k
This calculated reaction time (t) reflects the required time
for a given reaction mechanism (dictated by the reaction rate
constant [k] in Equation 10.6) and represents the minimum
amount of time required for groundwater to be in the treat-
ment interval or reactive gate of a PRB. For example, if the
influent concentration of TCE to a PRB is 1,000 µg/L and
the targeted cleanup goal is 5 µg/L and there is a confirmed
anaerobic biological first-order reaction rate of 0.1 day−1, the
calculated reaction time (t) is 53 days.1
The residence time (ϑ) in a PRB treatment interval or reac-
tive gate can be calculated by dividing the empty bed (or void)
volume of the PRB (of size length [L] multiplied by thickness
[T] multiplied by height [H] multiplied by the total porosity
[θT]) by the seepage velocity through the PRB (vgw):
L ´ T ´ H ´ qT
J= (10.11)
vgw
In continuing with this TCE example, suppose the hydrau-
lic conductivity (K), hydraulic gradient (i), and mobile
Remediation Engineering
porosity (θm) of the treatment interval of a continuous PRB
are 10  ft/day, 0.01 ft/ft, and 10%, respectively. The seepage
velocity (vgw) is calculated per Equation 10.11 to be 1 ft/day.
Therefore, in order to allow for 53 days’ worth of reaction time
logical PRB, a thickness of 53 ft is required. A conventional
excavator bucket is approximately 3–4 ft wide, and therefore,
this PRB thickness would require several excavated trenches
side by side, which increases the installation time and cost.
Here an advantage of abiotic reductive dechlorination with
ZVI is evident and related to the reaction time (t). According
to Ebert et  al., a geometric average first-order reaction rate
constant for dechlorination of TCE facilitated by ZVI is 3.6
day−1.37 The authors have field experience at sites with mea-
sured first-order reaction rate constants for dechlorination of
TCE facilitated by ZVI ranging from 0.2 to 6.6 day−1. Using
an average first-order reaction rate constant of 3.4  day−1 for
dechlorination of TCE facilitated by ZVI results in a reaction
time of approximately 1.6 days and a required PRB thickness
of 1.6 ft. This thickness is well within the installation capacity
of a conventional excavator.
This evaluation exemplifies the type of balancing design
decisions for the implementation of a PRB quite well. Option
1 is a single-pass continuous PRB with ZVI treatment reagent,
which, despite the higher cost of the ZVI treatment reagent
(Table 10.5), will likely have a lower installation cost because
it is a single PRB. Future regeneration of ZVI may be chal-
lenging and, depending on the geochemistry of the aquifer,
may shorten the operational time frame of the PRB. Option
2 is potentially a double-pass continuous PRB with organic
carbon treatment reagent, which may have a higher installa-
tion cost. Anaerobic biological PRBs can be equipped with
injection wells to recharge TOC and extend the operational
time frame of the PRB. The balancing criteria become quite
clear, and the need for understanding the CSM and treatabil-
ity comparison is apparent. Note that the 0.1  day−1 reaction
rate constant theorized for the sample anaerobic biological
PRB herein does not consider TCE sorption to the organic
material or other retardation of the contaminant transport
that will increase the residence time (ϑ) within the PRB treat-
ment interval, nor does the groundwater seepage velocity (vgw)
determined residence time (ϑ) consider the potential for TOC
to transport downgradient and extend the treatment thickness
of the PRB.
Therefore, the balance between the size of the PRB (which
dictates the residence time [ϑ]) and the selected reaction
mechanism (which dictates the reaction time [t]) presents the
design constriction for a PRB. Equations 10.10 and 10.11 are
solved simultaneously to ensure the effluent from the PRB
will meet the targeted objectives, and typically, safety fac-
tors are applied to account for anticipated losses in reactiv-
ity or increased seepage velocity (vgw) over time. Faster and
greater treatment can be achieved by either faster rate kinet-
ics (smaller reaction times [t]) or longer residence times
(ϑ), respectively. Increased residence time (ϑ) requires an
increased PRB size and thus higher costs. Depending on the
type of reaction mechanism utilized in the PRB, both of these
Reactive Walls
factors may have to be optimized. In some cases, an increased
residence time (ϑ) may be required. There are several options
available for increasing the residence time (ϑ):
• Increase the reactor volume (larger PRB).
• Install multiple reactive gates to reduce the flow
through each reactive gate (Qabs).
• Install reactive gates in series to achieve complete
reaction.
Physical reaction mechanisms have short reaction times (t),
and sufficient residence time (ϑ) is typically not a concern.
If it is, optimizing the air-to-water ratio or providing pack-
ing material to enhance the mass transfer efficiencies may
be warranted. Residence times (ϑ) required for the precipita-
tion, abiotic reduction, and chemical oxidation processes are
relatively small and will not be a concern in most situations.
Biodegradation processes are governed by the reaction rate
constant (k) of specific contaminants. An empirical parameter
used to estimate the allowable mass loading (C0) in biologi-
cal treatment systems is the food-to-microorganism ratio, the
unit of which is mass of contaminants/mass of viable biomass.
From this expression it can be noted that the higher the avail-
able biomass, the faster the reaction will be. The biomass con-
centration per unit volume of the PRB may be increased by
maximizing the available surface area to which the biomass
may attach.
10.4.3  Contaminant Distribution and Mass Flux
It is intuitive that the nature and extent of the groundwater
contamination to be remediated using a PRB would influ-
ence the design of the PRB. Based on the treatment objec-
tives, a PRB is typically a management strategy that serves
to cut off further contaminant transport offsite while active
remediation or natural attenuation proceed to reduce source
material. Therefore, it is important to understand the distribu-
tion of contamination from both lateral and vertical perspec-
tives. The type of contamination and the practical expectation
of concentrations that will transport through the PRB are of
paramount importance and directly influence the reaction
mechanisms considered and the treatment reagent loading.
The consumption and reduction in reactivity of the treat-
ment reagent are directly related to the contaminant mass
flux. Stoichiometric hand calculations, geochemical model-
ing, treatability testing, and the appropriate level of safety
factor are critical to placing a lasting quantity of treatment
reagent within a treatment interval or reactive gate. In  situ
reactions are difficult to predict, and while stoichiometry is a
poor indicator of the true treatment reagent consumption due
to geochemical scavenging and metabolic inefficiencies, it
does provide a minimum threshold of treatment reagent upon
which safety factors may be applied. Geochemical modeling
and treatability testing are vital to predicting how the contam-
inant mass flux will interact with the treatment reagent. Based
on the spatial location of the PRB, the influent contaminant
mass flux may be sustained for several years. It is important to
535
conservatively and practically predict the required treatment
reagent loading to the PRB to maintain treatment efficiency.
10.4.4 Longevity
With respect to a PRB, longevity is defined as the ability of the
PRB to sustain the critical performance criteria (i.e., hydrau-
lic capture, residence time [ϑ], and reactivity) for the requisite
operational lifetime.1 Therefore, failure of a PRB is identified
as the inability to meet one of these three criteria, which may
result in contaminant breakthrough downgradient of the PRB.
Based on the 200 PRBs that have been installed worldwide
and the approximately 20  years of performance monitoring
data, some broad generalizations can be made about the lon-
gevity of PRBs. However, it is important to note that aquifer
remediation may take several decades, which could outlast a
PRB that significantly outperforms its predicted operational
time frame.
The longevity of a PRB may be considered as follows1:
• Will the PRB effectively intercept the plume at least
consistent with a minimum level that is protective of
downgradient receptors?
• Will the residence time (ϑ) remain adequate?
• Will the PRB outlast the plume without requiring
major modifications of complete replacement?
• Will the comparatively higher capital cost for PRB
installation be recovered through savings realized
during the years of passive operation?
The greatest threat to the longevity of a PRB is passivation
of the treatment reagent, which can occur geochemically or
biologically and can influence reactivity and hydraulic cap-
ture. There is a host of literature available that summarizes
the potential for passivation and discusses the detailed geo-
chemical speciation of the mineral passivation as well as the
ultimate deleterious influence.95–110 Another consideration
that influences the longevity is the treatment reagent load-
ing, specifically in a biological PRB that does not include
a sparging system to continually provide oxygen. The
emplaced treatment reagent will dissolve and be utilized
over time and may require recharge. Building the option to
regenerate and/or recharge treatment reagent in PRBs is an
effective way to increase the longevity of a PRB, or at least
minimize the potential long-term cost of major modifica-
tions or complete replacement. Recharge and/or regenera-
tion of treatment reagent in a reactive gate is more favorable
than along a continuous PRB, but using recirculation may
expedite and reduce the recharge and/or regeneration cost in
a continuous PRB.
10.5  PERFORMANCE MONITORING
The treatment objectives of a PRB design are stated and
agreed to by stakeholders long before the implementation of
the remedy. Performance monitoring is a tenant of any in situ
remedial technology designed to ensure that the implemented
536 Remediation Engineering

remedy achieves the treatment objectives (also known as per-
formance objectives). Most PRBs have similar performance
objectives, which are to protect human health and the envi-
ronment and destroy and/or immobilize contaminants. In this
section, a discussion of relevant components of performance
monitoring to a PRB are presented.
A PRB performance monitoring well network is a balance
of the cost to install and monitor monitoring wells to perpe-
tuity and the necessity to demonstrate the effectiveness of the
PRB and collect O&M data to ensure it continues to operate as
designed. The ideal PRB performance monitoring well network
is the fewest monitoring wells possible that demonstrate hydrau-
lic and treatment objectives are accomplished. Several potential
arrangements of performance monitoring wells associated with
different PRB configurations are presented on Figure  10.22.
Reactive Reactive
cell Funnel medium
Plume Plume Gate
Pea
Pea gravel
gravel
(a) (b)
Reactive Reactive
cell cell
Plume Plume
(c) (d)
Reactive
Funnel medium
Plume
Pea
gravel
(e)
FIGURE 10.22  Potential performance monitoring well networks
for different permeable reactive barrier (PRB) configurations. (From
Gavaskar, A.R. et al., Permeable Reactive Barriers for Groundwater
Remediation Design, Construction, and Monitoring, Battelle Press,
Columbus, OH, 1998.) (a) Presents a continuous PRB with monitor-
ing wells within the treatment reagent to demonstrate effectiveness
and side gradient to confirm hydraulic capture. (b) Presents a funnel
and gate PRB with a similar concept as (a). (c, d) Present continuous
PRBs that have side gradient monitoring wells to confirm hydraulic
capture, but unique placement of monitoring wells to demonstrate
treatment. (c) Places monitoring wells within the treatment reagent
laterally and over the thickness to gauge performance within the
PRB. (d) Places monitoring wells just downgradient and further
downgradient to monitor treatment effectiveness and downgradient
extent of clean water flushing. Finally, (e) presents a similar concept
as (d) except for a funnel and gate configuration.
In each of the proposed performance monitoring well networks,
monitoring wells are located either upgradient, side gradient, or
downgradient depending on the particular objectives. The design
of a PRB performance monitoring network will have a site-spe-
cific component to it, but in general should provide sufficient
data to confirm treatment and trigger regeneration/recharge of
treatment reagent. Particular CSM anomalies (i.e., geochemi-
cal or hydrogeological) need to be considered to ensure the data
generated by the performance monitoring well network are as
representative and relevant as possible.
10.5.1 Performance Objectives and
Demonstration Considerations
Standard performance objective considerations for a PRB are
presented in Table 10.6 per the ITRC PRB design guidance
document.1 This section discusses specific considerations in
demonstrating compliance with the selected performance
objectives.
The first four performance objectives in Table 10.6 are
related to the hydraulic performance criterion. In Section
10.3.1, groundwater flow and transport modeling was dis-
cussed as a way to select locations for performance moni-
toring wells. The purpose of these performance monitoring
wells (or piezometers) would be to confirm that the hydrau-
lic orientation performance objectives are being met.
Based on review of the available PRB datasets, the most
reoccurring cause for poor PRB performance is improper
accounting for the site hydrogeology.15 Monitoring wells/
piezometers located upgradient, side gradient, downgra-
dient, and within the PRB is the best way to observe the
actual operation of the PRB. These data can then be used
to calibrate the groundwater model to be more predictive of
future operation.
The next set of performance objectives in Table 10.6
are related to the residence time (ϑ) and reactivity crite-
ria. Conventional groundwater monitoring for contaminant
concentrations is the first line of evidence that the PRB
is operating as designed. If further lines of evidence are
required per regulatory agencies, or if the contaminant
concentrations are not decreasing as expected, secondary
lines of evidence such as compound stable isotope analysis
(CSIA) and microbiological tools may be implemented to
demonstrate on a microscale that the reaction mechanisms
are viable and functional, and just require more time to
be observed on the macroscale of groundwater analytical
results. CSIA is an isotopic enrichment assessment that
provides unequivocal evidence of compound weathering.
It may help to determine whether a compound has under-
gone a chemical or biological transformation rather than a
nondestructive physical process such as dilution or sorp-
tion.1 Microbiological tools may include isotopic enrich-
ment, fatty acid analysis, and quantitative polymerase
chain reaction. These secondary analyses are applicable to
VOCs and PHs, but for metal analysis, esoteric (i.e., highly
specialized) analysis may be required such as high resolu-
tion spectroscopy and microscopy.
Reactive Walls 537

TABLE 10.6
Typical Hydraulic and Contaminant Performance Objectives and Evaluation Approaches for Permeable
Reactive Barriers
Performance Objective
Maintain hydraulic gradient per PRB
design.
Maintain appropriate surface water
recharge controls.
Maintain appropriate flow conditions
within the PRB.
Ensure the PRB is placed as intended
within the aquifer.
Meet MCLs, including secondary
MCLs.
Evaluate geochemical trends.
Control geochemical influences and
secondary by-products of the
targeted reactions
Description
The hydraulic gradient (i)—vertical and lateral direction
and magnitude—must be maintained within a specified
range consistent with the residence time (ϑ). This
prevents redirecting targeted groundwater under, over, or
around the PRB, and it avoids a sustained hydraulic
mound within or immediately upgradient of the PRB.
Excess or high-impact surface water recharge within the
PRB or adjacent (upgradient or downgradient) of the
PRB may negatively impact the hydraulic performance
by influencing hydraulic gradients (i) and contaminant
migration conditions.
Passivation and over compaction may all negatively affect
the flow conditions with the PRB. Some changes over
time are anticipated, but construction defects should (and
can) be avoided.
This objective covers placement of the PRB as well as
physical parameters (e.g., media density, porosity,
quality, and volume).
Maximum allowable contaminant (MCL) levels are set for
constituents of concern (COCs) in compliance
monitoring wells.
Graphical and statistical analysis to develop a
comprehensive understanding of the treatment process
and treatment reagent aging.
Treatment reagent passivation may result from
uncontrolled pH or oxidation–reduction potentials.
Evaluation Approach
Regular groundwater elevation monitoring,
groundwater flow, and transport modeling updates to
determine the most probable contaminant transport
direction and rate.
Establish engineering controls and monitor the
effectiveness of these controls during times of
potential surface water recharge conditions (such as
during precipitation events).
Perform singe-hole borehole dilution tests within the
PRB at regular intervals (3–5 years) after
construction.
Assess as-built conditions and compare to design
specifications; evaluation techniques may include
postconstruction hydraulic tests, borings to assess
placement of the PRB, geophysics, water-level
monitoring, and water-quality parameter monitoring.
This process is particularly important for
injection systems.
Regular monitoring of compliance monitoring wells
per regulatory requirements.
Trend analysis performed after each sampling event,
with geochemical modeling to support observations.
Analyze secondary parameters over time (regular
parameters and infrequent analysis).

Source: ITRC, Permeable reactive barrier: Technology update, The Interstate Technology and Regulatory Council PRB: Technology Update Team, Washington,
DC, 2011, http://www.itrcweb.org/Guidance/GetDocument?documentID=69.

10.5.2  Secondary Water-Quality Concerns
The chemical and biological reaction mechanisms discussed
in Sections 10.2.1.2 and 10.2.1.3 result in geochemical changes
to the ambient groundwater within and immediately down-
gradient of the PRB. Similar to more active and broader-scale
in situ remediation, these geochemical influences may result
in temporary exceedances of secondary water quality criteria.
The most persistent and concerning secondary water-quality
effects include nitrate (NO3−), sulfate (SO42−), pH, arsenic
(As3+ and As5+), and trihalomethanes (THMs), though this list
is not comprehensive. These are recognized as the most con-
cerning because these compounds are commonly observed,
and THMs, nitrate (NO3−), and arsenic (As3+ and As5+) have
primary maximum contaminant levels (MCLs).
It is important to note that these secondary water-quality
issues are typically attenuated as groundwater trans-
ports downgradient of the PRB and are not source-related
contaminants. However, as PRBs are used as downgradient
cutoff barriers, some consideration is necessary for an appro-
priate attenuation distance downgradient of the PRB prior to
offsite discharge.
10.6  PERFORMANCE CASE STUDIES
The design concepts discussed in this chapter are best demon-
strated through demonstration. Three case studies are summa-
rized in this section. The first (Elizabeth City, NC) is one of the
oldest ZVI PRBs in the United States, which has been heavily
monitored and reported on throughout its history. Numerous
publications are available discussing various components of
the PRB, and they have contributed significantly to the PRB
industry knowledge base. The second case study is an anaero-
bic biological PRB that was designed to address elevated con-
centrations of perchlorate in groundwater. The pilot-scale PRB
538 Remediation Engineering

was installed in 2009 and immediately demonstrated success
that led to two additional downgradient PRBs. The results were
consistent with expectations as the biological reduction path-
ways for perchlorate are well established. The third and final
PRB case study is a large-scale PRB that was implemented
for the remediation of chlorinated VOCs and used a one-pass
continuous trencher for installation.
10.6.1 Case Study 1: GETS Replacement
with a ZVI PRB
Case Study 1 is from a government-operated munitions
research and development facility located in the Eastern
United States. Washing and degreasing of metal parts prior
to a historical plating process generated waste TCE, which
reportedly flowed to a dry well and was discharged to the sus-
pected source area. Historical operations ceased in 1980, and
all infrastructures related to the TCE release were removed
and closed under the Resource Conservation and Recovery
Act in 1991. The location of the installed PRB and the sup-
porting performance monitoring well network are presented
on Figure 10.23. Concentrations of TCE (which range from
100s to 1,000s of µg/L) primarily impact an unconsolidated
aquifer of an approximated thickness of 45–60 ft. A strong
upward vertical gradient results in groundwater discharge
to the surface water body shown on Figure 10.23, and, as a
result, discharge to the surface water body was the driver for
remedial action. The regional hydrogeologic CSM is informed
by a robust network of investigative borings and monitor-
ing wells that have been carefully studied over decades of
environmental monitoring at the site. Groundwater flow and
transport models, continually refined with new observational
data, provide a detailed understanding of overland runoff and
surface water and aquifer groundwater flow. The PRB was
positioned in an ideal location (approximately 50 ft upgradi-
ent of the surface water body) as the upward vertical gradi-
ent supported a PRB treatment depth that was practical for
a conventional continuous trenching installation method to
approximately 35 ft.
An interim remedy of a GETS was operated from 1992
to 2007. The GETS was mandated by an interim Record of
Decision to intercept contaminated groundwater prior to dis-
charge to the surface water body. The GETS was referred to as
a hydraulic barrier and consisted of six extraction wells, with
ex situ treatment components (air stripping [with vapor phase
GAC] and GAC treatment). Effective removal was observed
with peak concentrations declining from 13,800  µg/L in
1997 to 4,500 µg/L in 2005. The maximum monthly aver-
age of extracted and treated groundwater from the GETS was
over 100 gallons per minute (gpm). Neglecting infrequent

PRB-10

W6-S PRB-4
W6-M PZ-3
PRB-3 D-SW-2
PRB-5
PRB-6
GW flow direction

SG-1

PZ-2
D-SW-8

Trend data provided

W2-S
on Figures 10.22 and
W2-M 41-9
10.23
PRB-2 41-8
PRB-1 PZ-1
PRB-7
PRB-8 D-SW-3 41-1
Legend
MWD-1
Staff gauge location
PRB-9
Surface water location
Wells in PRB network
Wells in MNA network
Permeable reactive
barrier
Area D
0 75 150 Golf course
D-SW-4
Ft

FIGURE 10.23  Case Study 1 Permeable reactive barrier layout. Boxed wells presented in follow-up groundwater elevation and trichloro-
ethene trends.
Reactive Walls
variations in production and assuming a consistent 80 gpm
flow rate from September 1992 to April 2007 (when the GETS
was shutdown) suggests that over 6.1 × 108 gal of groundwa-
ter was extracted and treated. With GAC changeouts and
labor and utility costs to operate the GETS, this represents
a significant O&M investment. Groundwater flow and trans-
port modeling and contaminant plume predictions anticipate
approximately 170  years of natural attenuation that will be
necessary to achieve regulatory cleanup goals, implying
that more than 7 × 109 gal of groundwater would have been
extracted and treated had the GETS been selected as the final
remedy. However, in March 2007, the U.S. EPA selected and
approved a continuous ZVI PRB to protect the surface water
body (Figure 10.23).
The governing design parameters were the ambient hydro-
geology and geochemistry and the allowable mass flux dis-
charge of TCE to the surface water body. The lateral extent of
TCE contamination is not uniform across the PRB. Therefore,
the 80 ft section (Section 1) in the southwest was constructed to
a depth of approximately 35 ft with a higher ZVI loading (55%)
in the treatment interval than the 220 ft section (Section 2) to
the northeast, which was installed to a depth of approximately
28 ft with a lower ZVI loading (45%). The installation of this
PRB is demonstrated on Figures 10.7 through 10.9, which were
referenced earlier as an example of the continuous trenching–
supported excavation-based installation method. The PRB was
constructed using a one-pass trencher, shown in Figures 10.7
and 10.8. The trench was excavated by the chain cutter system
(Figures 10.7 and 10.9), while the treatment reagent was fed
to the unit on a conveyor and backfilled through the hopper
(Figures 10.8 and 10.9). The trench is held open for back filling
by the side shields seen in Figures 10.7 and 10.9.
The following is a step-by-step consideration of the design
calculations presented in Sections 10.3.1 and 10.3.2:
• The average TCE influent concentrations to Sections
1 and 2 were approximated to be 2,000 and 350 µg/L,
respectively. The targeted TCE effluent concentra-
tions from Sections 1 and 2 were required to be
20 and 84 µg/L, respectively, to meet surface water
discharge limits.
• Bench-scale column treatability testing was con-
ducted to determine the appropriate ZVI loading
reactivity, considering the influent TCE concentra-
tions, for a long-term operational lifetime and the
reaction time (t) necessary to achieve the targeted
TCE effluent concentrations. The resultant reaction
constant (k) was determined to be 6.7 day−1, with cal-
culated reaction times (t) of 0.7 and 0.2 day, respec-
tively, for Sections 1 and 2.
• Based on the known hydraulic conductivity (K) and
mobile porosity (θm) of the treatment reagent backfill
and the ambient hydraulic gradient (i), the seepage
velocity (vgw) through the PRB was calculated to be
1.7 ft/day.
• Based on the reaction times (t) of Sections 1 and
2 (0.7 and 0.2 day, respectively) and a seepage
539
velocity (vgw) of 1.7 ft/day, the installed PRB thick-
ness was determined to be a maximum of 1.2 ft and
a minimum of 0.3 ft. The practical installation limit
using a one-pass trencher is approximately 1 ft, and
therefore, the PRB thickness varies along the entire
width from 1.1 to 1.2 ft.
The performance of the PRB since its installation in April
2007 has been consistent with groundwater flow and trans-
port modeling predictions and continued to exceed design
objectives as of July 2014. Hydraulically, groundwater eleva-
tion data do not suggest any hydraulic mounding upgradi-
ent of the PRB that would suggest reduced permeability or
suggest the potential for short-circuiting under or around
the PRB (Figure  10.24). The performance monitoring pro-
gram includes annual sampling for VOCs and select biogeo-
chemical parameters. The responses in TCE at representative
monitoring locations from Figure 10.23 are summarized on
Figure  10.25. Monitoring locations PRB-1 and PRB-3 rep-
resent TCE concentrations upgradient of Sections 1 and 2,
respectively. The trends at these locations demonstrate sus-
tained TCE after PRB installation, which was anticipated.
There is a noticeable decline in TCE over time after PRB
installation, which may be due to dissolved hydrogen gen-
eration facilitating reductive dechlorination upgradient of
the PRB. This is speculative as analytical data for dissolved
hydrogen (or even microbiological analysis) are not available.
The monitoring locations on the downgradient side of both
sections of the PRB (PRB-5 and PRB-7) show decreases in
TCE over time, with PRB-7 demonstrating a more expected
immediate decrease to below laboratory detection limits. The
trend of data at PRB-5 suggests effective treatment, but does
show detections downgradient of the PRB 4 and 5.5  years
after installation (Figure 10.25). These detections are well
below the targeted TCE effluent concentration, but represent
curious anomalies that should be noted during performance
monitoring observations of a PRB.
This case study presents a successful switch from a GETS
hydraulic barrier to a PRB, which has significant life cycle
cost-saving ramifications. Ongoing monitoring on a yearly
basis will be continued for decades, and the PRB strategy is
in line with the treatment objective of protecting the surface
water body.
10.6.2 Case Study 2: Anaerobic Biological PRB
for Perchlorate Treatment (Biowall)
Perchlorate (ClO4−) is enzymatically reduced to an innocuous
end product (chloride [Cl−]) to reduce or eliminate perchlo-
rate-impacted groundwater.7,111–120 To facilitate this biological
process, long-term carbon sources (walnut shells, mushroom
compost, and vegetable oil) may be added to the treatment
interval of a PBR. Release of organic carbon to groundwater,
via transport of groundwater through the treatment interval,
stimulates growth of bacteria downgradient from the treat-
ment zone. The bacteria then utilize perchlorate (ClO4−) as an
electron acceptor and reduce it to chloride (Cl−). Unlike less
540 Remediation Engineering

690

688

Groundwater elevation (ft amsl)

686

PRB-1
684 PRB-3
PRB-7
PRB-5
49-1
682
PRB install

680
9/1/2002 5/28/2005 2/22/2008 11/18/2010 8/14/2013

FIGURE 10.24  Case Study 1 Permeable reactive barrier (PRB) performance monitoring well network groundwater elevation response.
Groundwater elevations primarily remain consistent upgradient and downgradient of the PRB, suggesting that the constructed PRB has not
adversely interrupted the hydraulic gradient (i).

10,000

1,000
TCE concentration (µg/L)

100

PRB-1
PRB-3
10
PRB-7
PRB-5
41-9
1
PRB install

0.1
9/1/02 5/28/05 2/22/08 11/18/10 8/14/13

FIGURE 10.25  Case Study 1 Permeable reactive barrier (PRB) performance monitoring well network trichloroethylene (TCE) trends
since PRB installation. Results show near-immediate downgradient TCE reduction adjacent to the PRB as well as further downgradient.
Upgradient performance monitoring wells show initially sustained TCE concentrations, but subsequent reductions over time (potentially
related to upgradient propagation of abiotic reducing conditions).

soluble treatment reagents like ZVI, the TOC from the long-
term carbon sources may also migrate downgradient of the
PRB extending the treatment thickness of the PRB.
In situ biological reduction (IBR) using an anaerobic bio-
logical PRB was implemented at a site in central California to
address elevated dissolved-phase concentrations of perchlo-
rate (ClO4−) in excess of 1,000 µg/L (Figure 10.26). Given the
remote setting and site-specific ecological sensitivities, a PRB
was preferred to active injections. Historical site activities
included the development, manufacturing, and testing of solid
propellant rocket motors for the defense and space exploration
industries, which resulted in perchlorate (ClO4−) and VOC
contamination above relevant criteria (i.e., 6 µg/L).
The performance objectives of this PRB were to protect
the offsite receiving waters and effectively manage the poten-
tial onsite human and ecological risks. Widespread shallow
Reactive Walls 541

NS Pre-PRB data
36 2,280
(2009)
28,100
NS
0 200 400
2,280

99.3 1,780

3,280
GW flow 833 Location of PRB
NS
NS
27.1
NS
9,600 NS

4,280 NS 143
Not sampled (NS) NS 337 552.2
≤6 µg/L NS
2,310 932
6 < X < 1000 µg/L
3.7
≥1000 µg/L 2,710 652

NS
124 NS Pre-PRB data
(2014)
NS
NS

NS

NS NS

NS
GW flow NS Location of PRB
<0.05
<2.5
450
0.23
NS <0.05

3,000 <0.05 440

17 0.063 NS
0.16
310 760
NS
510 NS

FIGURE 10.26  Case Study 2 Permeable reactive barrier (PRB) performance monitoring well network before and after PRB installation
(2009 vs 2014). Gray circles symbolize monitoring wells that were not sampled. Green circles symbolize monitoring wells that are below
the 6 µg/L cleanup goal. Pink circles symbolize monitoring wells with perchlorate (ClO4−) concentrations greater than 6 µg/L but less than
1,000 µg/L. Red circles symbolize monitoring wells with perchlorate (ClO4−) concentrations greater than 1,000 µg/L. The PRB is shown as
a black trench; note the gap over the creek area due to ecological sensitivities.

source removal was selected to mitigate the surface soil to
surface water pathway. With the primary in situ focus being
perchlorate (ClO4−) and significant ecological disturbance
concerns, an anaerobic biological PBR provided the most effi-
cient approach to reliably treat perchlorate (ClO4−) and VOC
impacts in groundwater.
Geologic units relevant to the subject PRB include allu-
vial deposits overlying the Santa Clara Formation (SCF). The
alluvium consists of variable thicknesses of silts, clays, and
sandy clays and occurs in the valleys incised within the clayey
and impermeable SCF. Alluvial groundwater is typically
encountered between 5 and 30 ft bgs, following a gradient of
approximately 0.014 ft/ft with flow to the southeast. Aquifer
testing indicates a hydraulic conductivity of approximately
27 ft/day. The estimated Darcy flux through alluvial ground-
water is 0.4 ft/day. Groundwater within the SCF appears to be
hydraulically connected to the alluvial groundwater as evi-
denced through pumping tests.
The PRB extends in a direction perpendicular to the banks
of a small creek (Figure 10.26). Due to ecological disturbance
restrictions, the PRB is not continuous across the creek, and a
gap exists. The southern portion of the PRB crosses a road and
is approximately 222 ft in length with depths varying from 21
to 36 ft. The northern portion of the PRB is approximately122
ft in length with an average depth of 23.5 ft. The PRB was
constructed using hydraulic shoring with a guar gum (i.e., bio-
polymer slurry) and an excavator bucket. Contaminant flux
through the alluvial deposits is of larger concern than through
the SCF because alluvial groundwater seasonally contributes
to surface water. Additionally, the permeability of the coarse
lenses within the alluvial deposits is greater than the SCF,
resulting in further lateral transport. Therefore, the IBR PRB
542
was keyed into the SCF, and treatment reagent was applied
over the saturated alluvial deposits.
The subject PRB was constructed in September/October
2009 and was backfilled with 60% by volume gravel, 20% by
volume mushroom compost, 20% by volume walnut shells,
and 500 gal of vegetable oil. The analytical results to date indi-
cate that anaerobic conditions have been maintained within
and downgradient of the PRB since construction in the fall of
2009. The PRB backfill materials provide an adequate supply
of carbon to account for the flux of dissolved oxygen (approxi-
mately 5 mg/L), nitrate (NO3−; approximately 5 mg/L), and
perchlorate (ClO4−; >1000 µg/L). In order to facilitate future
TOC amendment if necessary, injection and monitoring wells
were installed along the PRB. The initial design specified
TOC for 2 years of operation; however, TOC concentrations
appear to be maintained 5  years after construction and the
injection wells have not been used.
The hydraulic conductivity (K) of the PRB treatment inter-
val was designed to match the natural setting as closely as
possible to avoid influencing the natural hydrogeologic flux,
which could result in preferential flow either around or chan-
neling through the PRB. Relevant hydrogeologic data sug-
gest that the natural Darcy flux (K*i) through the aquifer is
approximately 0.4 ft/day, and using a mobile porosity of 15%
in the treatment reagent, the seepage velocity (vgw) in the PRB
is approximately 2.5 ft/day.
Literature values for first-order biological reaction rate
constants (k) of perchlorate (ClO4−) from column stud-
ies range from 0.5 to 1.5 day−1 (average of 1 day -1 )*. The
Perchlorate
10,000
1,000
100
Perchlorate (µg/L)
10
1 130 ft DG center
0.1
0.01
10/10/06 11/18/10
FIGURE 10.27  Case Study 2 Permeable reactive barrier (PRB) performance monitoring well network perchlorate (ClO4−) historical and
post-PRB installation trends. Analytical results of perchlorate (ClO4−) upgradient of the PRB remains consistent, as expected. Perchlorate
(ClO4−) concentrations within the PRB, at 20 and 50 ft downgradient show positive treatment below or near the cleanup goal of 6 µg/L.
Mixed results 130 and 250 ft downgradient, potentially due to the gap in the PRB as a result of the creek bed ecological sensitivities.
Remediation Engineering
preconstruction 2009 data shown on Figure 10.26 suggest that
perchlorate (ClO4−) concentrations immediately upgradient
of the PRB range from approximately 4,300 to 9,600 µg/L,
and the regulatory MCL for perchlorate (ClO4−) is 6 µg/L.
Therefore, assuming an average influence perchlorate (ClO4−)
concentration of 6,950 µg/L, targeting an effluent perchlorate
(ClO4−) concentration of 6 µg/L with a reaction rate constant
(k) of 1  day−1, the reaction time (t) required for perchlo-
rate (ClO4−) treatment in the PRB is approximately 7  days.
This would theoretically require a PRB thickness of 17.5 ft.
However, the PRB was only installed with a 3 ft thickness.
As TOC dissolves into the groundwater, it travels with the
perchlorate (ClO4−) extending the IRZ downgradient of the
PRB. This ensures adequate contact time between the TOC
and perchlorate.
Perchlorate (ClO4−) concentrations in groundwater upgra-
dient of the PRB are consistently greater than 1,000 µg/L
(Figure 10.27), and TOC concentrations are less than 1 mg/L
(Figure 10.28). Perchlorate (ClO4−) concentrations at monitor-
ing wells within the PRB and 20, 50, 130, and 250 ft downgra-
dient of the PRB are summarized on Figure 10.27. Analytical
data for monitoring wells within the PRB are not available
until early 2012, but since then perchlorate (ClO4−) concentra-
tions are consistently several orders below the cleanup goal
(6 µg/L). Correspondingly, TOC concentrations at these mon-
itoring wells have been sustained between 10 and 100 mg/L
(Figure 10.28). Analytical data for monitoring wells 20 ft
downgradient of the PRB (also only available since 2012)
show only 1 exceedance of perchlorate (ClO4−) (Figure 10.27)
Upgradient
SW within PRB
Center within PRB
NE within PRB
20 ft DG center
20 ft DG NE
50 ft DG center
50 ft DG gap
50 ft DG NE
130 ft DG NE
250 ft DG center
250 ft DG gap
Perchlorate standard
PRB install
12/27/14
Reactive Walls
Total organic carbon
1000
100
TOC (mg/L)
10
1
0.1
01/14/04 02/22/08 04/01/12
FIGURE 10.28  Case Study 2 Permeable reactive barrier (PRB) performance monitoring well network total organic carbon (TOC)
­historical and post-PRB installation trends. Analytical results of TOC show decreasing trends five years after installation, with an initial
design lifetime of 2 years. TOC within, 20 and 50 ft downgradient of the PRB demonstrated considerable concentrations above background
conditions. TOC does not appear to transfer further than 50 ft downgradient, but the PRB was installed as a 3 ft wide trench. This suggests
TOC propagated ~47 ft downgradient of the constructed PRB.
and demonstrate consistent TOC concentrations above
10 mg/L (Figure 10.28). Analytical data for monitoring wells
50 ft downgradient of the PRB highlight in adverse influence
of the gap in the PRB as a result of the creek. Monitoring well
20C-13 (Figure 10.26) shows sustained perchlorate (ClO4−)
concentrations greater than 100 µg/L with negligible TOC
concentrations. This is contrary to monitoring wells 20C-45
and 20C-47 (50 ft downgradient of the center and northeast
section of the PRB, respectively), which show consistent per-
chlorate (ClO4−) concentrations at or below the cleanup goal
(6 µg/L; Figure 10.27) and TOC concentrations greater than
1 mg/L (Figure 10.28). Monitoring wells located 130 and
250 ft downgradient of the PRB do not show elevated TOC
concentrations (Figure 10.28), suggesting that no active geo-
chemical influence is observed at these distances. Perchlorate
(ClO4−) concentrations do, however, show some decreases,
likely due  to dilution from upgradient treated groundwater
transporting downgradient. For example, monitoring wells
locations 130 ft downgradient of the northeast section of the
PRB and 250 ft downgradient of the center of the PRB show
significant drops in perchlorate, consistent with a dilution sig-
nature (Figure 10.27). Monitoring well 20C-17 (Figure 10.25)
located 250 ft downgradient of the gap in the PRB suggests no
sign of influence (which is expected). Monitoring well 20C-16
(Figure 10.26) shows an order of magnitude reduction in per-
chlorate since construction of the PRB in 2009, but perchlo-
rate (ClO4−) concentrations remain somewhat stable around
100 mg/L, with minimal TOC.
543
Upgradient
SW within PRB
Center within PRB
NE within PRB
20 ft DG center
20 ft DG NE
50 ft DG center
50 ft DG gap
50 ft DG NE
130 ft DG center
130 ft DG NE
250 ft DG center
PRB install
05/10/16
The data evaluation for this case study suggests that the
PRB has more than exceeded its design life of 2 years, and
constructing the wall with a thickness of 3 ft when calcula-
tions suggested the PRB should be 17.5 ft did not adversely
influence perchlorate (ClO4−) treatment. Evidence of TOC
influence approximately 50 ft downgradient indicates that
TOC (from the treatment reagent and biopolymer slurry used
for hydraulic shoring) influenced the biogeochemistry signifi-
cantly downgradient. This case study highlights the practi-
cal observations that substantiate cost-saving decisions and
exploits the highly amenable perchlorate (ClO4−) biological
pathway.
10.6.3 Case Study 3: Long-Term Evaluation
of a ZVI PRB in Elizabeth City, NC
Several PRBs have been studied intensively and are well
reported in the literature. One such example is a ZVI PRB,
constructed at the U.S. Coast Guard facility in Elizabeth City,
North Carolina, in 1996. This case study was examined and
discussed in considerable detail in Chapter 7 with respect
to ZVI facilitated metals precipitation. The operation of the
PRB is described in detail by Puls et al.38 Additional literature
describes the results of this PRB, numerous years after instal-
lation.32 A site map showing the historical lateral extent of
the hexavalent chromium (Cr6+) contaminant plume, relevant
performance monitoring wells, and the ZVI PRB is presented
on Figure 10.29.
544 Remediation Engineering

Pasquotank river

MW46
MW35D
N
ML35
MW47 ML15
ML25
MW50 MW49
ML34 ML24
ML33 ML23 ML14
ML22 ML13
Building 78
ML32 ML21 ML12
ML11 Fe0
ML31 MW48
PRB

g/L
1 mg/L
MW38

5m
0.0
MW18

1 mg/L
MW compliance well

g/L
(5–10 ft screen)

5m
ML multilevel bundle 0 10 m
0
MW13
(6 in. screens) 0.
Approx. scale

Plating Groundwater
Hangar 79 flow direction
shop

FIGURE 10.29  Case Study 3 Permeable reactive barrier (PRB) performance monitoring well network layout. This PRB represents one
of the longest monitored PRBs in the remediation industry. (From Wilkin, R.T. et al., Chapter 6: Fourteen-year assessment of a permeable
reactive barrier for treatment of hexavalent chromium and trichloroethylene, in Permeable Reactive Barrier Sustainable Groundwater
Remediation, Naidu, R. and Birke, V. (Eds.), CRC Press, Boca Raton, FL, 2015.)

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 11 Emerging Trends in
Environmental Remediation
11.1 INFLUENCE OF BIG DATA ON
ENVIRONMENTAL REMEDIATION
Since the invention of the World Wide Web 25 years ago, a
lot of data sources collected in the past and currently being
collected have been digitized and become easily accessible.
Today, it is easy to locate, collect, and analyze digitized data
and information that would have taken weeks or months in the
past. The expanding access to huge data sets and emergence
of powerful and real-time technologies represent opportuni-
ties for analysis that were never possible in the past—thus
leading to the term “big data.” In a digitized world, big data
refers to the things one can do at a large scale that cannot be
done at a smaller one, to extract new insights or create new
forms of value, in ways that can change markets, organiza-
tions, the relationships between various stakeholders, and
more. It has been transformative within many industrial sec-
tors and has been heralded as the next frontier for innovation
and competitiveness.
Large volumes of data have accumulated within the reme-
diation industry primarily driven by the requirements of reg-
ulatory compliance and risk management. While this topic
might once have interested only a few “data geeks,” big data
is now relevant within our industry, and all stakeholders stand
to benefit from its application. In this section, we explore what
“big data” means for environmental restoration and the poten-
tial it has to yield insights that support more streamlined and
sustainable approaches to benefit all stakeholders—regulatory
agencies, responsible parties, researchers, remediation practi-
tioners, and local communities. In the past, we learned slowly
and gradually about natural attenuation of petroleum hydro-
carbons (PHCs) and chlorinated solvents from data collected
from thousands of sites. The concept of big data did not exist
at that time. The insights gained took several years to observe
mainly because of the poor access to the necessary “big data”
across many sites.
11.1.1 Remediation-Related Data Management
The gravity and impacts of big data may not be transparent
to remediation practitioners yet due to the fact that the mere
concept of environmental big data may still be an abstract or
amorphous concept. Remediation data management is  frag-
mented, and many different kinds of data are managed in
different formats and configurations. In addition, emphasis
was and is always placed on detailed evaluation and analy-
sis of data collected specific to individual sites. Big data rel-
evant to remediation can also be classified into structured and
unstructured data. Examples of structured data are cleanup
standards, performance monitoring, groundwater and soil
chemistry, geologic and hydrogeologic parameters, air quality
measurements, weather conditions, and compliance records.
Good examples of unstructured data are scientific papers, reg-
ulatory changes, site history, U.S. Geological Survey USGS
maps, aerial photographs, spill records, and permit renew-
als. What has been overlooked and ignored in our industry
so far is the vast trove of environmental data and information
related to but beyond the immediate purview of individual
site-specific needs (Table 11.1).
Environmental remediation data usually have multiple
dimensions (contaminant type, time, location, depth, differ-
ent variables, etc.) to be relevant for decisions. As a result,
there is a tremendous amount of data generated that can be
tapped into to develop insights. However, the evolution of
how these data are managed has been slow and unplanned.
Even though we are yet to see the big data revolution enter
the remediation domain, the industry is ready for harnessing
the available data, information, and the acquired knowledge
to be at the heart of gaining predictive insights and smart
decision-making. Important steps in this direction include
benchmarking the data for the remediation industry, develop-
ing standardized reporting standards, mapping the available
data and information, and prioritizing the analytical tools.
Another area to improve is to connect the different meth-
ods used for the collection and storage of environmental data
sets. Older data sets may have relied on pen and paper for
collection and storage. Recently, data sets housed solely in
Microsoft Excel seem to have become antiquated. Currently,
relational databases (e.g., Microsoft Access, EQUIS) are a
common method for storing data and querying focused data
sets. These are complemented by data collection devices, many
times handheld, that are configured to sync flawlessly with the
designed database. Some specialized relational databases are
designed to report certain metrics based on predetermined
big data evaluations. Conversely, many data repositories were
developed to house only the documents in which the data are
reported, such as state regulatory repositories. Several states,
however, have the raw data stored in online databases read-
ily accessible to the public (e.g., GeoTracker in California).
As  big data evaluations become more and more desirable,
storage of the data in its raw form is recognized as being much
more useful.
There are multiple ways to approach evaluation of reme-
diation big data sets. The most straightforward practice in the
past was simple correlation plots between two data types that
may be related (e.g., organic carbon concentration and total
CVOC concentration in ERD systems). If there is a strong
correlation between data sets, a simple linear relationship can
549
550 Remediation Engineering

TABLE 11.1
Existing Publically Available and Relevant Environmental Data Sets
Database
USEPA toxicology testing in
the twenty-first century
USEPA EPA’s toxicity
forecaster (ToxCast)
USEPA Enforcement and
Compliance History Online
USEPA Aggregated
Computational Toxicology
Resource
USEPA Integrated Risk
Information System
EJSCREEN
Global Earth Observation
System of Systems
(GEOSS)
Earth Resources Observation
and Science (EROS) Center
National Wetlands Inventory
(NWI)
National Water Information
System
State site databases
Description Type of Data
Develop better toxicity assessment methods to quickly and efficiently test 10,000 environmental chemicals and
whether certain chemical compounds have the potential to disrupt approved drugs
processes in the human body that may lead to negative health effects.
Toxicity data that can then be evaluated within the ToxCast tool.
Bring together various toxicity data to provide rapid and efficient methods Chemical properties and structure
to prioritize, screen, and evaluate thousands of chemicals. iCSS ToxCast
Dashboard that allows for easy access to related data
Online real-time database of (e.g., CAA, CWA) permits and enforcements/ Facility list; violations list
violations
Online warehouse of all publicly available chemical toxicity data Aggregates data from more than 1,000
public sources on over 500,000
chemicals
Identifying and characterizing the health hazards of chemicals found in the Toxicity values for use in risk
environment assessment (e.g., RfD, RfC, oral slope
factor)
EJSCREEN is an environmental justice mapping and screening tool that 12 environmental indicators (e.g., air
provides EPA with a nationally consistent data set and approach for quality data, proximity to NPL sites)
combining environmental and demographic indicators. A good example of 6 demographic indicators (e.g., percent
the power of integrating data sets in geographical analysis. low income)
12 environmental justice indices
The Group on Environmental Observation is a voluntary partnership of Global environmental data sets,
governments and organizations that created the GEOSS platform for including agriculture, biodiversity,
integration and analysis of global environmental data for study in multiple climate, disasters, ecosystems, energy,
areas of societal benefit. health, water management, and climate
EROS is a remotely sensed data management, systems development, and Remotely sensed, for example, satellite,
research field center for the USGS. data sets
U.S. Fish and Wildlife maintains the NWI to provide public access to Geospatial wetlands data
wetlands mapping and to provide a tool for reporting and predicting trends.
U.S. geological survey maintains this database of surface water and Water resource data including surface
groundwater data for use in managing water resources. water flow and levels, groundwater
levels, water quality, and water use
In some states, contaminated site data and water supply well data are housed Concentration data over time, well
in state databases. Examples are the GeoTracker database of environmental construction data, etc.
data for regulated facilities and the Groundwater Ambient Monitoring and
Assessment Program databases in California.

provide meaningful predictions. More sophisticated evalua-
tion techniques are also available and may include statistical
analyses (e.g., t-test, path analysis, Spearman rank correla-
tions) or data mining. Data mining looks for hidden patterns
in data that can be used to predict future behavior and has
been used extensively in the fields of health care, communi-
cations, insurance, retail, banking, manufacturing, education,
and bioinformatics. Techniques such as clustering, principal
component analysis, decision trees, Bayesian networks, and
neural networks are used in data mining to evaluate rela-
tionships among data sets and most significant variables and
develop models for prediction. If strong relationships are found
between data sets, the correlations and causal relationships
can be identified. This can be very powerful in developing
strategies for future decision-making. A very good example
in remediation is the reduction in operating and maintenance
costs by monitoring only the relevant and required parameters
for enhancing the performance and compliance of remedia-
tion systems.
What makes the emerging field of big data analysis in
remediation interesting is that the inherent value is not always
evident. In addition to compiling and maximizing value from
existing data, evaluators can integrate new data collected from
emerging technologies, industry trends and regulatory, and
other recent developments. Data analysis capabilities in the
remediation arena has been lagging, and a modern approach
for exploiting information from multiple data streams is essen-
tial for us to extract valuable insights. Traditional statistical
techniques were developed when it was time consuming to
analyze large data sets and may fall short of analyzing today’s
big data sets. Remediation industry should begin to embrace
techniques derived from web-based analytics, visualization,
and other computational tools that deliver clear, concise por-
trayals of the insights gained from the data.
Emerging Trends in Environmental Remediation 551

11.1.2 Types of Remediation Big Data
Big data in environmental remediation can come from
many sources and may be related to multiple individual
sites (site level), a group of related sites (portfolio level),
or across unrelated sites (global level). In some cases,
particularly large complex sites, significant amount of
­ sites) can be used to articulate knowledge and insights
data and information may be available collected over
many years (decades) and from hundreds of monitoring
wells that could be considered as a stand-alone big data
set. Figure 11.1a shows the relationship between these dif-
ferent levels of big data. Evaluation of site-level data sets
can provide insights into the relationships between natural
site conditions (e.g., ambient ­geochemistry, hydrogeologic
complexities), engineered systems (e.g., substrate addition),
remedy performance (e.g.,  concentration reductions), and
process troubleshooting (e.g., formation of by-products).
The two examples of big data at the site level are smart
characterization data and automated sensor(s) data, which
are discussed in more detail later. Big data evaluations at
a specific portfolio level (e.g., hundreds of petroleum retail
gained and predict performance and conditions across
an entire portfolio. Looking at data relationships across
­u nrelated sites (e.g., National Priority List (NPL) sites) can
provide insights related to specific industry-wide trends
and practices. A depiction of how global level data sets can
be used to turn data into gaining insights for improving
remediation practices is provided in Table 11.2.

Global level uses

Site Regulatory policy
Site level uses data development
Background determination Improved remediation
CSM development industry solutions
Technology focus
Remedial design
Adaptive management of Portfolio Contaminant focus
operations Site data Industry focus
data Site
Compliance reporting data
Performance evaluation
Closure strategy Global
data

Portfolio level uses

Technical improvements
Site
data
Site Reduction in irrelevant data
data
collection
Financial and regulatory risk
Site management
data Programmatic streamlining
Industry/sector trend
identification
(a)

Traditional data
Big data analysis
analysis

Site specific Site specific Site specific Site specific

Site specific data Data
data 1 data 2 data 3 data 1000
Investigative data (box charts)
Lithology
Hydrogeology Predictive modeling
Contaminant distribution
Geochemistry Big data (correlation and Information
Operational data analysis causation
patterns)
Performance data

Knowledge

Data
analysis
Outcomes (examples)
Outcomes Development of innovative solutions
Remedy design Opening the “black box” of emerging technologies Insights
Management of operations New paradigms of contaminant(s) fate and transport
Compliance reports Regulatory enhancements
Closure strategy

(b)

FIGURE 11.1  (a) Scales of environmental data sets and uses from data analysis. (b) Path of big data analysis in remediation.
552
TABLE 11.2
Examples of Big Data and Big Data Evaluations in Environmental Restoration
Reference(s) Description
Arcadis internal Catalogue measurements
evaluation1 of flame retardants in
indoor dust in peer-
reviewed literature and
evaluate spatial and
temporal variances
Schnobrich Evaluation of 85 ERD
et al.2 projects
Rice et al.3 Early evaluation of data
from 271 sites in
California with leaking
underground storage tank
(LUST) to evaluate
petroleum hydrocarbon
plume length and
stability
Adamson Evaluation of the
et al.4,5 cooccurrence and natural
attenuation of
1,4-dioxane and
chlorinated solvents in
groundwater
Connor et al.6 Review and summary of
13 studies on benzene,
MTBE and/or TBA
plumes
Lahvis et al.7 Evaluation of soil gas data
at sites impacted with
dissolved phase PHCs to
determine vapor intrusion
risk
Microbial An agglomeration of
Insights Inc. results generated by
molecular Microbial Insights and
biology results relevant environmental
database data from project sites
Schnobrich8 Comparative analysis of
multiple sites with active
enhanced reductive
dechlorination to evaluate
the overall rates of
dechlorination and length
of remedial time
observed at the field scale
Type of Data
Concentrations of flame
retardants in dust samples
in a variety of indoor
environments
Groundwater concentrations
of chlorinated solvents,
total organic carbon, pH,
and sulfate
Transcription of California
state file information from
271 sites into electronic
database based on standard
checklist
Groundwater concentrations
of chlorinated solvents and
1,4-dioxane
Compilation of multiple-site
data sets from the United
States containing data from
22 to >4000 sites each on
plume length and stability
Soil–gas measurements at
hundreds of petroleum
UST sites spanning a range
of environmental
conditions, geographic
regions, and a 16-year time
period (1995–2011)
Constituent concentrations,
geochemical data,
molecular data (e.g., qPCR
DNA results)
Groundwater concentrations
of chlorinated solvent, total
organic carbon, nitrate,
sulfate, and pH
Remediation Engineering
Evaluation Approach Outcome
Basic statistics based Scientific study of flame retardants in indoor
on different dust has been increasing rapidly since 2001
environmental with focus on polybrominated diphenyl ethers.
relationships Concentrations of in North American
residential settings appear to be decreasing,
while concentrations of replacement flame
retardant chemicals increase.
Linear regression; Results indicated that the maximum rate of
correlations degradation was independent of total organic
carbon concentration as long as reducing
conditions dominate and TOC remains
~10 mg/L above background.
Statistics and Early work on plume length and stability that
nonparametric supported the eventual establishment of the
graphical displays low threat closure policy for LUST sites in
California in 2012
GIS-based algorithms, Industry-wide paradigm shift in understanding
Wilcoxon rank sum of 1,4-dioxane fate and transport in
test, linear groundwater
regression,
Spearman rank
correlation
Statistical analysis Demonstrated that MTBE, TBA, and benzene
plume lengths are comparable at most sites.
Found consistency among data sets in
different geographic regions and in a variety
of hydrogeologic regimes.
Nonparametric This is an example of big data analysis
Kaplan–Meier informing regulatory policy: USEPA office of
statistics Research and Development recently cited
conclusions from this study, among others, to
provide technical recommendations to the
Office of Underground Storage Tanks for the
development screening criteria to identify
structures that are at risk from petroleum
vapor intrusion (Wilson et al.).
In progress In progress, but could provide predictive values
for a variety of microbial genetic targets
Linear regression; Identified half-lives of various carbon
correlations substrates. Correlated elevated sulfate
(>1000 mg/L), elevated nitrate (>500 mg/L),
and decreased pH (<6 s.u.) with decreased
chlorinated solvent degradation half-lives
(Continued )
Emerging Trends in Environmental Remediation 553

TABLE 11.2 (Continued )

Examples of Big Data and Big Data Evaluations in Environmental Restoration
Reference(s) Description
Arcadis internal Evaluate risk from soil gas
evaluation9 at 91 fuel service stations
with free product
Maguire et al.10 Remediation performance
and rebound of intensive
source depletion
technologies evaluated
where treatment targeted
DNAPL source zones
Type of Data
Soil–gas results for TO-15
Performance data from 59
sites where chemical
oxidation, enhanced
bioremediation, thermal
treatment, or surfactant/
cosolvent flushing were
implemented
Evaluation Approach Outcome
Comparison to Concluded the vapor intrusion pathway does
Michigan regulatory not pose a risk at 90 of the 91 sites. Paradigm
standards shift in ability to close petroleum sites under a
risk-based program in Michigan.
Quantification and Set expectations on achievable percent
comparison of data reduction and permanence of source zone
sets NAPL depletion.

Big environmental data evaluations can provide an intro-
spective look into the remediation “black box” and can remove
the dependence and bias toward specific remedial technologies
and provide the technical knowledge and insights for effec-
tive decision-making. At the portfolio level, it can lead to an
advanced understanding of remediation effectiveness or areas
for remedial optimization and can provide direction for future
efforts within the portfolio. At the global level, these types of
evaluations can lead to a paradigm shift in understanding the
effectiveness and limitations of specific technologies and thus
developing robust technical impracticability guidelines for cer-
tain types of complex sites. Predictive insights gained can also
help in refinement of existing or development of new regulatory
guidelines (e.g., alternate cleanup standards and risk-based reg-
ulations). Figure 11.1b illustrates how analysis of big environ-
mental data sets derived from global sets of site-specific data
could be used to transform data to information to knowledge
and insights. The ultimate question for environmental big data
evaluations is whether we can develop predictive insights from
all existing data sets. At this point in time, the authors feel the
answer is “yes, but not in all cases.”
11.1.2.1  Sustainability (Green Remediation) Data
Environmental sustainability practitioners have their own
big data challenges toward implementing green remediation
within the site restoration framework. The main concern is the
requirement by different stakeholders for different data and
reports under different formats. These stakeholders include
remediation system designers, government agencies, nongov-
ernmental organizations, supply chain partners, regulatory
agencies, and the public. Sustainability evaluations require
the incorporation of large amounts of data from sources
that are currently highly diverse (e.g., energy systems, water
meters, maintenance reports, field surveys, emission reports)
and disparate—hard copies, invoices, paper files, and elec-
tronic documents. At some operating facilities, the required
data reside within different departments such as operations,
maintenance, environmental, and accounting, thus making it
harder to gather in a timely and consistent manner. Yet it is
important for practitioners of green remediation to acquire
these diverse sets of data, standardize all the dynamic for-
mats, and analyze them.
11.1.2.2  Smart Investigation
The conventional approach to viewing and interpreting site
investigations data relies on 2-D data box figures, which were
adequate when characterization data sets only consisted of
a small number of permanent monitoring wells. When only
groundwater data are considered and interpolated, the result-
ing picture provides a distorted view of the mass distribution
in the source zone as well as the entire plume, since ground-
water sampling is inherently biased toward the most perme-
able zones.
However, the recent developments in smart investigations
have the potential for providing a systematic approach that
focuses on developing a 3-D interpretation of the aquifer
architecture through the application of big data (Figure 11.2).
We now recognize that contaminant transport must have a
mass flux–based perspective at all sites, and experience has
repeatedly shown that the majority of the mass flux occurs in
a small portion of the plume cross section within the aquifer.
As such, characterization methods have to integrate multiple
types of data to find the zone where mass flux is occurring.
The use of smart characterization methods, in place of tra-
ditional investigation methods, integrate dynamic, real-time,
high-density soil and groundwater sampling data with hydro-
stratigraphic interpretations and permeability mapping in
three dimensions. Big data concept is the framework behind
smart characterization methods, with thousands of data
points collected rapidly during an investigation. These meth-
ods provide streaming data sets in real-time enabling adaptive
decision-making to reduce investigation costs.
11.1.2.3  Tracer Testing Data
In heterogeneous aquifer systems, simulations and predic-
tions of groundwater flow and contaminant transport require
detailed knowledge of aquifer parameters and their spatial dis-
tribution. Tracer testing is a very efficient and versatile, mul-
tipurpose method to characterize subsurface properties and
to investigate the spreading of both reactive and nonreactive
554 Remediation Engineering

Estimated K TCE
150 ft/day
100 ft/day >100,000 μg/L

30 ft/day 10,000–100,000 μg/L

10 ft/day 1,000–10,000 μg/L

100–1000 μg/L
3 ft/day

10–100 μg/L
1 ft/day

1.0–10 μg/L
0.3 ft/day
<1.0 μg/L
0.1 ft/day

FIGURE 11.2  Real-time smart characterization results at a chlorinated solvent site. The color ramp columns at the left of each sound-
ing depict relative hydraulic conductivity (K) derived from HPT; the color ramp symbols to the right show TCE concentrations measured
through vertical aquifer profile groundwater sampling. Nearly 200 groundwater samples and 400 soil samples were combined with more
than 10,000 HPT estimates of relative K to generate the relative flux map shown in the following.

contaminants in groundwater. This can be achieved at the
whole range of investigative scales, and the testing can be
conducted to collect a whole range of data and information
to determine transport velocity, porosity, subsurface structure
and anisotropy, preferential flow paths, etc.
Tracer tests provide a database that can be applied to
support the design and operation of many remediation tech-
niques. These techniques include all injected reagent-based
remedies, permeable reactive barriers, dynamic ground-
water recirculation (DGR) systems, and pump-and-treat
remedies. While much tracer testing data and information
exist within the area of applied remediation hydrogeology,
recent applications employing novel tracer compounds and
test instrumentation are helping to expand this database by
adding unique data sets in the area of NAPL mobility, natu-
ral attenuation mechanisms, and a few other areas within
remediation.
11.1.2.4  Advent of Sensors
The next frontier in remediation can be harnessing the power
of automated monitoring with sensors designed to continu-
ously collect performance data such as contaminant concen-
trations, geochemistry, or hydraulics. We could extend the
benefits of real-time decision-making from smart character-
ization to performance monitoring. Imagine the possibilities
as we harness the power of a broader range of microsensors
capable of transmitting data on contaminant concentrations
and reagent distribution during in situ remediation. Or what
if we were able to track targeted microbial populations and
growth rates without the time-consuming specialized labo-
ratory analyses? Streaming technology can take the concept
of investigation and performance data collection and evalua-
tion to new dimensions by developing instrumentation from
the macro level down to the micro level. Today’s sensors are
powerful and inexpensive, network access to remote data is
increasing, scientific models are improving, and “big data”
algorithms for crunching data are also improving.
11.1.3 Opportunities for Gaining
Insightful Knowledge
11.1.3.1  Stratigraphic Flux
Smart investigation methods, relying on the fusion of mul-
tiple data sets, can link classical geological methods of inter-
pretation with a classification framework that describes the
3-D aquifer architecture in terms of contaminant transport
Emerging Trends in Environmental Remediation 555

potential. The advantage of this approach is that it builds on
sequence stratigraphy methods and provides insights regard-
ing how permeability distributions within elements of the
aquifer architecture control contaminant transport, cleanup
time frames, and realistic end points. This process is differ-
ent than the conventional stratigraphy approach by the fact
that the impacted aquifer system can be classified by the rela-
tive flux within the different segments. This stratigraphic flux
approach can also be used to develop quantitative metrics to
rank and prioritize remediation efforts.
The thousands of individual measurements, collected dur-
ing smart investigations, quickly overwhelm any traditional
approach to data evaluation. This means that specialized soft-
ware must be applied to allow 3-D viewing by fusing together
thousands of measurements from high-resolution borings
(Figure 11.3). Data fusion is needed because the high-density
data collected must be organized into the stratigraphic flux
framework, where permeability and concentration data are
combined to provide an indication of mass flux. Past meth-
ods of interpolation that ignore the permeability structure will
interpolate mass into storage zones even though the mass is
present almost exclusively in transport zones. These limita-
tions are overcome using data fusion and interpreting ground-
water, whole-core saturated soil, and permeability data
simultaneously. In the source zone, the approach will correctly
identify mass present in the slow advection and storage zones,
as well as the architecture of the zones. In the downgradient
segments of the plume, the data fusion approach will correctly
identify the permeable mass flux zones where all of the con-
taminant mass is present.
11.1.3.2  Developing and Validating Benchmarks
Benchmarking within the context of remediation prac-
tices can be interpreted as improving the performance of
technologies by continuously identifying, understanding,
and adapting new information and knowledge for devel-
oping best practices and processes. Many times, big data
evaluation can provide the benchmarks but more impor-
tantly can validate the benchmarks on a continuous basis.
For example, after the development of molecular targets
to quantify the subsurface population of Dehalococcoides
(DHC) microbial species, project teams started collecting
environmental samples at individual sites. In the case of
DHC, it will be worthwhile to conduct a big data analy-
sis to correlate these population counts to dechlorination
performance across hundreds of sites. The insights gained
would either validate or refute the suggested benchmark
derived from bench-scale studies. The commonly accepted
benchmark of 1 × 107 cells/L for a healthy microbial popu-
lation of DHC capable of complete dechlorination came
from academic research.11 It will be a worthwhile effort to
refine and reinforce this benchmark over time by evaluation
of big data from multiple sites with successful enhanced
reductive dechlorination (ERD) systems.

TCE relative flux (unitless)

>3,000,000

1,000,000

300,000

Estimated K TCVOCs
150 ft/day
100 ft/day >100,000 µg/L

30 ft/day 10,000–100,000 µg/L

10 ft/day 1,000–10,000 µg/L

100–1000 µg/L
3 ft/day

10–100 µg/L
1 ft/day

1.0–10 µg/L
0.3 ft/day
<1.0 µg/L
0.1 ft/day

FIGURE 11.3  Relative flux results based on the product of relative hydraulic conductivity and trichloroethene groundwater concentra-
tions. The color ramp shaded areas on the flux transects highlight >90% of the relative flux at the site.
556
Another example of benchmarking is from the insights
gained from analysis of performance data from more than
100 ERD sites.2,8 The authors performed a big data evalua-
tion of these ERD systems by evaluating chlorinated solvent
concentrations, total organic carbon, pH, and sulfate concen-
trations to quantify the half-lives of chlorinated solvents and
assess what factors affect the first-order decay rate. The rate
of chlorinated solvent degradation did not exhibit a linear
relationship with total organic carbon concentration; how-
ever, a threshold of 10 mg/L above background was related
to enhanced dechlorination rates. This led to refined designs
of target organic carbon concentrations for hundreds of future
projects resulting in cost savings, enhanced performance, and
faster cleanups.
Another ongoing effort within the remediation industry
that has great potential for developing benchmarks, but is
not yet there, is the growing database housed by Microbial
Insights. Microbial Insights is an environmental molecular
analysis company, and they have developed numerous molec-
ular targets to help practitioners understand the subsurface
microbiological population and their propensity toward bio-
remediation of soil and groundwater constituents of concern.
Recently, they started housing their results in a relational
database and asking practitioners to help provide additional
site data (e.g., constituent concentrations, geochemistry, and
performance data). With these data sets together, they may
be able to identify relevant benchmarks (similar to the DHC
example given earlier). This would allow practitioners to
apply future microbial results more directly in development
of site conceptual models and remedial technology screen-
ing. The challenge will be gathering the appropriate raw data,
at the required level of quality, from practitioners across the
industry on a continuing basis.
11.1.3.3  Natural Attenuation of 1,4-Dioxane
Our experience with natural attenuation of 1,4-dioxane pro-
vides a great example of how big data analytics can provide
insights and paradigm shifting perspectives on remediation of
emerging contaminants. Until recently, conventional wisdom
has been that 1,4-dioxane is not subject to the biodegradation
mechanisms of natural attenuation. But as we analyze more
and more data from dozens of sites, it is obvious that stable, if
not receding, 1,4-dioxane plumes are identified in our portfo-
lio of sites. With the advent of the microbial toolkit approach,
we can begin to connect the mechanisms of 1,4-dioxane atten-
uation to the presence of appropriate substrates that stimulate
1,4-dioxane biodegradation and the abundance and activity of
various genes encoding monooxygenase enzymes responsible
for such biodegradation. However, there are still challenges in
understanding why 1,4-dioxane attenuation appears to occur
at some sites but not others and which substrate(s) and mono-
oxygenase enzyme(s) are driving 1,4-dioxane biodegradation.
At many sites where 1,4-dioxane attenuation is apparent, the
mechanisms remain unclear. For instance, at some sites where
attenuation is apparent, 1,4-dioxane biodegradation potential
has not been demonstrated with microbial genetic evidence. It
may be that the particular monooxygenase enzymes capable of
Remediation Engineering
1,4-dioxane biodegradation under site-specific environmental
conditions have not yet been characterized or the appropri-
ate genetic targets have not been established. An analysis for
elucidating correlational and causational trends using the big
data gathered from the hundreds of 1,4-dioxane sites, across
the country, will provide the answers. Digging deeper into the
active microbial communities at many sites will lead us to
identify which monooxygenase enzymes are responsible and
how they can be enabled by engineered systems, allowing
more 1,4-dioxane sites to be cost-effectively managed with
natural and enhanced attenuation approaches.
11.1.3.4  LNAPL Management
How we view and manage sites with LNAPL has changed
recently and we no longer rely purely on LNAPL thicknesses
to assess how impacted the site is or how remediation is
progressing. Gone are the days (or at least they should be)
where we prepare LNAPL thickness contour plots and thick-
ness trend graphs. The evolution of industry knowledge and
insights on the topic has resulted in a change from a singu-
lar focus on the thickness of LNAPL in wells as a remedial
end point to evaluating the risk associated with the LNAPL,
the mobility and recoverability of the LNAPL, and the rate at
which the LNAPL is being naturally depleted. This shift was
possible due to the big data analysis performed on LNAPL
behavior from data collected from thousands petroleum sites
under different geologic and climatic conditions across the
country and the insights gained from that analysis.
The most important insight gained from the big data analy-
sis is that the mass removed by natural source zone deple-
tion (NSZD) is far greater than the mass recoverable by any
of the most efficient removal technologies. It is also apparent
that the rate of LNAPL depletion in the subsurface has been
greatly underestimated. The conventional wisdom was that
LNAPLs did not degrade, partly because it was thought that
the LNAPL conditions impeded degradation. Big data analy-
sis was used to evaluate the amount of carbon dioxide (CO2)
generated to establish a quantitative link with mass depleted.
In addition, the dominant microbial processes were exother-
mic and that the signature could be measured reliably with
simple temperature sensors (Figure 11.4). What was thought
to be anomalous temperature readings at multiple LNAPL
sites was actually translated to a game changing predictive
insight. As a result of big data fusion and advances in sen-
sor technology, we can envision being able to quantify NSZD
rates not just once or twice through CO2 monitoring but con-
tinuously through data logging. With refinement, we will be
able to understand temporal variability of the NSZD process,
improving the reliability NSZD rate estimates, and then make
better decisions about whether to manage the LNAPL or
remediate it.
While NSZD is receiving widespread acceptance in con-
cept, fully translating these concepts into regulatory policy
has been slow. Accumulating a big data set of LNAPL deple-
tion rates and performing a correlation analysis with mea-
sured NSZD indicator parameters (CO2 flux and subsurface
temperature increase) are crucial for the next step. Developing
Emerging Trends in Environmental Remediation
Temperature
ΔT
LNPL SMEAR zone
Depth
Background
temperature
Temperature where
LNAPL is present
FIGURE 11.4 Conceptual model of subsurface temperature
increase within the LNAPL zone. The temperature profile data are
cost-effective to collect at high resolution and over time. Current
initiatives are ongoing to develop reliable methods that convert the
temperature signal into a rate of petroleum depletion via calcula-
tion of the biogenic heat generated during hydrocarbon degradation
and assessment of thermodynamic heat flux from zones in which
LNAPL and soil gas methane are observed.
an established methodology, from the insights gained, to
quantify the NSZD rates for the regulatory community will
increase the strength of these arguments and inclusion as an
acceptable solution in lieu of active remediation.
11.1.3.5  Realistic Values of Porosities
We recognized early on that conventional hydrogeologic
approaches to designing in situ remediation systems, particu-
larly those relying on reagent injections, were not reliable. We
came to this understanding through a review of many in situ
chemical oxidation (ISCO) and ERD projects and through
performance monitoring and optimization of systems. For
a long time, practitioners relied on design assumptions that
incorporated the concept of effective porosity, often assumed
to be 20%, and transport based on the advection–dispersion
equation. The industry was also faced with reagent vendors
claiming that 5 gallons of reagent per foot of injection well
would lead to widespread reagent distribution and enable
injection well spacings in excess of 50 ft. Many early in situ
remedy designs applied this high-concentration, low-volume
injection strategy with less than satisfactory results. Often, we
would see little indication of the injected reagent or resulting
degradation reactions in downgradient performance monitor-
ing wells in addition to other adverse impacts.
To understand the disparity between early assumptions and
observed field results, a global data review of performance data
557
from dozens of sites was compared to the results using first
principles on hydraulics and contaminant transport. Based on
this analysis, we recognized that injection tracer testing was
essential to actually measure the volume–radius relationship
between injected reagents and radius of influence and then
determining what degree of postinjection expansion could
reliably be obtained during the drift phase. We would also
monitor tracer concentrations at wells downgradient to verify
flow direction and transport velocity, based on breakthrough
curve analysis. The flow within the permeable zones of the
aquifer led to observations that was consistent with transport
zone porosity of 5%–10% at most; many sites exhibited trans-
port zone porosities that were less than 5% (Figure 11.5).12
These insights gained from tracer testing data from hundreds
of sites were documented, and the term effective porosity was
dropped because of the tendency by many to assume that 20%
was realistic. Instead, we adopted the term mobile porosity,
owing to the fact that majority of the transport occurs in a small
segment of the aquifer. Through tracer testing, we have devel-
oped a new paradigm on in situ remediation via injection. The
basic premise is that injection-based remedies are controlled
by the permeability distribution within the hydrostratigraphy.
At the scale of injection, the majority of the reagent migrates
in a very small percentage of the aquifer, which is typically
5%–10% (Figure 11.5). This decrease in transport zone poros-
ity leads to several important insights for contaminant trans-
port and remediation design. Since the majority of flow occurs
in only the mobile pore space, groundwater flows at much
higher velocity than expected. This phenomenon also implies
that the initial benefits of remedial actions may be observed
downgradient faster than expected and injected remediation
reagents will be distributed greater distances than expected.
The immobile porosity, acts as a storage zone and molecular
diffusion, causes solutes to move into and out of these zones at
rates that have an impact on remediation timescales.
11.1.3.6  Large Plume Management
Remediation of large plume sites, meaning sites for which the
scale of the plume is measured in miles and time frames are
measured in decades, can in themselves generate “big data.”
At these scales, monitoring wells can number in the hun-
dreds, annual analytical data can number in the thousands (for
decades), and real-time operational data is constantly gener-
ated. In most cases, these data sets are incorporated into quar-
terly and annual reports in an unstructured manner and lying
dormant in bookshelves or file cabinets. Even though these
data come from an individual site, it really is “big remediation
data” with a potential of giving valuable insights toward cost-
effective remediation of these large plumes.
An important perspective developed at the Reese Air Force
Base (AFB) site through “big data” analysis helped us to drasti-
cally cut back on pumping rates, look at the plume in segments
and combine remedies, and identify the mass flux to clean up
the site within the stipulated 10 years. Figure 11.6a and b pres-
ent the contrast in the understanding of plume configuration,
dimensions, and flow direction after this analysis was com-
pleted. This example clearly indicates that big data sets may be
558 Remediation Engineering

25

20

Frequency (%)
15

10

Greater than 0.30

Less than 0.03

0.03–0.06

0.06–0.09

0.09–0.12

0.12–0.15

0.15–0.18

0.18–0.21

0.21–0.24

0.24–0.27

0.27–0.30
Measured mobile porosity θm

FIGURE 11.5  Frequency distribution of measured mobile porosity (θm) values from tracer tests completed at dozens of different sites
across the United States.

embedded within large, complex, and long duration remedia-
tion sites and a detailed analysis may provide valuable insights.
Effective management of large plume remediation proj-
ects requires real-time data analysis to identify what to focus
on for remediation and to implement informed decisive and
adaptive operations. Figure 11.7 is an example of the ongo-
ing data generation from one such large plume site, where
groundwater monitoring and operational data generated from
12 different remedial systems, including large-scale in  situ
reactive treatment, recirculation systems, groundwater extrac-
tion, and agricultural treatment systems for the remediation
of hexavalent chromium in groundwater. The example in
Figure 11.7 represents a small fraction of the data that is col-
lected at this site, which is on the scale of approximately 1
mile by 2 mile area and includes operation of more than 180
remediation wells and data collection from more than 700
monitoring wells. The data sets generated are evaluated on
a monthly to quarterly frequency to adapt the remedy, guid-
ing which injections and extraction wells to turn on and off,
changes to r­emedial well flow rates, and changes to organic
carbon injection rates. Advanced data management and ana-
lytical techniques could greatly improve the ability to quickly

Legend
TCE contour (1 µg/L)
TCE contour (10 µg/L)
TCE contour (100 µg/L)

2000 ft
(a)

FIGURE 11.6  (a) Assumed configuration and dimensions of the groundwater plume at Reese Air Force Base site in 2005. (Continued)
Emerging Trends in Environmental Remediation 559

(b)

FIGURE 11.6 (Continued )  (b) Known configuration and dimensions of the same plume in 2006 after the big data analysis. The blue line
shows the focused mass flux within the highly permeable zones.

Operational data Analytical data

Monitoring wells 600 ft

Water level Flowrate Remedial wells Hexavalent chromium Nitrate

FIGURE 11.7  A small subset of operational and analytical data collected and evaluated to make informed operational decisions at a large
plume site in southern California.

assimilate and analyze large accumulating “big data” at large
plume sites, providing insights to more efficiently manage
remediation and reduce overall remedial time frames.
11.1.4 The Future
A robust debate is ensuing over whether big data will or should
result in a decision-making paradigm shift that emphasizes
correlation identification over causation analysis. It can be
argued that correlation is an adequate basis for action in many
situations because correlations can be found much faster and
cheaper than causation. Many also think that for most every-
day needs, knowing what and not why is good enough.
The pairing of high-resolution, fast-paced collection of big
data during smart investigations with augmented reality and
virtual reality technologies will enable all remediation stake-
holders to have a better vision of the conceptual site model
(CSM) and the progress of remediation. Augmented reality
technology would allow clients to walk the actual site with
a tablet in hand and visualize the subsurface conditions and
plume configuration based on their current location. Virtual
reality technology would allow all stakeholders to take a site
walk from anywhere in the world.
We now have the opportunity to replace the old model of
data collection systems with a network and array of sensors
and continuous feedback loops. For example, now we realize
that finding the flux through smart characterization enables
one to tailor the remedies along the plume trajectory and opti-
mize the technologies based on plume maturity. By focusing
on collecting the right data during the remedy implementation,
we can optimize the performance of the system to account
for the emerging behaviors that we see develop that were not
obvious based on the CSM before remediation commenced.
By operating the system dynamically, one can systematically
learn about the remedy performance by responding to a posi-
tive or negative feedback loop and continuously calibrate the
560
CSM. As we improve our approach to individual sites, there
is an opportunity to learn from hundreds of sites by analyzing
the big data and developing impactful insights on optimizing
the configuration and operation of remediation systems. This
could lead to the development of expert systems that could
break down the barriers of specialized knowledge and pro-
vide decision support to practitioners at multiple levels.
The concept of data fusion provides the foundation for
making the most of big data and it is more than statistical
evaluations and they sometimes elucidate relationships that
were not apparent. Data fusion requires an understanding
of the underlying information contained in the data, so that
one can combine different data sets to identify key relation-
ships that lead to game changing insights of the process or
concept of interest. The aim may be to go beyond the cor-
relation between data sets and identify the cause and effect
relationship. Sometimes breakthroughs are obtained by start-
ing at first principles and challenging conventional wisdom.
Sometimes, aggregating big data enables one to see beyond
the limitations that small data sets provide. Environmental
remediation successes are inherently site specific, but under-
standing the key drivers that affect implementation of vari-
ous technologies or behavior of contaminants or developing a
strategy that will enable optimization of multiple technologies
requires a big data perspective.
11.2 LARGE CONTAMINATED GROUNDWATER
PLUMES CAN BE CLEANED UP
Large contaminated groundwater plumes were viewed within
the remediation industry very similar to how health-care prac-
titioners looked upon a chronic disease within the health-care
industry. The emphasis was always on treating and managing
the symptoms since the assumption was finding a cure that was
difficult and very expensive. However, in the recent past, fun-
damental paradigm shifts have taken place in the understand-
ing of contaminant fate and transport, and many remediation
practitioners have started to believe that large plumes can be
cleaned up within a reasonable time frame and costs.13 The
contrast between the old thinking and the new thinking with
respect to the cleanup of large plumes is shown below.
Old Thinking
Large plumes cleanup is impracticable and thus the only solution is to
contain and manage them.
Focus is always on containment.
Back diffusion is difficult to overcome and results in cleanup time frames
of 30 to more than 100 years.
Modeling is used for decision-making.
New Thinking
Large plumes can be cleaned up within reasonable time frames and
cost-effectively.
Focus on the mass flux and remove the mass that moves.
Back diffusion can be overcome. The term “back diffusion” may be an
over simplification of very, very slow advection.
Data drive decisions.
Remediation Engineering
The term “large plume” obviously highlights scale as being
the critically defining attribute; however, it is worth identify-
ing other attributes that are equally important for defining a
large plume.
• Physical scale: Large dissolved plume footprints can
be several thousand feet long (half a mile or longer)
and hundreds of feet wide (Figure 11.8). In some
instances, the impacted aquifer thickness may be
hundreds of feet or more.
• Advective scale (time): The natural advection of
­contaminants from the source area to the leading
edge of the plume is several decades or longer.
• Cost scale: The projected cost to clean up is tens of
millions of dollars or more.
• Multiple technologies: Multiple remediation tech-
nologies may be required, in both space and time.
• Complexity: There may be multiple contaminant
sources with different locations, constituents, and
release times also involving multiple stakeholders.
Large plumes cover a wide range of contaminated aquifer
s­ cenarios, but they all share four common characteristics:
1. Large plumes occur in productive aquifers with
high rates of groundwater flow and the potential
to transport dissolved contaminants over large
distances.
2. Large plumes comprise compounds that are not
degraded chemically or biologically under natural
aquifer conditions.
3. Large plumes occur when contaminant compounds
do not interact chemically with the aquifer matrix—
either the aquifer matrix has limited sorptive capac-
ity or the contaminant cannot be sorbed due to its
molecular structure.
4. For most contaminants, there must be a large source
mass to generate a large volume of groundwater that
exceeds regulatory criteria.
Many of the large plumes under treatment today were dis-
covered more than 25 years ago. And more large plumes are
being added to the national inventory every year as new risk-
bearing compounds are recognized. During the past 15 years,
there has been steady progress moving smaller plume sites to
closure, through improved technology and increasingly risk-
based regulatory standards. Over that same time, there has
been little progress for large plumes and the total inventory
appears to be increasing due to the recognition of emerging
contaminants.
11.2.1 Introduction
The remediation industry, now three decades old, continues to
evolve. This is driven by many factors: technological develop-
ments, a need to address emerging contaminants, regulatory
changes, economic factors, and sustainability considerations.
These have created both challenges and opportunities at
Emerging Trends in Environmental Remediation 561

Legend LTM year 4 (2012–2013)

Monitoring well RDX groundwater plume
Extraction well 2–9 μg/L 100–499 μg/L
Operational unit boundary 10–49 μg/L 500–999 μg/L
MAAP boundary 50–99 μg/L 1000–3999 μg/L
Line or area
Drainage ditch
LTM year 3 (2011–2012)
RDX concentrations
Inferred RDX isopleth 0 0.25 0.5 1
Miles
Aerial source: ESRI world imagery service
accessed via ArcGIS 10 on 3/13/2012 Graphic scale

FIGURE 11.8  Good example of a large plume. RDX plume at the Milan Army Ammunition Plant, Tennessee.

different stages of the industry’s evolution. Although many
things have changed with time, one of the most difficult prac-
tical challenges remains—namely, how to deal with large
contaminated groundwater plumes. Presumptive thinking in
the past emphasized containment and management of these
large plumes rather than focusing on mass removal and site
closures.
There are some major differences in how we approach the
design and implementation of large plume remediation sys-
tems in comparison to the common practices of remediation
system design. The sheer magnitude and scale driven com-
plexities associated with large plumes cause logistical and cost
challenges for designing a full-scale remediation system from
a small-scale field design test. For example, overdesigning a
full-scale system is often recommended to ensure a robust
remediation system, but the economic and logistical implica-
tions at large scale are greatly magnified and can render the
approach impracticable. Adaptive operation and optimiza-
tion based on real-time performance data are necessary for
large-scale systems, whereas they are not widespread practice
at the smaller scale.
Beyond the system scale-up challenges, these plumes
are large enough for a single large plume to be impacted by
paleochannels, changes in depositional environments, discon-
tinuous confining units, faults, sinkholes, ephemeral streams,
wetlands, springs, and surrounding supply wells. Thus, simple
conceptualizations of dissolved plume behavior often do not
describe the behavior of large plumes. Thus, the increased
complexity requires the development of CSMs at multiple
scales to adequately understand plume conditions, resulting
in unique design considerations for specific portions of the
plume that in many cases may require multiple technologies.
11.2.2 Back Diffusion Can Be Overcome
The field of remediation hydrogeology has experienced
a renaissance over the last few years as practitioners and
researchers have reexamined solute transport processes
562
within the context of groundwater remediation, particularly
restoration of large groundwater plumes. This reevaluation
of long-established theoretical concepts, supported by sig-
nificant amounts of field data, tracer studies, and more pre-
cise field investigation techniques, has increased the overall
understanding of contaminant fate and transport and plume
evolution. A new framework has emerged with the recognition
that plume development and transport are mostly influenced
by advection and diffusion rather than advection and disper-
sion.12,13 The emergence of diffusion as a critical process was
a radical concept for most practitioners as the majority of rele-
vant textbooks and peer-reviewed publications always empha-
sized dispersion as a significant contributor to the behavior of
contaminant plumes while stressing the insignificance of dif-
fusion.14–16 Increased understanding of advection–diffusion
effects has also driven a shift in the design and implementa-
tion of remediation systems, particularly the ones employing
in  situ technologies. Design strategies for reagent delivery,
well spacing, and estimation of reagent volumes have changed
in comparison to the past design approaches. The advection–
diffusion theory has also breathed new life into how we rely
on pump-and-treat systems for groundwater restoration, par-
ticularly in large plume cleanup where diffusive mass flux is
increasingly important with scale. However, the importance
of diffusion has also been used by most practitioners as evi-
dence for the claims as to why we cannot remediate contami-
nated groundwater plumes to low cleanup standards. Reliance
on the concept of back diffusion has now become the common
basis for the claims as to why it is impossible to reach the low
maximum contaminant levels (MCLs).
In spite of this pervasive pessimism, there is sufficient
amount of evidence and observations counter to this belief,
where diffusion has been shown to be a mechanism to rely upon
for achieving successful restoration of groundwater plumes. We
explore the importance of diffusion and introduce the concept
of dual-directional diffusion with an understanding of the large-
scale impacts of small-scale processes. The framework for this
evaluation centers around trying to answer the following ques-
tions: How should we conceptualize diffusion at the site scale?
When does diffusion limit reaching remediation end points?
Are there aquifer structures where diffusion helps? How can we
assess the effects of diffusion? Is the concept of back diffusion
an over simplification of very, very slow advection?
The significance of diffusion processes is becoming
increasingly clear in evaluating long-term monitoring data
for sites undergoing active remediation. Over the history of
the remediation industry, the reduction of contaminants to
less than MCLs has been “the metric” for success, usually
enabling sites to be declared “closed.” Today, even those
aggressive metrics are being challenged in some jurisdictions
with acceptable levels being lowered to be less than risk-based
goals and in a few instances to less than quantification limits
before project complete can be declared. We would suggest
that recent insights into aquifer structure and its influence on
contaminant transport will enable us to sometime meet these
aggressive goals and, more importantly, enable us to under-
stand when those end points are not possible.
Remediation Engineering
Much of the perspectives presented here does not differ
from current discussions within the industry. Flux-focused
remedies for large plumes centered on achieving orders of
magnitude declines provide value and improve environmental
quality. Where achieving the MCLs is a necessity, we offer
that dual-directional diffusion represents a viable assimilation
process and represents a paradigm shift in site remediation.
An improved understanding of the magnitude of diffusion
relative to the assimilative capacity of the aquifer needs to
be further explored. We currently do not have the technology
necessary or the monitoring tools that we need, but we can
speculate that this dual-directional diffusion process exists
and contributes to plume attenuation based on an understand-
ing of the conceptual treatment mechanisms and evidence
from the field.
11.2.3 Importance of Combined Remedies
for Cleaning Up a Large Plume
In this section, we explore the site conditions and restoration
process that resulted in cleanup of the Reese AFB plume to
successfully achieve MCLs in less than 8 years. At the scale
of the Reese plume’s footprint, an approach focusing on mass
flux hinged on adaptive operation and optimization using
real-time performance data. This strategy required treatment
system components that could be relocated or augmented to
adjust treatment configurations and drive the overall rate of
cleanup—in contrast with the “fixed” operational configura-
tion typically employed to control plumes of this magnitude.
The experience and the knowledge gained at Reese are now
being transferred to solve similar challenges on many other
large, complex plumes across the United States where the
conditions are right and are being built upon to further refine
and push the boundaries of what is possible.
An honest refinement of the CSM, unburdened by alle-
giance to historic precedent, was integral to the success of
the Reese project. Thirty years ago, the concept of a CSM had
much narrower definition and was grounded in the belief that
complex systems could be adequately represented by simple
equivalents. Today, CSMs are significantly more detailed as
a result of greater resolution from advanced characterization
techniques, improved knowledge of source mass behavior,
and the ability of modeling techniques to simulate the effect
of fine-scale processes on contaminant fate and transport.
Therefore, while CSMs remain a “streamlined” understand-
ing of site conditions, modern CSMs incorporate far more
information than their forebears to ensure that they are truly
representative of the complex site conditions.
Selection of a combined remedy approach was integral
to the success at this site by providing flexible framework to
meet the contractual objective to clean up the entire plume in
less than 10 years. This was a critical element of the revised
strategy, given that the 700 acre footprint of the plume made
it necessary to restore an average of 2–3 acres of aquifer per
week. The individual components of the revised remedy were
directly tied to the CSMs of the sequential plume segments and
different approaches to address source mass and diffuse plume
Emerging Trends in Environmental Remediation 563

200
Traditional Legend Traditional
180 A
P&T A: Invasion P&T projection
B: Washout
160 C: Back diffusion
D: Late term
140
Concentration (μg/L)
B DGR
120

100

80 C

60

40
D
20
Compliance

1995 1997 1999 2001 2003 2005 2007 2009 2011 2013
Date

FIGURE 11.9  Data from a monitoring well within a large plume undergoing active remediation.

areas. Recognition of the complex structure of the plume and
the need to complement the modified pump-and-treat system
necessitated the implementation of different approaches within
each subarea of the plume. The two primary remedial technol-
ogies used at the site were directed groundwater recirculation
(DGR) and engineered reductive dechlorination (ERD).
The most important design innovation that drove the suc-
cess of the Reese AFB project was the reliance on DGR to
overwhelm aquifer heterogeneities and overcome the impacts
of matrix controlled back diffusion through enhanced ground-
water flushing (Figure 11.9). Faster cleanup rates (2–3 acres/
week) were achieved by creating the conditions to accelerate
contaminant mass flushing by strategically moving more pore
volumes of water.17 This was achieved by manipulating the
water levels to create vertical gradients across less permeable
zones and establish flow through zones where contaminant
mass was stored. The combined result of the two concepts
mentioned earlier is the enhancement of advective contami-
nant transport that occurs through the mobile fraction of the
aquifer, while also increasing mass recovery from storage
zones through advection and diffusion. This awareness led to
the most important component of the Reese plume remedy,
which included a dynamic treatment approach reliant on rou-
tine monitoring data to continually focus groundwater extrac-
tion from wells containing the most mass. In addition, well
design specifications included the placement of extraction
and injection well screen intervals across multiple fine- and
coarse-grained stratigraphic layers to overwhelm the natural
heterogeneity of the aquifer and ensure contaminant removal.
11.2.4 Unique Success
saved U.S. taxpayers at least $30M, and looking back on the
success, there are a few clear takeaways:
• Honest challenging of the conceptual model allowed
an initial breakthrough with the configuration of
the  existing remedy, cutting operational flow rates
(and costs) needed to achieve containment while
increasing the rate of contaminant mass recovery.
• The application of DGR was extremely successful,
likely due to removal of contaminant mass sequestered
in fine-grained aquifer materials by dual-­directional
diffusion, driven by the strategic recirculation of clean
water. While the different components of the com-
bined remedy were a success as well, it likely would
have been possible and more cost-effective to rely on
DGR to clean up the entire plume.
• The adaptive operation and frequent modification
of the remedy configuration (including the installa-
tion of new infrastructure) optimized concentration
gradients on a regular basis to drive flushing of the
contaminant mass from the aquifer.
The methods used to clean up the aquifer under Reese AFB
are being replicated in numerous places with tremendous
results. While this will not be true for every site with a large
or complex contaminant plume in groundwater (the site condi-
tions must be conducive), we are clearly able to achieve what
was unthinkable just a decade ago (Figure 11.10). This shows
that the recent advancements being made in investigation and
remediation techniques are supporting the real possibility of
large-scale restoration, in a world where clean groundwater is
one of our most important natural resources.

The scale of the groundwater restoration achieved at Reese

AFB, to support unrestricted use of an aquifer formerly con-
taminated with trichloroethene (TCE) over a 3 mile long
footprint, is unprecedented (Figure 11.10). The site cleanup
also made good fiscal sense. It was estimated the cleanup has
11.3  MANAGING EMERGING CONTAMINANTS
The list of emerging contaminants will remain a moving tar-
get as new chemical compounds are continuously being pro-
duced and science continuously improves its understanding of
564
FIGURE 11.10  This figure presents the unique success achieved at the Reese Air Force Base site in Lubbock, TX, in cleaning up a 3 mile
long large plume contaminated with trichloroethene.
current and past contaminants. In reality, emerging contam-
inants have now become a fashionable and trendy research
area. However, we also have to realize that emerging contami-
nants and emerging issues about environmental contamina-
tion have been around without our knowledge for millennia
and we can hope that as the scientific knowledge advances, we
can manage these contaminants better and reasonable regula-
tions will be in place.
The EPA has defined an emerging contaminant as a chemi-
cal or material characterized by a perceived, potential, or real
threat to human health or the environment or by a lack of pub-
lished health standards. A contaminant also may be emerging
because of the discovery of a new source or a new pathway
to humans. Some states are also developing their own lists of
emerging contaminants.
11.3.1 Background
Toxic Substances Control Act inventory contains about 84,000
contaminants registered for commercial use. Only 2400
of those are high production volume chemicals (more than
1 ­million pounds/year) that require detailed toxicological
testing.18 The Safe Drinking Water Act Amendments (1996)
required the United States Environmental Protection Agency
(USEPA) to publish a contaminant candidate list (CCL) every
5 years to identify potential substances for future regulation.19
Monitoring data are collected from drinking water utilities to
Remediation Engineering
determine whether a contaminant is detected at a frequency
and in concentrations to warrant further analysis and research
on potential health effects and possible regulation. From the
CCL, a minimum of five candidates must be selected to be
considered for regulation within a 5-year period. The first CCL
(CCL1) was published in March, 1998, and contained 50 chem-
ical and 10 microbial contaminants and included compounds
like perchlorate, MTBE, and RDX. The second list (CCL2) was
published in February, 2005, and the third (CCL3) in 2008.20
A few new analytical methods have been developed over
the last few years by the USEPA. Most of these are directed
toward the measurement of CCL chemicals and drinking water
under the unregulated contaminants monitoring rule (UCMR).
USEPA and other researchers are convinced that chemicals that
are not normally sampled or treated are able to pass through
treatment systems, and unregulated disposal methods may
have documented impacts on surface water and groundwater
systems in the future. While all the stakeholders are still not
in agreement of an exact list, there will be plenty of candidate
compounds to be on the list. Examples of emerging contami-
nants currently in the spotlight and under scrutiny are cyclic
ethers (e.g., 1,4-dioxane, tetrahydrofuran), 1,2,3-trichloropro-
pane (1,2,3-TCP), pesticides, chromium (VI), endocrine dis-
rupting compounds (EDCs), perfluorinated compounds (PFCs),
polybrominated diphenyl ether (PBDE), perchlorate, fuel oxy-
genates (e.g., MTBE, TBA, ethanol), energetics, dechlorina-
tion/disinfection by-products, and nitrosamines (e.g., NDMA).
Emerging Trends in Environmental Remediation
In February 2015, the USEPA published the draft CCL-4,
the new drinking water priority contaminant list for regula-
tory decision-making and information collection. The con-
taminants listed either occur or are anticipated to occur in
drinking water systems and will be considered for poten-
tial regulation. The draft CCL-4 contains 100 chemicals or
chemical groups and 12 microbial contaminants.21 Many of
the chemicals and all of the pathogens on this list are the same
as what was previously on the CCL-3. Notable changes to the
list were the removal of perchlorate and strontium that are
scheduled for regulation.
The compound 1,4-dioxane gained its notoriety due to its
industrial use as a stabilizer in 1,1,1-trichloroethane. It is now
understood that 1,4-dioxane is considerably more widespread
due to its use in personal care products and detergents, vari-
ous chemicals, electronics, fibers, and pharmaceuticals. Data
from the EPA’s unregulated contaminant monitoring rule
(UCMR3) published in June 2015 indicate that 1,4-dioxane
has been detected in 6.7% of public water supplies at con-
centrations above the drinking water health advisory level of
0.35 µg/L.21 Figure 11.11 illustrates the geographic distribu-
tion of 1,4-dioxane in public water supplies above the health
advisory level. 1,4-Dioxane is a cyclic ether that is not only
miscible in water but forms a positive azeotrope. 1,4-Dioxane
has a very low octanol water partitioning coefficient (log Kow
of −0.27) and Henry’s constant (5 × 10 −6), making it prone to
migrate in groundwater and unaffected by conventional treat-
ment technologies like air stripping and adsorption to granu-
lar activated carbon (GAC). Further, the historical perspective
has been that 1,4-dioxane is not prone to biodegradation and
Legend
1,4-Dioxane MRL exceedances
Al locations
FIGURE 11.11  1,4-Dioxane public water supply sampling results from the United States Environmental Protection Agency unregulated
contaminant monitoring rule 3. Based on results reported through June 2015, nearly 7% of public water supplies tested showed exceedances
of the health advisory levels for 1,4-dioxane. (From Richardson, S.D. and Kimura, S.Y., Anal. Chem., 87, 546, 2015.)
565
that natural attenuation rates are too slow under typical aqui-
fer conditions to provide much benefit when managing these
plumes. Fortunately, this perspective is changing, as we will
discuss later.
PFCs, also referred to as fluorotelomer acids, alcohols,
and sulfonates, have been manufactured for more than
50 years and have been used to make stain repellents (such
as Teflon) that are widely applied to fabrics and carpets.
They are also used in the manufacture of paints, adhesives,
waxes, polishes, electronics as well as grease-proof coatings
for food packaging. PFCs are unusual chemically, in which
they are hydrophobic and lipophobic and contain one of the
strongest chemical bonds (C–F) known. Because of these
properties, they are highly stable in the environment. Two of
these PFCs, perfluorooctane sulfonate (PFOS) and perfluo-
rooctanoic acid (PFOA), are currently receiving a great deal
of attention as emerging contaminants in the United States.
While PFOS and PFOA were the first fluorinated surfactants
to receive considerable attention, research is expanding
beyond these two contaminants to other perfluorinated acids
and alcohols. PFCs are released to the environment either
through usage of the PFCs containing products or by deg-
radation of their precursors. Most research being conducted
on PFCs is focused on determining their sources, fate, trans-
port, and treatment.
Pharmaceuticals, hormones, and EDCs have become impor-
tant emerging contaminants in recent years. Pharmaceuticals
have been present in our world’s waters since humans began
experimenting with medicines. However, product prolif-
eration and ready access to pharmaceuticals coupled with
566
burgeoning human population have significantly increased
the loading of these compounds into the environment due to
incomplete removal in wastewater treatment or point-source
contaminations. Pharmaceuticals are introduced not only by
humans but also through veterinary uses for livestock, poul-
try, and fish farming.
Because drinking water standards for pharmaceuticals
have not been established at this time and little has been
published on safe long-term exposure levels, it is challeng-
ing to determine health-based treatment goals for drinking
water treatment. In the absence of such information, each
community must determine whether it will wait for more
information or take proactive measures to treat and remove
the pharmaceutical contaminants despite the costs and uncer-
tain benefits. Based on screening levels for most compounds
exposure to drinking water would not be expected to cause
adverse health effects. However, research examining new and
future pharmaceutically active ingredients and exposure to
mixtures of compounds, particularly for sensitive population
groups, should continue. Significant impetus for research and
regulatory activities involving EDCs over the past few years
emanated from public perceptions of risk, often fueled by
highly charged or visible manifestations of possible effects in
humans, aquatic life, and wildlife.
1,2,3-TCP is a synthetic chemical that is also known as
allyl trichloride and trichlorohydrin. It is a colorless, heavy
liquid with a sweet but strong odor and is produced via the
chlorination of propylene. Historically, 1,2,3-TCP has been
used as a paint or varnish remover, degreasing agent, and in
the production of pesticides. 1,2,3-TCP mainly got into the
subsurface environment through the use of soil fumigants.
There have been other instances of industrial use of 1,2,3-TCP
as a chemical intermediate.
TCP is not likely to sorb to soil based on its low soil
organic carbon–water coefficient; therefore, it is likely to
leach from soil into groundwater. However, its solubility in
water is low. TCP evaporates from surface soil and water and
gets photooxidized when in the atmosphere. As of 2015, TCP
was not regulated as a contaminant by the federal govern-
ment; only the State of California has regulated this emerging
contaminant.22
11.3.2 Emerging Contaminants
Currently in the Spotlight
The definition and terminology associated with “emerging
contaminants” have evolved rapidly in the past few years.
The current term of art “contaminant of emerging concern”
(CEC) is being applied to compounds where the risk to human
health and the environment is not entirely understood and is
thus “emerging.” The realization that CECs represent an ever-
growing list of compounds, some with widespread presence
and limited options for treatment, has driven a significant
amount of industry focus and investment to find cost-effective
solutions. This has been fueled in part by individual states
developing drinking water or health-based standards that vary
widely, are very low, and change over time, as opposed to EPA
Remediation Engineering
establishing a federal MCL. The result is a patchwork of stan-
dards that are both difficult to understand and a challenge for
compliance.
In this section, we will focus only on 1,4-dioxane and
PFAS (perfluoroalkyl substances) because they represent
currently relevant CECs at two different points in the CEC
life cycle and maturation process. 1,4-Dioxane has been an
issue for nearly a decade in several states but only recently
has it become a more universal driver for private sector and
public sector stakeholders. Treatment technologies are evolv-
ing and we as an industry are developing more cost-effective
and reliable restoration options. In contrast, PFAS is truly
emerging in the United States as EPA is working to estab-
lish a consensus on toxicology and states begin to prepare to
adopt cleanup standards. The better known PFAS compound
PFOS has been identified internationally as persistent organic
pollutants (PoPs) and its production severely restricted, with
PFOA (known as “C8”) also currently under consideration to
be classed as a PoP by this international treaty. Analytical
methods, toxicology, and treatment technologies are evolv-
ing in parallel for both, but there is still much uncertainty for
stakeholders as they prepare to manage their liabilities.
The lessons learned from restoration and treatment of now
“mainstream” contaminants indicate that there will be ways
to cost-effectively remediate CECs in groundwater, even if
they are difficult-to-treat contaminants. To start, we will look
at the historic evolution of attitudes and practices related to
chlorinated solvents, as a benchmark for today’s CECs. Then
we will consider some of the notable strides being made with
1,4-dioxane and PFAS—that offer both parallels to the his-
tory of chlorinated solvents and the ability to build on the past
and short-circuit what might otherwise be a more lengthy path
to meaningful advances.
11.3.2.1  Lessons Learned from the Past
The evolution of chlorinated solvent remediation was influ-
enced not only by changing regulatory and economic factors
but also by the type and chemical characteristics of the target
contaminants. The need to contain contaminated groundwa-
ter led to universal application of pump-and-treat systems for
source control and mass removal during the early stages of
this evolution. The need for alternative cost-effective solu-
tions with faster cleanup times fostered continuous innova-
tion and led to development of soil vapor extraction, in  situ
air sparging, and chemical oxidation during the 1990s. Early
industry perception was that chlorinated solvents were recal-
citrant and not susceptible to natural attenuation but evidence
of anaerobic degradation surfaced during the early and mid-
1980s. Still, it was another decade before formal guidance
documents were published, and almost two decades before
enhanced biodegradation became widely accepted as a lead-
ing treatment technology.
Decades of assessing the fate and transport of chlori-
nated solvents and other highly soluble compounds have
also enlightened our understanding of how stratigraphy, per-
meability, and advection/diffusion relationships influence
plume evolution. The result has been a broad awareness that
Emerging Trends in Environmental Remediation 567

plumes are commonly spatially thin and flux-focused, which
has sharpened our investigation and remediation approaches.
For the current suite of CECs, the thought process is still
developing around the environmental behavior, transforma-
tion mechanisms, and how best to apply remedial strategies
to achieve focused, efficient cleanup. However, our previous
experience with chlorinated solvents allows some optimism
as the scientific body of evidence grows and allows us to iden-
tify, develop, and deploy remediation solutions for emerging
contaminants such as 1,4-dioxane and PFAS.
11.3.2.2 1,4-Dioxane
The recent pattern of regulation for CECs makes it difficult
for stakeholders to develop consistent risk management strat-
egies that provide certainty in outcomes. The trend has been
for EPA to develop health-based advisories and for individual
states to develop a widely variable patchwork of cleanup stan-
dards. Considering 1,4-dioxane as an example, EPA initially
developed its health-based drinking water advisory level of
0.35 µg/L in 2006 and reviewed the results in 2012. Since that
time, slightly more than half of the states have adopted drink-
ing water criteria, which are often the driver for remediation.
Standards currently range from 200 µg/L in Iowa (based on
statewide standards for a protected groundwater source23 to
0.25 µg/L in New Hampshire (as a reporting limit require-
ment for all public water supplies (see Figure 11.12), but the
trend has been to adopt increasingly lower standards in states
that have been slow to move, while others have revisited the
numbers and are adopting lower standards.
Another challenge is the lack of real-time characteriza-
tion tools for emerging contaminants. For common contami-
nants, like chlorinated VOCs, there are a range of real-time
methods for cost-effective real-time characterization (mobile
lab analysis, membrane interface probe), which occupy a
critical portion of the characterization toolbox for these com-
pounds. Real-time analytical methods have been developed
for 1,4-dioxane using solid phase microextraction and direct
sampling ion trap mass spectroscopy or gas chromatography/
mass spectroscopy.
11.3.2.3 PFAS
PFAS is a more recent addition to the CEC roster and rep-
resents a very broad class of more than 6000 organofluorine
compounds that have been extensively used in personal, com-
mercial, and industrial applications ranging from nonstick
and flame/heat resistant fabrics and coatings, water repellant
and stain resistant fabrics and coatings, surfactants, lubricant
additives, and firefighting foams. The most familiar fluo-
ropolymers include polytetrafluorethylene (PTFE), which is
used in nonstick coatings and waterproof fabrics. Common
PFAS include stain-resistant coatings and aqueous film
forming foams (AFFFs) used in firefighting at airports and

ND VT
WA MT
NA 1.5*
0.438* NA MN
ME
1
SD 3.2
ID WI
OR NA
NA 3 NY
NA WY MI
40* NH
NA IA 85*
NE 0.25
200* PA MA
NA
IL IN OH NA RI 0.3
NV UT CO 6.7* 6.7 NJ NA
7.7* WV
NA NA KS MO 10* CT
0.35 DE 3
8.49* 61* KY 6.1* VA
CA 0.46* NA 6.1
DC MD
1 OK TN NC NA
NA 6.1*
NA AR 3
AZ NM
0.46 SC
6.1* 6.72 AL
MS GA NA
NA NA
TX 6.09*
LA
9.1* 6.1*

FL
3.2*

State
NM
1,4-Dioxane state 6.72 States color coded using the EPA cancer risk
drinking water level for 1,4-dioxane (0.35 µg/L) as follows
standard µG/L
HI
Not available
0.67*
AK Less than or equal to 0.35 µg/L
77* Less than or equal to 3.5 µg/L
Less than or equal to 35 µg/L
Greater than 36 µg/L
Notes:
0 1000 2000 0 200 400 *Drinking water standard not available state 0 150 300
groundwater cleanup standard provided for
Miles Miles reference Miles
µg/L = Microgram per liter
NA = Not available

FIGURE 11.12  1,4-Dioxane groundwater cleanup standards as of November 2015. Only 33 states have established groundwater cleanup
standards for 1,4-dioxane at the present time.
568
industrial facilities. AFFFs comprise proprietary mixtures of
multiple types of fluorinated chemicals including but not lim-
ited to perfluoroalkyl carboxylates, perfluoroalkyl sulfonates,
perfluoro betaines, perfluoro sulfonamides, perfluoro sulfon-
amidoethanol, perfluoro thioamido amino carboxylates, per-
fluoro sulfonamido amines, and fluorotelemer sulfonates.
The PFAS group of compounds comprises PFCs and poly-
fluorinated compounds. With PFCs, all the carbons atoms in
the alkyl chain are saturated with fluorine atoms, whereas
polyfluorinated compounds have carbon-to-hydrogen bonds
in the alkyl chain, that is, the alky chain is not fully satu-
rated with fluorine atoms. PFOS and PFOA are the best
known PFCs, which are octanoates (contain 8 carbon atoms);
however, multiple analogous compounds exist with varying
carbon chains lengths from C2 to C16 that comprise other
perfluorinated sulfonic acids (PFSAs) and perfluorinated car-
boxylic acids (PFCAs), collectively referred to as perfluoro-
alkyl acids (PFAAs). PFAAs have been found to be resistant
to biodegradation and are dead-end daughter products to the
thousands of other PFAS, which biotransform in the environ-
ment to yield PFAAs that may remain unaltered in soil and
groundwater indefinitely. Biodegradation of PFOS and PFOA
has been evaluated under conventional wastewater treatment
conditions24 and natural aquifer conditions25; however, evi-
dence to support the occurrence of biological degradation of
these compounds is lacking, with a similar recalcitrance evi-
dent for other PFAAs.
There is a natural “biological funneling” in which a whole
host of PFAS compounds (fluortelomers, betaines, sulfon-
amides, etc.), with various differing perfluorinated alkyl chain
lengths and functional groups, biotransform to form persis-
tent dead-end daughter products—the PFAAs. The funda-
mental current concern here is how to identify, quantitatively
measure, and assess the toxicology of this myriad of PFAS
compounds and the range of recalcitrant PFAAs which they
form.24,25 An example of these biotransformation processes is
often seen in biological wastewater treatment plants, where
significantly more PFOS and PFOA are often measured at the
outflow than inflow. The apparent increase is explained by the
fact that many PFAS compounds enter the sewage treatment
plant uncharacterized and are biotransformed to PFAAs of
various chain lengths with PFOS and PFOA often being the
only analytes assessed.
PFAS may also be subdivided into two broad classes, long
and short chains, with long-chain PFCAs comprising those
that have seven or more perfluorinated alkyl carbon atoms
(e.g., PFOA and PFNA) and PFSAs with six or more perfluo-
rinated alkyl carbon atoms (e.g., PFHxS and PFOS). Short-
chain PFAAs are not considered by the European Union as
a persistent, bioaccumulative, and toxic substance as a result
of diminished bioaccumulation potential; however, there are
currently limited data regarding their toxicology and they are
thought to be as persistent as long-chain PFAAs, given their
structural similarities. The term PFAS “precursor” is applied
to those long-chain PFAS compounds that biotransform to
yield long-chain PFAAs. However, there will also be many
short-chain PFAS compounds that biotransform to evolve
Remediation Engineering
short-chain PFAAs, which will also be persistent and are
g­ enerally very mobile in aquifer systems.
In their anionic forms, PFOS and PFOA are water soluble
and have moderate organic carbon partitioning with log Koc
of 2.57 and 2.06, respectively. Recent studies have found that
transport potential of PFAS compounds is also based on the
charge on the functional group(s) of the PFAS where anionic
species are the most mobile, followed by zwitterionic spe-
cies, and cationic species have the lowest mobility and may
create immobile source zones.26 Conventional treatment of
groundwater using GAC may be more viable for long-chain
PFAS than short but costs of treatment are high compared to
conventional contaminants.27 GAC has a very limited sorp-
tive capacity for PFAS in general and this decreases as the
carbon chain lengths diminish; therefore, there is a question
of whether GAC can treat short-chain PFAS cost-effectively.
Because the GAC used to sorb PFAS has to be regenerated at
specialized facilities at elevated temperatures over 1200°C,
treatment costs are also higher for PFAS.
The EPA recently issued provisional health advisory
­levels for PFOS (70 ppt) and PFOA (70 ppt) in 201228; how-
ever, final consensus regarding toxicology and cleanup levels
have not yet been attained in the United States. The occur-
rence of PFOS and PFOA in public drinking water supplies
has heightened public awareness, and the indications are that
EPA will finalize its review in the next year. As described
earlier, PFOS and PFOA comprise only two of the thousands
of PFAS compounds that are of potential concern. From an
international perspective, the trend in Europe has also been
to regulate a broader range of PFAS compounds, such as
C4–C10 PFAAs. The European Union has set an environ-
mental quality standard of 0.65 ng/L for PFOS in surface
waters. Additional information regarding PFAS regulation
in the European Union and current perspective of fate and
effects is currently being evaluated.
Current commercially available analytical methodologies
are not capable of quantifying the full suite of PFAS com-
pounds that will exist in soil and groundwater. Because many
PFAS compounds in the soil and groundwater will be progress-
ing through a biotransformation funnel that leads to PFAAs
as dead-end daughter products, this provides a very signifi-
cant analytical chemistry challenge. Some recent solutions to
address this analytical challenge are discussed in the following.
Characterization of PFAS challenges practitioners on sev-
eral fronts. Laboratory analytical methods are in some cases
being developed at the same time that our working under-
standing of the chemicals themselves is growing. The fact
that PFAS compounds stratify in water as they migrate to
the air–water interface means that sampling of groundwater
needs to be taken from the surface of the water table and labo-
ratory analytical methods must involve very vigorous shaking
of all water samples before a subsample is removed. Specific
sampling protocols must be adopted, which also avoid the use
of glass or metals, as PFAS bind to these materials. Samples
should be collected using polyethylene or polypropylene con-
tainers and equipment, avoiding contact with materials that
may contain PFAS such as PTFE.
Emerging Trends in Environmental Remediation
The commercially available analytical method for
PFAS is by EPA Method 537 (which employs liquid chro-
matography with tandem mass spectrometry [LCMSMS])
to analyze a suite of only 14 PFAAs (including PFOA and
PFOS), following the published methodology with report-
ing limits ranging from 0.005 to 0.020 µg/L. These report-
ing limits are being evaluated to achieve EPA’s very recent
health advisory levels of 70 parts per trillion for PFOS and
70 parts per trillion for PFOA or a combined concentration
of 70 parts per trillion. However, this method does not cur-
rently report the results for the full range of the more simple
PFAAs, many fluorotelomers, or many thousands of other
PFAS compounds that biotransform in the environment to
produce PFAAs as dead-end daughter products. In order to
fully understand the potential extent of PFAS contamina-
tion in the environment, additional laboratory techniques
are being developed including expanding the range of ana-
lytes for EPA Method 537 (and similar LCMSMS methods)
to include up to 39 PFAS compounds.29
Development of other more advanced techniques and
alternative approaches are now being used commercially for
the first time. For example, there are two methods in devel-
opment used to quantify total organic fluorine (similar to a
total TPH analysis for PHCs) including particle-induced
gamma-ray emission (PIGE) and adsorbable organofluo-
rine (AOF) analysis using combustion ion chromatography.
There are two methods in development to analyze a much
more comprehensive range of PFAS compounds. The first
is the total oxidizable precursor (TOP) assay, which rapidly
converts PFAS compounds into PFAAs using a conventional
hydroxyl radical–based chemical oxidation method (replicat-
ing what microorganisms in the environment would achieve
after many years) to provide a range of PFAAs that are detect-
able by LCMSMS.29 The second is liquid chromatography
quadrupole time-of-flight mass spectrometry (LC-QTOF-
MSMS), which is a semiquantitative method revealing the
empirical formula of multiple PFAS compounds by assess-
ing the accurate mass of the PFAS’s molecular ions, to four
decimal places of a Dalton. The TOP assay approach shows
promise because it quantifies the sum of PFAS that could
be converted to PFAAs in the environment by simulating
PFAS biotransformation. This allows assessment of the hid-
den PFAS mass using the existing LCMSMS methods, with
a slightly expanded range of PFSAs and PFCAs quantified.
There is value in doing this analysis before and after the PFAS
are partially digested by oxidized reaction to assess both the
free PFAAs and the PFAAs that were hidden in the form of
thousands of PFAS compounds currently not detectable. The
TOP methodology has revealed that for AFFF impacted sites,
the existing analytical LCMSMS methods are only detect-
ing some 30% of the total PFAAs mass hidden in PFAS, with
some analytes such as perfluorohexanoic acid being evolved
from PFAS to give an increase in concentration of more than
200-fold. While the TOP assay is now commercially available
in the United Kingdom, it is not available in the United States.
The PIGE method is currently being commercially developed
and is available in the United States.
569
Because real-time analytical methods are in the nascent
stages of development for PFAS, the only available option for
mapping concentrations is off-site lab analysis, tied with con-
ventional sampling. This creates the risk of relying on sparse
data sets with limited horizontal and vertical resolution. Such
data sets cannot convey the important geologic and hydro-
geologic context necessary to accurately interpret source and
plume behavior, limiting the ability to develop reliable CSMs
and remedial strategies.
11.3.2.4 Developing Advancements in
Management of 1,4-Dioxane and PFAS
While we acknowledge the challenges associated with
emerging contaminants, we believe that practitioners and
stakeholders can capitalize on the lessons learned from
decades of continuous improvement regarding character-
ization and remediation of chlorinated solvents and other
recalcitrant contaminants. We understand the benefits that
a flux-based perspective can bring to focus remedies and
how combined remedy strategies can be used to optimize
performance and improve certainty in outcomes. Successful
remediation of CECs such as 1,4-dioxane and PFAS requires
that we apply a toolkit of different approaches that are tai-
lored to meet the conditions not only at each different site
but conceivably in different areas of the same plume. The
areas where these opportunities are developing most rapidly
include
• Smart characterization to map contaminant mass
flux and focus remedies
• Source treatment to accelerate mass reduction and
reduce contaminant flux
• Dilute plume treatment to optimize management of
long-term groundwater cleanup
Table 11.3 provides a summary of the analytical and treat-
ment methods that are currently available for 1,4-dioxane and
PFAS. The following discussions explore the opportunities in
site characterization and several specific treatment techniques
that show promise for more cost-effective management of
these (and other) CEC plumes in groundwater.
11.3.2.4.1  Smart Characterization
Restoration strategies for 1,4-dioxane and PFAS are often
developed based on the idea that the plumes are diffuse,
because source area concentrations are typically measured
in the low milligrams per liter (mg/L) (e.g., 1–10 mg/L) and
distal portions of the plume show dilute concentrations in the
single digit to tens of µg/L. The challenge is one of scale and
perspective. Because the cleanup standards for 1,4-dioxane,
PFOS, and PFOA can be less than 1 µg/L, source concentra-
tions of 1,4-dioxane and PFOS/PFOA are often four to five
orders of magnitude higher than the cleanup goal. The result
is that successful cleanup for 1,4-dioxane and PFOS or PFOA
might require more than 99.99% treatment efficiency, which
is a similar frame of reference for CVOC dense nonaqueous
phase liquids (DNAPLs).
570 Remediation Engineering

TABLE 11.3
Summary of the Current Understanding of Remediation Options for 1,4-Dioxane and PFAS
1,4-Dioxane PFAS
(Commonly used laboratory analyses include USEPA (Commercially available laboratory analysis using USEPA 537;
522, USEPA 8260B [SIM with isotopic dilution] and other laboratory methods in development including TOP Assay,
USEPA 8270D [SIM with isotopic dilution]) LC-QTOF-MS, PIGE Spectroscopy, and AOF)
Noteworthy information provided if
appropriate and references provided Noteworthy information provided if appropriate
Remedy Status for emerging technologies Status and references provided for emerging technologies

Source Treatment
ISCO Commercial Activated/unactivated persulfate, Emerging Lab scale (ScisoR® for PFOS/PFOA).30
ozone, Fenton’s reagent
Enhanced in situ Emerging Pilot and full scale systems N/A —
bioremediation
In situ thermal Commercial Pilot testing N/A —
Stabilization N/A — Commercial Carbon and other commercially available additives
such as RemBind™ and MatCARE™.
Soil removal Commercial Not typical Commercial —
Groundwater Treatment
Advanced Commercial Ozone/hydrogen peroxide, UV light/ N/A —
oxidation hydrogen peroxide
processes
Emerging Granulated activated carbon and Emerging —
hydrogen peroxide used to generate
super oxide radicals34
Sorptive media N/A Full scale systems Commercial PFAS sorption to carbon is very low, ineffective for
(GAC) short-chain PFAS; carbon consumption is high.
Sorptive media Commercial Synthetic media Commercial Commercially available additives such as RemBind™,
(other) MatCARE™, and PerfluorAd (emerging).
N/A — Commercial Ion exchange media.31
Cometabolic Emerging Pilot scale N/A —
Microbially Emerging Lab scale N/A —
driven Fenton
reaction
Ultrafiltration N/A — Commercial Reverse osmosis and nanofiltration.
Sonochemical N/A — Emerging [32,33]
Bioreactor Emerging Pilot testing N/A Unknown
MNA
Aerobic Emerging Lab scale N/A Unknown
Anaerobic Emerging Lab scale N/A Unknown
Cometabolic Emerging Lab and pilot scale N/A —
Fungi Emerging Lab scale N/A —
Other biological Emerging Field scale N/A —

Technologies are categorized as follows: commercial, when several examples of field-scale deployment are available or based on authors direct experience;
emerging, when literature reports results in lab or pilot scale; N/A, when limited data were available to document application.
Notes: GAC, granular activated carbon; SIM, selective ion monitoring; TOP, total oxidizable precursors; QTOF MS, quadrupole time-of-flight mass
spectroscopy; PIGE, particle-induced gamma-emission; AOF, adsorbable organofluorine; Other biological, evidence for degradation via iron-
reducing bacteria.

In the column on Smart Characterization,13(b) we noted that
mass flux is typically concentrated in the permeable trans-
port zones but that diffusion into fine-grained storage zones
along the advective transport pathway can lead to instances
where the “source” center of mass is often offset from the spill
location in mature plumes. The high solubility and limited
organic carbon partitioning of 1,4-dioxane and PFAS make it
more likely that storage zones along the transport trajectory
will serve as “sources” for back diffusion after the advective
plume has long since passed. The key is using high-resolution
Emerging Trends in Environmental Remediation 571

hydrostratigraphy and sampling techniques to target the flux
and distinguish contaminant mass transport zones from mass
storage zones. Real-time analytical methods are available
today for 1,4-dioxane, and efforts are underway to develop
quantitative screening approaches to evaluate total PFAS. In
the interim, it is important that we resist temptation to revert
to the use of monitoring wells to characterize these sites.
Figure 11.13 shows the results of smart characteriza-
tion applied to a former fire training area. We used a mass
flux transect approach that combined the hydraulic profiling
tool and vertical aquifer profile groundwater sampling with
fixed laboratory analysis by EPA Method 537. The resulting
3-D interpretation of the PFOS plume clearly shows that the
majority of the mass discharge is concentrated within a frac-
tion of the plume footprint. The geometry of the plume and
mass distribution suggests that focused treatment along the
core could significantly reduce the mass flux. While addi-
tional source characterization is necessary to evaluate the
residual mass at the fire training area and potential benefits of
source treatment, the results indicate that a flux-based remedy
strategy could enable focused treatment of the PFOS plume.
11.3.2.4.2  In Situ Chemical Oxidation
Treatment of high concentrations of 1,4-dioxane in ground-
water is typically accomplished using varieties of advanced
oxidation processes, combined with conditioning tailored to

PFOS plume
0.4–1 µg/L

A´ 1–10 µg/L
10–100 µg/L
>100 µg/L

A 0 200΄ 400΄

Scale (ft)
(a)

A A΄

–10

–20
Elevation

–30
PFOS plume
0.4–1 µg/L
–40
1–10 µg/L

–50 10–100 µg/L

>100 µg/L

0 250 500 750 1000 1250 1500 1750 2000

(b) Feet

FIGURE 11.13  Smart characterization results for perfluorooctane sulfonate (PFOS) at a former fire training area. Based on application of
mass flux transects using HPT and VAP groundwater sampling, the core of the plume is concentrated in the vertical and horizontal dimen-
sions. As a result, the majority of perfluorooctane sulfonate mass discharge is concentrated in less than 20% of the aquifer volume: (a) plan
view of the plume and (b) cross-sectional view of the plume.
572
the site geochemistry for best results. Recent applications of
regenerable media show promise under the right geochemi-
cal conditions, particularly with higher influent concentra-
tions. As shown in Table 11.3, source treatment methods using
ISCO via persulfate, ozone, and Fenton’s chemistry have also
been successfully applied and proven in the field. In one
example, we applied persulfate chemistry in a pilot to evalu-
ate options for full-scale treatment. As ISCO applications are
less effective when contaminant mass has diffused into the
less permeable portions of the aquifer stratigraphy, oxidants
with greater longevity are preferable as they are better suited
to target such stored contaminant mass. This makes persul-
fate a good choice. The free radical cascade developed during
persulfate applications also yields hydroxyl, perhydroxyl, and
superoxide radicals and can be engineered with a variety of
activation chemistries.
Data collected following one field persulfate injection for
1,4-dioxane treatment is presented in Figure 11.14. Initial per-
sulfate bench-scale treatability testing was completed using
site soil and groundwater to assess 1,4-dioxane and chlori-
nated VOC treatment using chelated iron, alkaline, and ambi-
ent (persulfate alone) activation techniques.34 Both alkaline
and ambient activation chemistries demonstrated near com-
plete removal of 1,4-dioxane within 7 days of reaction (with
chelated iron showing no change), and ambient persulfate
activation (approximately 5% by weight) was selected for
field trial. As shown in Figure 11.14, significant destruction
of both 1,1-dichloroethene and 1,4-dioxane was observed
­following injection. Some rebound was observed approxi-
mately 6 months postinjection (and following complete per-
sulfate exhaustion), which was attributed to the presence of
1,4-dioxane within the interbedded sand and clay injection
1000
1,4-Dioxane and 1,1-DCE concentration (µg/L)
800
600
400
200
0 0
–50
FIGURE 11.14  Field data collected from monitoring well within radius of persulfate injection influence. 1,4-Dioxane treatment reduced by
90% postinjection. Observed 1,4-dioxane rebound following persulfate consumption attributed to retained diffuse mass in fine-grained soils.
Remediation Engineering
area hydrostratigraphy. This example demonstrates the via-
bility of various persulfate oxidation approaches to achieve
complete oxidation and also demonstrates that successful
oxidation performance will require design and deployment
to account for mass in lower-permeability storage zone and
appropriate injection hydraulic principles—as with any other
mainstream contaminants.
Source treatment options for PFAS have generally been
limited to excavation and treatment of vadose zone soils.
Because treatment is generally limited to high-­temperature
thermal methods (>1200°C), many facilities in North
America and Europe have stockpiled and contained these
materials pending development of more cost-effective
methods. Considerable efforts are being expended to eval-
uate ISCO as a source treatment option, but PFAS is not
an easy target. The strength of the carbon–fluorine bond
makes achieving complete in  situ PFAS destruction infea-
sible with most standard oxidation chemistries. While the
hydroxyl radical discussed for 1,4-dioxane is sufficient to
oxidize PFAS precursors to various perfluorinated carboxyl-
ate or sulfonate intermediates29—as utilized to perform the
TOP assay digest—it is insufficient for complete destruc-
tion of PFAS compounds. In fact, it mobilizes many PFAS.
A variety of chemical oxidation methodologies have been
attempted including Fenton’s and modified Fenton’s, acti-
vated persulfate, sonolysis, ozonolysis, sonochemical, pho-
tocatalysis, and zerovalent iron, in addition to others and
various combinations of these techniques. While some of
these have been demonstrated effective for specific PFAS
compounds, such as PFOA, they either are not applicable for
in situ treatment or have not been effective for the full suite
of regulated PFAS constituents—notably PFOS.
75
1,4-Dioxane
1,1-DCE 60
Sodium persulfate
Sodium persulfate (g/L)
45
30
15
0 50 100 150 200 250 300 350
Time relative to injection (days)
Emerging Trends in Environmental Remediation
Focused research over many years has evaluated oxidant
and activator combinations to cause degradation of PFOS.35–37
Recent laboratory work has demonstrated that a specific
method of activated persulfate oxidation is capable of min-
eralizing PFOS via a hypothesized series of mechanisms that
include both oxidation and reduction. As defluorination is
observed, creation of a redox couple involving both chemi-
cal oxidation and chemical reduction, likely forming reductive
radicals or solvated electrons, is theorized. The decreases in
PFOS concentrations and fluoride evolution are only observed
when a specific activation method is employed.36(a–c),37
Demonstrated to be effective for treatment of a variety of
C4–C8 perfluorinated carboxylates and sulfonates, ongoing
work has been focused on confirming that complete oxida-
tion is achieved—opposed to the generation of incomplete
PFAS oxidation by-products. Fluoride analysis can be used
to assess the total fluoride released during oxidation for com-
parison to the equivalent stoichiometry based on PFOS loss.
Comparative PFOS and F results are currently being final-
ized, but the results are currently looking very positive. With
additional work ongoing, results and field-derived data are
expected for publication during 2016.
11.3.2.4.3  Dynamic Groundwater Recirculation
The benefits of DGR to remediate large plumes in ground-
water, not simply capturing and controlling the plumes,
have been discussed recently.13 The basic premise behind
the approach is that adaptively changing the reinjection and
withdrawal patterns on a frequent basis accelerates flush-
ing in the advective transport zones, while maintaining a
state of disequilibrium between the transport and storage
zones to enhance the back diffusion of stored contaminant
mass. Because 1,4-dioxane and PFAS plumes often exhibit
displacement between the center of mass and the release
location, DGR is well suited to remediate large plumes
where conventional source treatment technologies would be
impracticable and cost prohibitive.
Treatment technologies currently exist to enable suc-
cessful application of DGR for restoration efforts involving
1,4-dioxane. While further advancement is required for cost-
effective treatment of PFAS using DGR, additional technolo-
gies are emerging, with significant emphasis being placed on
regenerable sorptive media, ultrafiltration, and advanced oxi-
dation processes.
11.3.2.4.4  Biological Degradation
As indicated earlier, there is significant evidence in the litera-
ture of aerobic biotransformation of the PFAS compounds to
PFAAs as recalcitrant dead-end daughter products. There are
no data indicating that PFAAs will attenuate via any biodeg-
radative processes. Our understanding of biological degrada-
tion of 1,4-dioxane is maturing, thanks to the application of
molecular biology tools including biomarkers, genetic enzyme
analysis, and compound specific isotope analysis. Before the
advent of molecular biology tools, it was possible to use plume
retraction as a line of evidence for natural attenuation, but the
mechanism for mass reduction was not clearly understood.
573
Recent research indicates increasing potential for biodeg-
radation of 1,4-dioxane through aerobic, cometabolic, and
anaerobic pathways.38–40 While field data are emerging and
processes are not understood at all sites and conditions,38
completed meta-data analysis showed significant evidence
for ongoing natural degradation at some California and Air
Force sites. Molecular biology tools now enable one to use
genetic testing to evaluate potential pathways and confirm
that bacteria are actively transforming 1,4-dioxane.39 These
recent developments provide practitioners a necessary line of
evidence to evaluate natural attenuation at sites or to enhance
in situ bioremediation through the addition of substrates that
facilitate cometabolic processes.
In one example, historical manufacturing practices at a
former automotive manufacturing facility, now RACER,
resulted in release of CVOCs and 1,4-dioxane to groundwa-
ter in both a perched groundwater zone and deeper under-
lying weathered rock aquifer. Groundwater concentration
trends and geochemical data suggested intrinsic reductive
dechlorination of CVOCs in the perched zone and cor-
related to a shrinking 1,4-dioxane plume footprint, while
trends within the deeper aquifer were less straightforward.
As part of the remedy selection process, additional lines
of evidence were needed to support a natural attenuation
approach in the perched zone and determine if bioreme-
diation was an appropriate strategy in the deeper aquifer.
Here we focus on the natural attenuation assessment of the
perched zone.
Molecular biology tools were used to evaluate biodegra-
dation perched zone (Figure 11.15). The first step included
collection and analysis of dissolved gas samples to quantify
the concentrations of cometabolic substrates (i.e., methane
and propane) and electron acceptor (i.e., oxygen). The sec-
ond step included deployment of Bio-Trap® samplers for
30 days at similar locations to collect microbial samples for
DNA and RNA molecular analyses. The DNA-based molec-
ular analyses quantified soluble methane monooxygenase
(SMMO) and propane monooxygenase (PMO) functional
gene targets, an indication of the potential for the sub-
surface microbial population to cometabolically degrade
1,4-­d ioxane. The RNA-based molecular analyses quanti-
fied similar targets in an effort to identify active generation
of these enzymes under current conditions by the intrinsic
microbial population.
The dissolved gas analyses yielded elevated concentrations
of methane (>1000 µg/L) in the perched zone. Dissolved oxy-
gen was lower in the perched plume (200 µg/L) and propane
was not detected at any of the sample locations. DNA-based
analyses indicate potential for both SMMO and PMO pro-
duction by indigenous microorganisms. RNA-based analy-
ses identified SMMO activity at most locations but not PMO
activity (as expected based on the dissolved gas analyses).
These results provide an additional line of evidence in sup-
port of a natural attenuation approach. When combined with
stable and decreasing concentration trends, the results suggest
feasibility in implementing a natural attenuation approach in
the perched zone.
574 Remediation Engineering

Legend
Approximate extent LNAPL
VOCs in perched GW> DW criteria
1,4-Dioxane in perched GW> 8.5 µg/L
(a)

1.E+06 2000

1800
1.E+05
1600

Methane and dissolved oxygen (µg/L)

1400
1.E+04
RNA: transcript copies
DNA: cells/bead

1200

1.E+03 1000

800
1.E+02
600

400 SMMO DNA

1.E+01
SMMO RNA
200 Methane
ND DO
1.E+00 0
MW-12-09 MW-14-62 MW-14-60 MW-03-07 MW-02-02(6)

1.E+06 2000

1800
1.E+05
Propane and dissolved oxygen (µg/L)

1600

1400
RNA: transcript copies

1.E+04
DNA: cells/bead

1200

1.E+03 1000

800
1.E+02
600

400
1.E+01 PPO DNA
200 PPO RNA
Propane
ND ND ND ND ND ND 0 Propane ND
1.E+00
MW-12-09 MW-14-62 MW-14-60 MW-03-07 MW-02-02(6) DO
(b)

FIGURE 11.15  1,4-Dioxane natural attenuation case study results. (a) Upper panel shows perched 1,4-dioxane plume in pink and high-
lights locations where dissolved gases were sampled and bio-traps were deployed. (b) Summary of dissolved gas and molecular analyses in
the perched zone. Solid bars represent DNA results for soluble methane monooxygenase (SMMO) (top graphs) and propane monooxygenase
(PMO) (bottom graphs). Open bars represent RNA results for SMMO (top graphs) and PMO (bottom graphs). Solid circles represent
methane (top graphs) and propane (bottom graphs). Solid triangles represent dissolved oxygen. Open symbols and ND markers represent
values less than reporting limit (250 cells/bead for DNA or 250 transcript copies for RNA).
Emerging Trends in Environmental Remediation
11.3.2.5  Current State of the Science
The challenges associated with emerging contaminants such
as 1,4-dioxane and PFAS might seem insurmountable, given
the low standards being promulgated coupled with their per-
sistence in the environment and perceived resistance to treat-
ment. However, there are opportunities to leverage our lessons
learned over the past two decades with chlorinated solvents
and other “mainstream” contaminants that were once classi-
fied as emerging.
Notably, we understand how to use smart characteriza-
tion methods to develop an understanding of contaminant
flux as part of the CSM, so that we can focus on restora-
tion efforts and tailor remedies to match the conditions and
risks at the source and in downgradient/distal portions of
a plume. Similarly, advances in analytical methods and
the science behind remediation technologies support faster
development of more cost-effective options for character-
ization and treatment. This includes methods for evaluating
natural attenuation and optimizing biological degradation
for 1,4-dioxane and advanced methods to characterize and
apply in  situ reductive/oxidative approached to destroy
PFAS in  situ, all of which should accelerate the pace of
developing ways of managing 1,4-dioxane and PFAS more
cost-effectively.
While the patchwork of regulatory standards and devel-
oping understanding of toxicology is still a source of uncer-
tainty for stakeholders in the United States and globally,
collaboration among the regulatory and stakeholder com-
munities is occurring more effectively now than in the past,
which fosters innovation. We are optimistic that the chal-
lenges of emerging contaminants will be shorter lived than
our past experience with chlorinated solvents. Continued
focus on improving key elements in our remediation toolkit
is essential to be sure we capitalize on our lessons learned
and translate them into more certainty in outcomes for all
stakeholders.
11.4 MANAGING VAPOR
INTRUSION CONCERNS
The assessment and mitigation of the vapor intrusion (VI)
exposure pathways have recently become the most highly
researched and regulated field in the environmental indus-
try. VI generally occurs when there is migration of volatile
compounds from contaminated soils and groundwater into
an overlying building. Volatile compounds can emit vapors
that may migrate through subsurface soils and in air spaces of
overlying buildings in ways similar to that of radon gas seep-
ing into homes. The process of volatilization of contaminants
has evolved from that of simply guiding remediation strategy
to that as an essential element that governs contaminant trans-
port in the saturated zone.
Common volatile contaminants include
• Petroleum compounds (PHCs)
• Chlorinated and nonchlorinated volatile organic
compounds
575
• Select semivolatile organic compounds
• Some inorganic analytes, such as elemental mercury,
radon, and hydrogen sulfide
In extreme cases, the vapors may accumulate in dwellings or
occupied buildings to levels that may pose
• Near-term safety hazards (e.g., explosion)
• Acute health effects
• Aesthetic problems (e.g., odors)
In buildings with low concentrations of volatile chemicals,
the main concern is whether the chemicals may possess
unacceptable risk of chronic health effects due to long-term
exposure to these low levels. A complicating factor evaluating
the potential chronic risk from VI is the potential presence
of some of the same chemical emission sources within the
building. Household solvents, gasoline, and cleaners can pose,
separately or in combination with VI, a significant human
health risk.
The simple conceptual model of the VI pathway that is pre-
sented in Figure 11.16 illustrates a source of contamination
in soil and groundwater and the upward movement of VOCs
from this source toward and into buildings.
There are tens of thousands of sites in the United States
with gasoline, solvents, or mixtures of other volatile chemi-
cals in shallow soil and/or groundwater. Almost all of these
sites are being managed under federal or state regulatory pro-
grams, and many have undergone some form of remediation.
Historically, cleanup decisions were based on concerns asso-
ciated with potential direct exposure to affected soil and/or
groundwater, without consideration of the potential inhalation
exposure if vapors migrated from shallow soil or groundwater
into buildings. Within the last 5  years, however, regulatory
agencies have placed increased emphasis on VI as a pathway
contributing to the exposure of workers or residents occupy-
ing affected buildings.
However, according to several field studies reported
in the literature, evidence of VI is usually observed for
chlorinated solvents, whereas the occurrence of PHCs
VI is extremely rare and generally associated with high-
concentration sources located in close proximity to the
building foundations.41 The behavior observed for PHCs is
mainly ascribed to the degradation processes taking place
in the vadose zone under oxygen-rich conditions by ubiq-
uitous soil microbes, which typically reduce the potential
of petroleum VI relative to that of chlorinated compounds.
Aerobic biodegradation in the vadose zone can significantly
attenuate petroleum vapors by several orders of magnitude.9
Nevertheless, VI is still considered a critical pathway in
many sites contaminated by PHCs. This is in large part due
to the overly conservative regulatory screening criteria and
guidelines that are generally adopted for the assessment of
this migration pathway.
Regulatory interest in VI coincidentally increased at the
same time that EPA was reevaluating the toxicity of several
volatile chemicals including TCE, which has been detected
576
HVAC
system Potentially exposed
individual
Basement
HVAC 5
system
Paint
can
Workbench
Crack
Vadose
zone soils
Groundwater containing COCs
FIGURE 11.16  Conceptual description of vapor intrusion concerns.
at thousands of sites across the country.41,42 EPA has released
updated guidance on VI issues, has recently requested VI
evaluations as part of the 5-year review of some Superfund
sites, and has used this issue to reopen some previously
issued records of decision at sites where TCE is the primary
chemical of interest. In turn, media reports of VI investi-
gations, particularly stories of chemical vapors potentially
entering homes and commercial buildings, have heightened
public concern.
Often times today, the VI pathway is a dominant factor in
apparent risk at a site and long-term vapor control or cleanup
is a requirement. The focus of vapors in risk assessment has
led to a number of regulators elevating soil vapor to an envi-
ronmental media of concern on its own, similar to historic
treatment of soil and groundwater. This has required an evolu-
tion in thought as CSMs now must integrate soil, groundwa-
ter, and soil vapor data into a comprehensive story.
Historically, equilibrium relationships have been used
for groundwater–vapor (Henry’s law) and soil–­groundwater
systems (sorption coefficients—Kd). As more coincident
soil and soil vapor data are being collected in recent years,
the need has arisen to interpret the data in the context of
local contaminant sources and the surrounding media those
sources have impacted. When addressing soil vapor outside
of NAPL source areas, local vapor sources are typically
VOCs dissolved in water, which can be groundwater in the
saturated zone or residual soil moisture found in the unsatu-
rated zone.
Soil VOC data can be very heterogeneous because of the
tortuous path that percolating NAPL or VOCs dissolved in
infiltrating groundwater takes through the subsurface. VOCs
in soil vapor and groundwater have greater mobility in the
subsurface and can create vapor clouds and groundwater
plumes, respectively. Because of this greater mobility, the
Remediation Engineering
5 Indoor background source
Cracks
4 Vapor infiltration through
building envelope
4
3 Vapor migration through
3 soil column
2 2 Volatilization from source
1 Source
1
extents of VOCs in soil vapor and groundwater are often
times less heterogeneous than the concentration distributions
found in soil data.
Therefore, it has become necessary to establish expected
relationships between soil and soil vapor data, just like for
soil–groundwater and groundwater–vapor systems previously.
Although the soil concentrations in equilibrium with soil
vapor are low when compared to typical risk-based cleanup
goal concentrations, the soil concentrations can sustain soil
vapor concentrations well above vapor risk standards. So in
certain circumstances, low VOC soil concentrations become
a continuing source to soil vapor and prevents site closure.
On June 11, 2015, the USEPA released two technical guides
for investigating and mitigating the VI pathway.41,42 USEPA
also updated the VI screening level calculator to be consis-
tent with the technical guide and the soon-to-be-released June
2015 USEPA Regional Screening Levels. These documents
supersede the draft guidance released by USEPA in 2002 and
include:
• OSWER Technical Guide for Assessing and
Mitigating the Vapor Intrusion Pathway from
Subsurface Vapor Sources to Indoor Air (VI
Technical Guide)
• Technical Guide for Addressing Petroleum Vapor
Intrusion at Leaking Underground Storage Tank
Sites (PVI Technical Guide)
The VI Technical Guide applies to all sites being evaluated
under federal land cleanup statutes by USEPA, other federal
agencies, state and tribal governments, and brownfield grant-
ees. Several key updates have been made since the issue of the
draft guidance in 2002—these updates are summarized in the
accompanying table.
Emerging Trends in Environmental Remediation
The PVI Technical Guide is a new document applicable
to PHC and non-PHC fuel additive sites. The release of this
guidance may result in the reopening of some cases where the
potential for PVI was identified but not evaluated. The PVI
Technical Guide proposes a similar approach to assessing and
mitigating PVI as presented for overall VI pathway investiga-
tions in the VI Technical Guide.
11.5 MANAGEMENT OF COAL
COMBUSTION RESIDUALS
Coal combustion residuals (CCRs), also referred to as coal
ash, is produced primarily from the burning of coal in coal-
fired power plants. Coal ash includes a number of by-products
produced from burning coal, including:42
• Fly ash, a very fine, powdery material composed
mostly of silica made from the burning of finely
ground coal in a boiler
• Bottom ash, a coarse, angular ash particle that is
too large to be carried up into the smoke stacks so it
forms in the bottom of the coal furnace
• Boiler slag, molten bottom ash from slag tab and
cyclone type furnaces that turns into pellets that have
a smooth glassy appearance after it is cooled with
water
• Flue gas desulfurization material, a material leftover
from the process of reducing sulfur dioxide emis-
sions from a coal-fired boiler that can be a wet sludge
consisting of calcium sulfite or calcium sulfate or a
dry powered material that is a mixture of sulfites and
sulfates
Coal ash is disposed of or recycled in different ways depend-
ing on the type of by-product, the processes at the plant, and
the regulations the power plant has to follow. Coal ash is the
second largest waste material generated in the United States
behind only household trash. Power generation companies
struggle to find economic ways to get rid of it. In the United
States, about 40% of the material is recycled in useful appli-
cations such as making concrete and system wallboard. But
the sheer volume of coal ash produced and the economics of
handling it is such that the other half must be disposed of as
waste.
11.5.1  Coal Ash Disposal Practices
The most desirable and environmentally least harmful way to
dispose of coal ash is to recycle it. In the United States, coal
ash is considered as nonhazardous solid waste suitable for nor-
mal landfilling. Today, two major disposal methods are used
for the disposal of coal ash: “dry” and “wet” disposal. Dry
disposal, where CCRs are disposed of in dry or slightly moist
conditions in landfills, is carried out like conventional back
filling or earthmoving operations. Wet disposal or “lagoon-
ing” implies the mixing of CCR with water at the plant site
577
FIGURE 11.17  A coal ash pond. (From http://appvoices.org/2009/​
07/01/2398/.)
and the subsequent hydraulic conveying of the slurry through
pipelines either to a single or to a series of artificial lagoons
where the slurry is discharged (Figure 11.17).
Management options have to be developed with stable and
accessible disposal site surfaces in mind. Stability of the sur-
face largely depends on the amount of residual water and the
ash’s drainage capacity. It is furthermore affected by charac-
teristics such as particle size distribution, content of pozzo-
lanic layers, and exposure to wetting and drying cycles. Ash
ponds need to be observed regularly using geotechnical meth-
ods to manage the risk of base failure. Unstable sites need to
be reinforced.
CCRs are disposed in off-site landfills or disposed in on-
site landfills or surface impoundments. Approximately 40%
of the CCRs generated are beneficially used, with the remain-
ing 60% disposed in surface impoundments and landfills.43
CCR disposal currently occurs at more than 300 active on-site
landfills, averaging more than 120 acres in size with an aver-
age depth of over 40 ft, and at more than 700 active on-site
surface impoundments, averaging more than 50 acres in size
with an average depth of 20 ft. If disposing and managing
CCR in large storage ponds or landfills are not managed prop-
erly, contaminants can leak over time and cause an array of
environmental problems.
11.5.2  CCR Regulations
Coal ash is primarily made up of silicon, aluminum, calcium,
and iron oxides, with lesser amounts of other metal oxides and
sulfur. It also contains traces of mercury, cadmium, chromium,
lead, arsenic, and other metals, as well as boron, nitrates, and
fluoride. The composition is similar to common rocks and soils,
as well as volcanic ash, which has been used as a construction
material as far back as the ancient Romans. However, alkaline
ash contains small amounts dioxins and polyromantic hydro-
carbons substances that could end up in the environment.43
Since coal ash contains certain contaminants mentioned
earlier and also because of the recent incidents of ash pond
failure, EPA has been evaluating the safety of coal ash.
The agency developed a new set of rules that went into effect
578
in October, 2015, on coal ash management under the Resource
Conservation and Recovery Act (RCRA), which is the nation’s
primary law on handling solid waste.42
EPA finalized national regulations to provide a compre-
hensive set of requirements for the safe disposal of coal com-
bustion residuals (CCRs) from coal-fired power plants. The
final rule is the culmination of extensive study on the effects
of coal ash on the environment and public health. The rule
establishes technical requirements for CCR landfills and
surface impoundments under subtitle D of the RCRA, the
nation’s primary law for regulating solid waste. The final rule
makes a number of changes from the proposal including pro-
viding greater clarity on technical requirements in response to
questions received during the comment period (EPA).44
These regulations address the risks from coal ash dis-
posal—leaking of contaminants into groundwater, blowing of
contaminants into the air as dust, and the catastrophic fail-
ure of coal ash surface impoundments. Additionally, the rule
sets out recordkeeping and reporting requirements as well as
the requirement for each facility to establish and post-specific
information to a publicly accessible website. This final rule
also supports the responsible recycling of CCRs by distin-
guishing safe, beneficial use from disposal.
11.5.3 Pond Closure
Utilities nationwide are facing a range of regulatory, environ-
mental, operational, and financial pressures to close or con-
sider closing their coal ash ponds. Many factors can influence
the decision to close an ash pond: regulatory requirements,
plant operational future, switching from wet to dry ash han-
dling at the plant, and capacity of the pond.
Closure and remediation solutions for coal ash ponds or
impoundments can vary greatly. A successful closure strategy
must also account up-front for the future use of the site, par-
ticularly with retiring plants. Facilities with prime real estate
or redevelopment potential may require stricter cleanup lev-
els. Site-specific conditions such as wetlands, surface stabil-
ity, and the geotechnical properties of the pond itself and the
settled ash are important to evaluate. It is also important to
evaluate as part of the closure strategy, to see if there is a via-
ble market for the pond material. Geotechnical and environ-
mental investigations, community relationships, regulatory
permitting, and construction management are all important
facets of closure planning.
Among the choices for closure solutions are capping,
dewatering and/or stabilizing, consolidating into a new land-
fill, disposing off site, or converting to managed wetlands
or any combination of these options. A successful closure
approach should account for the site layout, pond size, dewa-
tering requirements and constructability methods, final site
use, and integration of all site activities.
11.5.4 Recycling
Scientists have looked at coal ash for at least a century seeking
remedies and opportunities for recycling. In some European
Remediation Engineering
countries, such as Denmark, where there is no landfill space,
all the ash is recycled. China provides subsidies to promote
coal ash recycling. Today, about half the concrete produced in
the United States consists of some fly ash—up to 40%—as a
substitute for limestone based Portland cement. Among other
applications, fly ash is used as material to make bricks, ceramic
tiles, and plaster and also as structural fill for road construction.
Fly ash is beneficial in construction and as structural fill
for its physical properties. Its composition reduces the amount
of cement and water needed to make concrete and produces
denser concrete with improved mechanical and chemical
properties and make it stronger and more durable. For exam-
ple, fly ash can nearly double the life of a highway. Beyond
the economics, there are many environmentally beneficial
considerations in using fly ash. For example, for every ton of
fly ash used in place of Portland cement, about 1 ton of CO2
emissions is eliminated. It also reduces a portion of the fossil
energy required, pollution generated, and the environmental
impacts to mine, transport, and process the raw materials.
The synthetic gypsum formed during flue gas desulfuriza-
tion is used like naturally mined gypsum to produce wall-
board, also known as sheet rock. About half the wall board
manufactured in the United States is produced from power
plant gypsum. Synthetic gypsum is typically of higher purity
than mined gypsum.
Among other coal ash materials, bottom ash is a coarse
material too large to float in flue gas, so it falls through grates
into a hopper in the bottom of the coal furnace. It is typically
used as filler in concrete and as fill material for road construc-
tion. Boiler slag is molten bottom ash that turns into pellets
with a smooth glassy appearance after it is cooled with water.
It is useful as grit for sandblasting and polishing, roofing shin-
gles, filler in asphalt, and a substitute for sand in snow and ice
traction control.
11.6  NANOMATERIALS IN THE ENVIRONMENT
Nanotechnology and nanomaterials (NMs) are expected
to bring tremendous benefits to the society and at the same
time can also potentially pose risks to the environment and
human health. Definitions of NMs depend on the disciplinary
background and working environment of the person using the
term. For us to evaluate the impacts of NMs introduced in the
environment, research should be performed in understanding
carefully selected and narrowly defined material properties.
Such well-defined material properties are of fundamen-
tal importance to conduct an in-depth nano-toxicological
research based on structure–response relationships.45
For a given amount of granular matter, the number of
particles increases with decreasing particle size. In addition,
finer granularity changes the material properties. Smaller
particles tend to show increased diffusivity, permeation pro-
pensity, reactivity, and solubility. These observations raise
concerns that nanoscaled materials may show unanticipated
specific toxicity (i.e., toxicity per unit mass), in comparison to
microscaled and larger particles present in the environment.
Emerging Trends in Environmental Remediation
Although most stakeholders understand quantification of
exposure and hazards as being the important parts of envi-
ronmental risk assessment, two initial components are criti-
cally important but sometimes overlooked. These are problem
formulation and prioritization. These will help us define the
actual concern in the context of the environment as well as
how it should be addressed for one or more NMs. They also
will help us prioritize whether it is worth investing time and
money on more detailed quantification of environmental
impacts for any given material. This process is influenced by
many factors, including scientific evidence, public opinion,
and perception of risks and benefits.
11.6.1 Natural Particles
Much debate still exists regarding the nomenclature associ-
ated with nanoscience and nanotechnology. For the purpose
of this discussion, the definition of NM is a material with one
dimension less than 100 nm. Within this group of materials,
nanoparticles (NP), defined as materials with at least two
dimensions between 1 and 100  nm, are particularly impor-
tant. NPs have always existed in our environment, from both
natural and anthropogenic sources. NPs in air were tradition-
ally referred to as ultrafine particles, while in soil and water,
they were called as colloids, with a slightly different size
range (1–1000 nm (µm)).45,46
In urban atmospheres, diesel and gasoline fueled vehicles
and many combustion outlets have contributed for many years
particulate material within a wide range of sizes, including
NMs and particles. In addition, there is the natural background
presence of NPs and materials in the atmosphere, although at
much smaller concentrations compared to the ones produced
by anthropogenic activities. Research focused on ultrafine
particulate materials is a continuing effort especially on their
effects on human health, especially on respiratory systems.
In aquatic systems, colloid is the usual terminology used
to describe particles in the 1 nm to 1 µm size range. Natural
aquatic colloids include, for example, fine clay particles,
humic and fulvic acids as well as colloidal inorganic spe-
cies such as metallic ions and precipitates. Their small size
and large surface area per unit mass make them important
binding phases for both organic and inorganic contami-
nants. Although dissolved species are defined as those that
pass through a 0.45 µm−1 filter, this fraction will also include
a certain amount of colloidal species whose bioavailability
and physical behavior are quite different from truly soluble
organic or inorganic species. Thus, it is important to differen-
tiate the behavior of dissolved, colloidal, and particulate spe-
cies in the environment.46,47
It has been recognized for some time that NMs possess
enhanced or even unique mechanical, catalytic, and optical
properties and electrical conductivity primarily because of
their nanosize. The result has been an exponential growth
over the past decade in the development of new manufactured
or engineered NMs and their exploitation by burgeoning nan-
otechnology industries. The range of nanotechnology prod-
ucts is now extensive and can be broken down into a number
579
of different compound classes, including carbonaceous NMs;
metal oxides; semiconductor materials, including quantum
dots; zerovalent metals such as iron, silver, and gold; and
nanopolymers, such as dendrimers. A variety of products are
now being generated, including NPs as well as nanofibers,
nanowires, and nanosheets, and the range and types of NMs
are continually expanding.
11.6.2 Fate of Nanomaterials in the Environment
Given the increasing production of NMs of all types, the
potential for their release in the environment and subsequent
effects on ecosystem health is becoming an increasing con-
cern that needs to be addressed, especially by regulatory agen-
cies. In doing so, it is necessary first to determine the fate and
behavior of manufactured NMs in the environment. Do they
retain their nominal nanoscale size and original structure and
reactivity in aquatic and soil/sedimentary systems? Does an
association exist with other colloidal and particulate constitu-
ents? What are the effects of solution and physical (e.g., flow)
conditions? Is their effect on aquatic and sedimentary biota
different from that of larger particles of the same material? Do
biota, such as biofilms and invertebrates, modify the behav-
ior of NMs? Answers to these and other questions will guide
the setting of regulatory guidelines that will provide adequate
protection to ecosystems while permitting the advantages that
nanotechnology offers to be fully developed.44–47
Manufactured NMs enter the environment through inten-
tional releases as well as unintentional releases such as atmo-
spheric emissions and solid or liquid waste streams from
production facilities. Deliberate release of NMs includes
their use to remediate contaminated soils including the use
of iron NPs used to remediate groundwater. Filtration of NPs
from stack emissions requires a new generation of nanostruc-
tured sorbents for their effective removal. In addition, NPs in
paints, fabrics, and personal health-care products, including
sunscreens and cosmetics, enter the environment proportional
to their use. Emitted particles will ultimately deposit on land
and surface water bodies, although treatment to avoid aggre-
gation may result in enhanced buoyancy of these NPs when
compared with NPs from other sources, such as the ones aris-
ing from diesel emissions.
NPs reaching land have the potential to contaminate soil,
migrate into surface water and groundwater, and interact with
biota. Particles in solid wastes, wastewater effluents, direct dis-
charges, or accidental spillages can be transported to aquatic
systems by wind or rainwater runoff. With increasing control
of fugitive releases arising within the manufacturing process,
the biggest risks for environmental release come from spill-
ages associated with the transportation of manufactured NPs
from production facilities to other manufacturing sites, inten-
tional releases for environmental applications, and diffuse
releases associated with wear and erosion from general use.
Manufacture, use, and potential release of NMs have pre-
ceded evaluation of risk to ecosystems, including humans.
Currently, there are no factual data on concentrations of NMs in
the environment and certainly none on their physicochemical
580
forms or distribution, although models have been used to
estimate potential releases and loads. The development of
techniques to measure and characterize NMs in atmospheric,
aquatic, and terrestrial environments is an important immedi-
ate research priority in order to facilitate quantitative ecologi-
cal risk assessment. These assumptions and approaches must
be taken with caution and modified to deal with the issues of
particle fate and behavior, bioavailability, and toxicity that are
central to quantitative ecological risk assessment of NMs. In
fact, environmental chemists, toxicologists, and risk assessors
might be well served to preface research on NPs with a primer
on colloid fate, behavior, and toxicity.
As noted previously, characterization of NP fate and
behavior in the environment is needed to quantify exposure
scenarios. Related to this, differences in speciation (between
dissolved, colloidal, and particulate phases) due to dissolution
and aggregation of NPs under environmental conditions are
also important. It is worth noting here that these are char-
acteristics usually unfamiliar to most remediation engineers,
environmental toxicologists, chemists, and risk assessors,
although they have now been progressively addressed in the
context of toxicology and ecotoxicology of NMs. Clearly,
the need for interdisciplinary collaboration among biolo-
gists, chemists, physicists, and material scientists is essential.
Once exposure scenarios are characterized, populations and
organisms potentially at risk must be identified. Quantitative
assessments of organism response to NP exposure must be
conducted to facilitate effects assessment. Once exposure and
effects assessment are complete, risk characterization can be
accomplished.
It is obvious from the earlier discussion on NM effects that
much research is needed in air, freshwater, marine, and soil
ecosystems. Since the ultimate sink for NPs may be sediment
and soils, more testing with organisms that inhabit these eco-
systems is essential. However, research to date has dramati-
cally illustrated the need for standardized testing protocols
with NPs. This is particularly pressing in soil and sedimen-
tary systems where progress in the development of standard-
ized protocols and characterization are lagging far behind
testing in aquatic systems.
11.7  MANAGING E-WASTES
E-waste and waste electrical and electronic equipment (WEEE)
describe discarded appliances that use electricity. E-waste
describes waste electronic goods, such as computers, televi-
sions, and cell phones, while WEEE also includes traditionally
nonelectronic goods such as refrigerators and ovens.48 The dis-
tinction between E-waste and WEEE is becoming less sharp
due to the advent of pervasive computing, where programmable
microprocessors are incorporated into electrical equipment,
such as refrigerators, which are not normally considered elec-
tronic items. However, it is the rapid growth of computing that
is driving E-waste production and every few years, more than a
billion computers will be retired (Figure 11.18).
E-Waste is chemically and physically distinct from other
forms of municipal or industrial waste; it contains both
Remediation Engineering
FIGURE 11.18  Disposal of e-waste in a landfill.
valuable and hazardous materials that require special han-
dling and recycling methods to avoid environmental contami-
nation and detrimental effects on human health. Recycling
can recover reusable components and base materials, espe-
cially the precious metals. However, due to lack of facilities,
high labor costs, and tough environmental regulations, rich
countries tend not to recycle E-waste. Instead, it is either land-
filled or exported from rich countries to poor countries, where
it may be recycled using primitive techniques and little regard
for worker safety or environmental protection. Although ille-
gal under the Basel Convention of 1992, E-waste exportation
continues through clandestine operations, legal loopholes,
and by countries that have not ratified the convention.
The global production of E-waste will change as econo-
mies grow and new technologies are developed. For any given
country, the total number of computers and other potential
E-waste items is strongly correlated with the country’s GDP,
because electrical and electronic items are essential for the
functioning of all but the most primitive economies. It is rea-
sonable to assume that economic growth of emerging econ-
omies will result in more E-waste production. There is an
exponential relationship between wealth and number of com-
puters and that the richest billion people have 75% of all com-
puters. Changes in technology will also affect the global mass
of E-waste produced. Short innovation cycles of hardware
have led to a high turnover of devices. The lifespan of cen-
tral processing units in computers dropped from 4–6 years in
1997 to an average of 2 years in 2005.48
The advent of liquid crystal displays will reduce the aver-
age weight of a desktop. More significantly, the increasing
prevalence of laptop and netbook computers, which weigh just
1–3  kg, will significantly reduce the average mass of a dis-
carded computer. In the case of netbooks, computing power
and associated potential E-waste production has been shifted
from the end user to remote computing “clouds,” supported
by warehouses of shared machines, which may be located in
another country. There is a lack of information on E-waste
generation from these computing warehouses. E-waste growth
from increasing wealth and shorter innovation cycles may be
offset by miniaturization and outsourcing of computing power.
Emerging Trends in Environmental Remediation
11.7.1  Contamination from E-Wastes
Potential contaminants associated with e-waste have been
reported. Their concentration in the environment depends on the
type, age, production region, and quantity of electronic goods
that are processed as well as their dismantling methods. E-waste
composition has dramatically changed in the recent years as
manufacturers are urged to use green materials and clean pro-
duction processes. For example, lead content tends to decrease.
Heavy metals are largely present in e-wastes, especially Cu used
for wires and also Cr, Ni, Zn, Cd, and Hg as well as many other
metals and rare earth elements. Because of huge air emissions
or liquid leaking, very high amounts of metals are concentrated
in landfills or dispersed in the environment despite recycling.49
Most of organic contaminants are original components of
e-wastes and are often released mainly during open air burn-
ing or dismantling. They include polychlorinated biphenyls,
polybrominated biphenyls, and phthalate esters widely used
as plasticizers in polyvinyl chloride resins for electronic
products, as well as PBDEs, dechlorane plus, and hexabro-
mocyclododecanes, representatives of brominated or chlori-
nated flame retardants mixed into plastics. On the other hand,
some new contaminants are also produced by crude e-waste
recycling activities. For example, polycyclic aromatic hydro-
carbons (PAHs) and halogenated PAHs are commonly gener-
ated by open combustion or flaming; dioxin-like substances,
such as polychlorinated dibenzo-p-dioxins, polybrominated
dibenzo-p-dioxins, and polychlorinated dibenzofurans, are
produced by improper incineration.
The recovery of materials at the recycling yards is carried out
with little regard for the health and safety of the workers and with
no regard for the environment (Figure 11.18). These practices
have resulted in severe contamination of the workplaces with a
range of toxic metals as well as persistent and toxic organic con-
taminants. Many studies extend current knowledge on the con-
sequences of poor management of the large and ever-growing
waste stream of obsolete electrical and electronic goods, particu-
larly through crude recycling operations. It was concluded that
there is recent increase in the prevalence of e-waste recycling in
locations, beyond those countries more commonly associated
with such activities, especially China and India. This informa-
tion demonstrates the urgent need for action to address the man-
agement of hazardous e-waste, both the need for tighter controls
on the transboundary movement of such wastes and also on the
manner in which they are recycled. Furthermore, this study high-
lights the need for the redesign of new electronic goods to avoid
the use of hazardous chemical components during their manu-
facture, not least to facilitate safer and more effective disman-
tling and component separation at the products’ end of life.48–50
Ultimately, however, the manufacturers of electronic prod-
ucts must take responsibility for the entire life cycle of their
products, even before it is a global legal requirement. This
includes responsibility at the products’ end of life, such as
through take back and recycling schemes offered free of charge
and globally (wherever their products are sold). To achieve the
necessary goals, these schemes must be highly publicized
and accessible, of a high quality, and, where necessary, offer
581
adequate financial compensation to support collection and
recycling in order to minimize the transfer of e-waste to the
informal recycling and disposal sector. Increased levels of
scrutiny of the take-back (collection) chain as well as improve-
ments in product identifiability will help to better identify
“leaks” from the formal to informal channels. Greater indi-
vidualization of a producer’s responsibility for its own branded
products will drive efforts to verify the producer’s own take-
back rates and more readily enable identification of its own
products at the end of their lives, thereby offering greater
opportunities for closer scrutiny of the take-back chain.
The combination of improved regulation and greater
responsibility on the part of producers not only can enable
verification that e-wastes are recycled and disposed of in the
best achievable manner to minimize impacts on human health
and the environment but can also provide producers with
financial and other incentives that will encourage the design
of products with greater life spans, which are safer and easier
to repair, upgrade, and recycle and which avoid the use of haz-
ardous chemicals during their manufacture.
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Appendix: Physical Properties of Common
Environmental Contaminants
Molecular Henry’s Law Vapor Pressure
Compound Weight Constant (atm m3/mol) (mm Hg) Solubility (mg/L) Log koc
A
Acenaphthene 154.21 7.92 × 10−5 (25°C) 0.00155 (25°C) 3.47 (25°C)  1.25
Acenaphthylene 152.20 2.8 × 10−4 0.0290 (20°C) 3.93 (25°C)  3.68
Acetaldehyde  44.05 6.61 × 10−5 (25°C) 760 (20.2°C) Miscible Unavailable
Acetic acid  60.05 1.23 × 10−3 (25°C) 11.4 (20°C) Miscible Unavailable
Acetic anhydride 102.09 3.92 × 10−6 (20°C) 5 (25°C) 12% by wt. (20°C) Unavailable
Acetone  58.08 3.97 × 10−5 (25°C) 266 (25°C) Miscible 20.43
Acetonitrile  41.05 3.46 × 10−6 (25°C) 73 (20°C) Miscible  0.34
2-Acetylaminofluorene 223.27 — — —  3.20
Acrolein  56.06 4.4 × 10−6 (25°C) 265 (25°C) 200,000 (25°C) 20.28
Acrylamide  71.08 3.03 × 103 (20°C) 7 × 10−3 (20°C) 2.155 g/L (30°C) Unavailable
Acrylonitrile  53.06 1.10 × 10−4 (25°C) 110–115 (25°C) 80,000 (25°C) 21.13
Aldrin 364.92 4.96 × 10−4 6 × 10−6 (25°C) 0.011 (25°C)  2.61
Allyl alcohol  58.08 5.00 × 10−6 (25°C) 20 (20°C) Miscible  0.51
Allyl chloride  76.53 1.08 × 10−2 (25°C) 360 (25°C) —  1.68
Allyl glycidyl ether 114.14 3.83 × 10−6 (20°C) 3.6 (20°C) 141 g/L Unavailable
4-Aminobiphenyl 169.23 3.89 × 10−10 (25°C) 6 × 10−5 842 (20°C–30°C) 2.03
(20°C–30°C)
2-Aminopyridine  94.12 — Low 100 wt.% at 20°C Unavailable
Ammonia  17.04 2.91 × 10−4 (20°C) 10 atm (25.7°C) 531 g/L (20°C) 0.49
n-Amyl acetate 130.19 3.88 × 10−4 (25°C) 4.1 (25°C) 1.8 g/L (20°C) Unavailable
sec-Amyl acetate 130.19 4.87 × 10−4 (20°C) 10 (35.2°C) 0.2 wt.% (20°C) Unavailable
Aniline  93.13 0.136 (25°C) 0.6 (20°C) — 1.41
o-Anisidine 123.15 1.25 × 10−6 (25°C) 0.1 (30°C) 1.3 wt.% (20°C) Unavailable
p-Anisidine 123.15 — — 3.3 (Room temp.) Unavailable
Anthracene 178.24 6.51 × 10−5 (25°C) 1.95 × 10−4 (25°C) 0.075 (25°C) 4.41
Antu 202.27 — ≈0 (20°C) 600 (20°C)
B
Benzene  78.11 0.00548 (25°C) 95.2 (25°C) 1,800 (25°C) 1.92
Benzidine 184.24 3.88 × 10−11 (25°C) 0.83 (20°C) 500 (25°C) 1.60
Benzo[a]anthracene 228.30 8.0 × 10−6 1.1 × 10−7 (25°C) 0.014 (25°C) 6.14
Benzo[b]fluoranthene 252.32 1.2 × 10−5 (20°C–25°C) 5 × 10−7 (20°C) 0.0012 (25°C) 5.74
Benzo[k]fluoranthene 252.32 0.00104 9.59 × 10−11 (25°C) 0.00055 (25°C) 6.64
Benzoic acid 122.12 7.02 × 10−8 0.0045 (25°C) 3,400 (25°C) 1.48–2.70
Benzo[ghi]perylene 276.34 1.4 × 10−7 (25°C) 1.01 × 10−10 (25°C) 0.00026 (25°C) 6.89
Benzo[a]pyrene 252.32 <2.4 × 10−6 5.6 × 10−9 (25°C) 0.0038 (25°C) 5.60–6.29
Benzo[e]pyrene 252.32 4.84 × 10−7 (25°C) 5.54 × 10−9 (25°C) 0.0038 (25°C) 5.6
Benzyl alcohol 108.14 Insufficient vapor pressure data 1 (58°C) 42,900 (25°C) 1.98
for calculation at 25°C
Benzyl butyl phthalate 312.37 1.3 × 10−6 (25°C) 8.6 × 10−6 (20°C) 42.2 (25°C) 1.83–2.54
Benzyl chloride 126.59 3.04 × 10−4 (20°C) 1 (22.0°C) 493 (20°C)  2.28
α-BHC 290.83 5.3 × 10−6 (20°C) 2.5 × 10−5 (20°C) 2.0 (25°C) 3.279
β-BHC 290.83 2.3 × 10−7 (20°C) 2.8 × 10−7 (20°C) 0.24 (25°C) 3.553
γ-BHC 290.83 2.5 × 10−7 (20°C–25°C) 1.7 × 10−5 (20°C) 31.4 (25°C) 3.279
Biphenyl 154.21 4.15 × 10−4 (25°C) 10−2 (25°C) 7.5 (25°C) 3.71
bis(2-Chloroethoxy) methane 173.04 3.78 × 10−7 1 (53°C) 81,000 (25°C) 2.06
(Continued)

583
584 Appendix: Physical Properties of Common Environmental Contaminants

Molecular Henry’s Law Vapor Pressure

Compound Weight Constant (atm m3/mol) (mm Hg) Solubility (mg/L) Log koc
bis(2-Chloroethyl) ether 143.01 1.3 × 10−5 1.55 (25°C) 10,200 (25°C) 1.15
bis(2-Chloroisopropyl) ether 171.07 1.1 × 10−4 0.85 (20°C) 1,700 (20°C) 1.79
bis(2-Ethylhexyl) phthalate 390.57 1.1 × 10−5 (25°C) 6.2 × 10−8 (25°C) 0.4 (25°C) 5.0
Bromobenzene 157.01 2.4 × 10−3 (25°C) 4.14 (25°C) 409 (25°C) 2.33
Bromochloromethane 129.39 1.44 × 10−3 (24°C–25°C) 141.07 (24.05°C) 0.129 M (25°C) 1.43
Bromodichloromethane 163.83 2.12 × 10−4 50 (20°C) 4,500 (0°C) 1.79
Bromoform 252.73 5.6 × 10−4 5.6 (25°C) 3.130 (25°C) 2.45
4-Bromophenylphenyl ether 249.20 1.0 × 10−4 0.0015 (20°C) No data found 4.94
Bromotrifluoromethane 148.91 5.00 × 10−1 (25°C) 149 (20°C) 0.03 wt.% (20°C) 2.44
1,3-Butadiene  54.09 6.3 × 10−2 (25°C) 2105 (25°C) 735 (20°C) 2.08
n-Butane  58.12 9.30 × 10−1 (25°C) 1820 (25°C) 61 (20°C) Unavailable
2-Butanone  72.11 4.66 × 10−5 (25°C) 100 (25°C) 25.57 wt.% (25°C) 0.09
1-Butene  56.11 2.5 × 10−1 (25°C) 2.230 (25°C) 222 (25°C) Unavailable
Butoxyethanol 118.18 2.36 × 10−6 0.76 (20°C) Miscible Unavailable
n-Butyl acetate 116.16 3.3 × 10−4 (25°C) 15 (25°C) 5,000 (25°C) Unavailable
sec-Butyl acetate 116.16 1.91 × 10−4 (20°C) 10 (20°C) 0.8 wt.% (20°C) Unavailable
tert-Butyl acetate 116.16 — — — Unavailable
n-Butyl alcohol  74.12 8.81 × 10−6 (25°C) 7.0 (25°C) 74,700 (25°C) Unavailable
sec-Butyl alcohol  74.12 1.02 × 10−5 (25°C) 13 (20°C) 201,000 (20°C) Unavailable
tert-Butyl alcohol  74.12 1.20 × 10−5 (25°C) 42 (25°C) Miscible Unavailable
n-Butylbenzene 134.22 1.25 × 10−2 (25°C) 1.03 (25°C) 1.26 (25°C) 3.40
sec-Butylbenzene 134.22 1.14 × 10−2 (25°C) 1.81 (25°C) 309 (25°C) 2.95
tert-Butylbenzene 134.22 1.17 × 10−2 (25°C) 2.14 (25°C) 34 (25°C) 2.83
n-Butyl mercaptan  90.18 7.04 × 10−3 (20°C–25°C) 55.5 (25°C) 590 (22°C) Unavailable
C
Camphor 152.24 3.00 × 10−5 (20°C) 0.18 (20°C) 0.12% (20°C) Unavailable
Carbaryl 201.22 1.27 × 10−5 (20°C) 6.578 × 10−6 (25°C) 0.4105 (25°C) 2.42
Carbofuran 221.26 3.88 × 10−8 (30°C–33°C) 2 × 10−5 (33°C) 700 (25°C) 2.2
Carbon disulfide  76.13 0.0133 360 (25°C) 2,300 (22°C) 2.38–2.55
Carbon tetrachloride 153.82 0.024 (20°C) 113 (25°C) 1.160 (25°C) 2.35
Chlordane 409.78 4.8 × 10−5 1 × 10−5 (25°C) 1.85 (25°C) 5.57
cis-Chlordane 409.78 Insufficient vapor pressure data No data found 0.051 (20°C–25°C) 6.0
for calculation at 25°C
trans-Chlordane 409.78 Insufficient vapor pressure data No data found No data found 6.0
for calculation at 25°C
Chloroacetaldehyde  78.50 — 100 (20°C) About 50 wt.%, Unavailable
forms a hemihydrate
α-Chloroacetophenone 154.60 — 0.012 (20°C) Miscible Unavailable
4-Chloroaniline 127.57 1.07 × 10−5 (25°C) 0.025 (25°C) 3.9 g/L (20°C–25°C) 2.42
Chlorobenzene 112.56 0.00445 (25°C) 11.8 (25°C) 502 (25°C) 1.68
o-Chlorobenzylidene 188.61 Not applicable, reacts with 3.4 × 10−5 (20°C) Not applicable, reacts Not applicable,
malonitrile water with water reacts with water
p-Chloro-m-cresol 142.59 1.78 × 10−6 No data found 3,850 (25°C) 2.89
Chloroethane  64.52 0.0085 (25°C) 1064 (20°C) 5,740 (20°C) 0.51
2-Chloroethyl vinyl ether 106.55 2.5 × 10−4 26.75 (20°C) 15,000 (20°C) 0.82
Chloroform 119.38 0.0032 (25°C) 198 (25°C) 9,300 (25°C) 1.64
2-Chloronaphthalene 162.62 6.12 × 10−4 0.017 (25°C) 6.74 (25°C) 3.93
p-Chloronitrobenzene 157.56 <6.91 × 10−3 (20°C) <1 (20°C) 0.003 wt.% (20°C) 2.68
1-Chloro-1-nitropropane 123.54 1.57 × 10−1 (20°C–25°C) 5.8 (25°C) <0.8 wt.% (20°C) 3.34
2-Chlorophenol 128.56 5.6 × 10−7 (25°C) 1.42 (25°C) 28,000 (25°C) 2.56
4-Chlorophenyl phenyl ether 204.66 2.2 × 10−4 0.0027 (25°C) 3.3 (25°C) 3.6
Chloropicrin 164.38 8.4 × 10−2 23.8 (25°C) 1.621 g/L (25°C) 0.82
Chloroprene  88.54 3.20 × 10−2 200 (20°C) — —
Chlorpyrifos 350.59 4.16 × 10−6 (25°C) 1.87 × 10−5 (25°C) 2 (25°C) 3.86
Chrysene 228.30 7.26 × 10−20 6.3 × 10−9 (25°C) 0.006 (25°C) 5.39
(Continued)
Appendix: Physical Properties of Common Environmental Contaminants 585

Molecular Henry’s Law Vapor Pressure

Compound Weight Constant (atm m3/mol) (mm Hg) Solubility (mg/L) Log koc
Crotonaldehyde  70.09 1.96 × 10−5 30 (20°C) 18.1 wt.% (20°C) Unavailable
Cycloheptane  98.19 — — 30 (25°C) Unavailable
Cyclohexane  84.16 1.94 × 10−1 (25°C) 95 (20°C) 58.4 (25°C) Unavailable
Cyclohexanol 100.16 5.74 × 10−6 (25°C) 1 (20°C) 36,000 (20°C) Unavailable
Cyclohexanone  98.14 1.2 × 10−5 (25°C) 4 (20°C) 23,000 (20°C) Unavailable
Cyclohexene  82.15 4.6 × 10−2 (25°C) 67 (20°C) 213 (25°C) Unavailable
Cyclopentadiene  66.10 — — 0.0103 mol/L at Unavailable
room temperature
Cyclopentane  70.13 1.86 × 10−1 (25°C) 400 (31.0°C) 164 (25°C) Unavailable
Cyclopentene  68.12 6.3 × 10−2 (25°C) — 535 (25°C) Unavailable
D
2,4-D 221.04 1.95 × 10−2 (20°C) 0.0047 (20°C) 890 ppm (25°C) 1.68
p,p9 DDD 320.05 2.16 × 10−5 1.02 × 10−6 (30°C) 0.160 (24°C) 4.64
p,p9 DDE 319.03 2.34 × 10−5 6.49 × 10−6 (30°C) 0.0013 (25°C) 6
p,p9 DDT 354.49 5.2 × 10−5 1.9 × 10−7 (25°C) 0.0004 (25°C) 6.26
Decahydronaphthalene 138.25 39.2 (25°C) 1 (22.5°C) 0.889 ppm (25°C) Unavailable
n-Decane 142.28 1.87 × 10−1 (25°C) 1.35 (25°C) 0.022 (25°C) Unavailable
Diacetone alcohol 116.16 — 1 (22.0°C) Miscible Unavailable
Dibenz[a,h]-anthracene 278.36 7.33 × 10−9 ≈10−10 (20°C) 0.00249 (25°C) 6.22
Dibenzofuran 168.20 Insufficient vapor pressure data No data found 10 (25°C) 3.91–4.10
for calculation at 25°C
1,4-Dibromobenzene 235.91 5.0 × 10−4 (25°C) 0.161 (25°C) 16.5 (25°C) 3.2
Dibromochloromethane 208.28 9.9 × 10−4 76 (20°C) 4000 (20°C) 1.92
1,2-Dibromo-3- 236.36 2.49 × 10−4 (20°C) 0.8 (21°C) 1,000 at room 2.11
chloropropane temperature
Dibromodifluoromethane 209.82 — 688 (20°C) — —
Di-n-butyl phthalate 278.35 6.3 × 10−5 1.4 × 10−5 (25°C) 400 (25°C) 3.14
1,2-Dichlorobenzene 147.00 0.0024 (25°C) 1.5 (25°C) 145 (25°C) 3.23
1,3-Dichlorobenzene 147.00 0.0047 (25°C) 2.3 (25°C) 143 (25°C) 3.23
1,4-Dichlorobenzene 147.00 0.00445 (25°C) 0.4 (25°C) 74 (25°C) 2.2
3,39-Dichlorobenzidine 253.13 4.5 × 10−8 (25°C) 1 × 10−5 m/L (22°C) 3.11 (25°C) 3.3
Dichlorodifluoromethane 120.91 0.425 (25°C) 4.887 (25°C) 280 (25°C) 2.56
1–3-Dichloro-5,5- 197.03 Not applicable, reacts with — 0.21 wt.% (25°C) Not applicable,
dimethylhydantoin water reacts with water
1,1-Dichloroethane  98.96 0.00587 (25°C) 234 (25°C) 5,060 (25°C) 1.48
1,2-Dichloroethane  98.96 9.8 × 10−4 (25°C) 87 (25°C) 8,300 (25°C) 1.15
1,1-Dichloroethylene  96.94 0.021 591 (25°C) 5,000 (25°C) 1.81
trans-1,2-Dichloroethylene  96.94 0.00674 (25°C) 410 (30°C) 6,300 (25°C) 1.77
Dichlorofluoromethane 120.91 ≈2.42 × 10−2 (20°C–30°C) 760 (8.9°C) 1 wt.% (20°C) 1.57
sym-Dichloromethyl ether 114.96 Not applicable, reacts with — Decomposes Not applicable,
water reacts with water
2,4-Dichlorophenol 163.00    6.66 × 10−6 0.089 (25°C) 4,500 (25°C) 2.94
1,2-Dichlorophenol 112.99 0.00294 (25°C) 50 (25°C) 2,800 (25°C) 1.71
cis-1,3-Dichloro-propylene 110.97 0.00355 43 (25°C) 2,700 (25°C) 1.68
trans-1,3-Dichloropropylene 110.97 0.00355 34 (25°C) 2,800 (25°C) 1.68
Dichlorvos 220.98 5.0 × 10−3 0.0527 (25°C) ≈1 wt.% (20°C) 9.57
Dieldrin 380.91 2 × 10−7 1.8 × 10−7 (25°C) 0.20 (25°C) 4.55
Diethylamine  73.14 2.56 × 10−5 (25°C) 195 (20°C) 815,000 (14°C) Unavailable
2-Diethylamino-ethanol 117.19 — 1 (20°C) Miscible Unavailable
Diethyl phthalate 222.24 8.46 × 10−7 0.22 (60.7) Pa 1,000 (25°C) 1.84
(25°C)
1,1-Difluorotetrachloroethane 203.83 — 40 (19.8°C) — —
1,2-Difluorotetrachloroethane 203.83 1.07 × 10−1 (20°C) 40 (19.8°C) 0.01 wt.% (20°C) 2.78
Diisobutyl ketone 142.24 6.36 × 10−4 (25°C) 1.7 (20°C) 0.05 wt.% (25°C) Unavailable
Diisopropylamine 101.19 — 60 (20°C) Miscible Unavailable
(Continued)
586 Appendix: Physical Properties of Common Environmental Contaminants

Molecular Henry’s Law Vapor Pressure

Compound Weight Constant (atm m3/mol) (mm Hg) Solubility (mg/L) Log koc
N,N-Dimethylacetamide 115.18 — 1.3 (25°C) Miscible Unavailable
Dimethylamine  45.08 1.77 × 10−5 (25°C) 1520 (10°C) Miscible Unavailable
p-Dimethylaminoazobenzene 225.30 — — 13.6 (20°C–30°C) 3
Dimethylaniline 121.18 4.98 × 10−6 (20°C) 1 (29.5°C) 1,105.2 (25°C) Unavailable
2,2-Dimethylbutane  86.18 1.943 (25°C) 319.1 (25°C) 21.2 (25°C) Unavailable
2,3-Dimethylbutane  86.18 1.18 (25°C) 234.6 (25°C) 19.1 (25°C) Unavailable
cis-1,2-Dimethylcyclohexane 112.22 3.54 × 10−1 (25°C) 14.5 (25°C) 6.0 (25°C) Unavailable
trans-1,4- 112.22 8.70 × 10−1 (25°C) 22.65 (25°C) 3.84 ppm (25°C) Unavailable
Dimethylcyclohexane
Dimethylformamide  73.09 — 3.7 mm (25°C) Miscible Unavailable
1,1-Dimethylhydrazine  60.10 2.45 × 10−9 (25°C) 157 (25°C) Miscible 20.7
2,3-Dimethylpentane 100.20 1.73 (25°C) 100 (33.3°C) 5.25 (25°C) Unavailable
2,4-Dimethylpentane 100.20 3.152 (25°C) 98.4 (25°C) 5.50 (25°C) Unavailable
3,3-Dimethylpentane 100.20 1.84 (25°C) 82.8 (25°C) 5.94 (25°C) Unavailable
2,4-Dimethylphenol 122.17 6.55 × 10−6 (25°C) 0.098 (25°C) 7,868 (25°C) 2.07
Dimethyl phthalate 194.19 4.2 × 10−7 0.22 ± 0.7 Pa 4,320 (25°C) 1.63
(25°C)
2,2-Dimethylpropane  72.15 2.18 (25°C) 1.287 (25°C) 33.2 (25°C) Unavailable
2,7-Dimethylquinoline 157.22 — — 1.795 (25°C) —
Dimethyl sulfate 126.13 2.96 × 10−6 (20°C) 0.5 (20°C) 2.8 wt.% (20°C) 0.61
1,2-Dinitrobenzene 168.11 <1.47 × 10−3 (20°C) <1 (20°C) 0.015 wt.% (20°C) Unavailable
1,3-Dinitrobenzene 168.11 2.75 × 10−7 (35°C) 8.15 × 10−4 (35°C) 0.05 wt.% (20°C) 2.18
1,4-Dinitrobenzene 168.11 4.79 × 10−7 (35°C) 2.25 × 10−4 (35°C) 0.01 wt.% (20°C) Unavailable
4,6-Dinitro-o-cresol 198.14 1.4 × 10−6 5.2 × 10−5 (25°C) 250 (25°C) 2.64
2,4-Dinitrophenol 184.11 1.57 × 10−8 (18°C–20°C) 0.00039 (20°C) 6000 (25°C) 1.25
2,4-Dinitrotoluene 182.14 8.67 × 10−7 1.1 × 10−4 (20°C) 270 (22°C) 1.79
2,6-Dinitrotoluene 182.14 2.17 × 10−7 3.5 × 10−4 (20°C) ≈300 1.79
Di-n-octyl phthalate 390.57 1.41 × 10−12 (25°C) 0.0014 mm (25°C) 3 (25°C) 8.99
Dioxane  88.11 4.88 × 10−6 (25°C) 37 (25°C) Miscible 0.54
1,2-Diphenylhydrazine 184.24 4.11 × 10−11 (25°C) 2.6 × 10−5 (25°C) 221 (25°C) 2.82
Diuron 233.11 1.46 × 10−9 (25°C–30°C) 2 × 10−7 (30°C) 42 (25°C) 2.51
n-Dodecane 174.34 24.2 (25°C) 0.057 (25°C) 0.008 (25°C) Unavailable
E
α-Endosulfan 406.92 1.01 × 10−4 (25°C) 10−5 (25°C) 0.530 (25°C) 3.31
β-Endosulfan 406.92 1.91 × 10−5 (25°C) 10−5 (25°C) 0.280 (25°C) 3.37
Endosulfan sulfate 422.92 Insufficient vapor pressure data No data found 0.117 3.37
for calculation
Endrin 380.92 5.0 × 10−7 7 × 10−7 (25°C) 0.26 (25°C) 3.92
Endrin aldehyde 380.92 3.86 × 10−7 (25°C) 2 × 10−7 (25°C) 0.26 (25°C) 4.43
Epichlorohydrin  92.53 2.38–2.54 × 10−5 (20°C) 13 (20°C) 60,000 (20°C) 1
EPN 323.31 — 0.0003 (100°C) — 3.12
Ethanolamine  61.08 — <1 (20°C) Miscible Unavailable
2-Ethoxyethanol  90.12 — 4 (20°C) Miscible Unavailable
2-Ethoxyethyl acetate 132.18 9.07 × 10−7 (20°C) 2 (20°C) 23 wt.% (20°C) Unavailable
Ethyl acetate  88.11 1.34 × 10−4 (25°C) 94.5 (25°C) 100 mL/L (25°C) Unavailable
Ethyl acrylate 100.12 1.94–2.59 × 10−3 (20°C) 29.5 (20°C) 1.5 wt.% (20°C) Unavailable
Ethylamine  45.08 1.07 × 10−5 (25°C) 400 (2.0°C) Miscible Unavailable
Ethylbenzene 106.17 0.00868 (25°C) 10 (25.9°C) 152 (25°C) 1.98
Ethyl bromide 108.97 7.56 × 10−3 (25°C) 386 (20°C) 0.9 wt.% (20°C) 2.67
Ethylcyclopentane  98.19 2.10 × 10−2 (25°C) 40 (25.0°C) 245 (25°C) Unavailable
Ethylene chlorohydrin  80.51 — 8 (25°C) Miscible Unavailable
Ethylenediamine  60.10 1.73 × 10−9 (25°C) 10 (21.5°C) Miscible Unavailable
Ethylene dibromide 187.86 7.06 × 10−4 (25°C) 11 (25°C) 3,370 1.64
Ethylenimine  43.07 1.33 × 10−7 (25°C) 250 (30°C) Miscible 0.11
Ethyl ether  74.12 1.28 × 10−3 (25°C) 442 (20°C) 6.05 wt.% (25°C) Unavailable
(Continued)
Appendix: Physical Properties of Common Environmental Contaminants 587

Molecular Henry’s Law Vapor Pressure

Compound Weight Constant (atm m3/mol) (mm Hg) Solubility (mg/L) Log koc
Ethyl formate  74.08 2.23 × 10 (25°C)
−4 194 (20°C) 118,000 (25°C) Unavailable
Ethyl mercaptan  62.13 2.74 × 10−3 (25°C) 527.2 (25°C) 1.3 wt.% (20°C) Unavailable
4-Ethylmorpholine 115.18 — 6.1 (20°C) Miscible Unavailable
2-Ethylthiophene 112.19 — 60.9 (60.3°C) 292 (25°C) Unavailable
F
Fluoranthene 202.26 0.0169 (25°C) 5.0 × 10−6 (25°C) 0.265 (25°C) 4.62
Fluorene 166.22 2.1 × 10−4 10 (146°C) 1.98 (25°C) 3.7
Formaldehyde  30.03 3.27 × 10−7 400 (233°C) Miscible 0.56
Formic acid  46.03 1.67 × 10−7 at pH 4 35 (20°C) Miscible Unavailable
Furfural  96.09 1.52–3.05 × 10−6 (20°C) 2 (20°C) 8.3 wt.% (20°C) Unavailable
Furfuryl alcohol  98.10 — 0.4 (20°C) Miscible Unavailable
G
Glycidol  74.08 — 0.9 (25°C) Miscible Unavailable
H
Heptachlor 373.32 0.0023 4 × 10−4 (25°C) 180 ppb (25°C) 4.34
Heptachlor epoxide 389.32 3.2 × 10−5 2.6 × 10−6 (20°C) 0.350 (25°C) 4.32
n-Heptane 100.20 2.035 (25°C) 45.85 (25°C) 2.24 (25°C) Unavailable
2-Heptanone 114.19 1.44 × 10−4 (25°C) 2.6 (20°C) 0.43 wt.% (25°C) Unavailable
3-Heptanone 114.19 4.20 × 10−5 (20°C) 1.4 (25°C) 14,300 (20°C) Unavailable
cis-2-Heptene  98.19 4.13 × 10−1 (20°C) 48 (25°C) 15 (25°C) Unavailable
trans-2-Heptene  98.19 4.22 × 10−1 (25°C) 49 (25°C) 15 (25°C) Unavailable
Hexachlorobenzene 284.78 0.0017 1.089 × 10−5 0.006 (25°C) 3.59
Hexachlorobutadiene 260.76 0.026 0.15 (20°C) 3.23 (25°C) 3.67
Hexachlorocyclopent adiene 272.77 0.016 0.081 (25°C) 1.8 (25°C) 3.63
Hexachloroethane 236.74 0.0025 0.8 (30°C) 27.2 (25°C) 3.34
n-Hexane  86.18 1.184 (25°C) 151.5 (25°C) 9.47 (25°C) Unavailable
2-Hexanone 100.16 0.00175 (25°C) 3.8 (25°C) 35,000 (25°C) 2.13
1-Hexene  84.16 4.35 × 10−1 (25°C) 186.0 (25°C) 50 (25°C) Unavailable
sec-Hexyl acetate 144.21 4.38–5.84 × 10−3 (20°C) 4 (20°C) 0.013 wt.% (20°C) Unavailable
Hydroquinone 110.11 <2.07 × 10−9 (20°C–25°C) 1 (132.4) 70,000 (25°C) 0.98
I
Indan 118.18 — — 88.9 (25°C) 2.48
Indeno[1,2,3-cd] pyrene 276.34 2.96 × 10−20 (25°C) 10−10 (25°C) 0.062 7.49
Indole 117.15 — — 3,558 (25°C) 1.69
Indoline — — 10,800 (25°C) 1.42
1-Iodopropane 169.99 9.09 × 10−3 43.1 (25°C) 0.1065 wt.% 2.16
(23.5°C)
Isoamyl acetate 130.19 5.87 × 10−2 (25°C) 4 (20°C) 0.2 wt.% (20°C) 1.95
Isoamyl alcohol  88.15 8.89 × 10−6 (20°C) 2.3 (20°C) 26,720 (22°C) Unavailable
Isobutyl acetate 116.16 4.85 × 10−4 (25°C) 20 (25°C) 6,300 (25°C) Unavailable
Isobutyl alcohol  74.12 9.25 × 10−6 (20°C) 10.0 (20°C) 8.7 wt.% (20°C) Unavailable
Isobutyl benzene 134.22 1.09 × 10−2 (25°C) 2.06 (25°C) 33.71 (25°C) 3.9
Isophorone 138.21 5.8 × 10−6 0.38 (20°C) 12,000 (25°C) 1.49
Isopropyl acetate 102.13 2.81 × 10−4 (25°C) 73 (25°C) 18,000 (20°C) Unavailable
Isopropylamine  59.11 — 478 (20°C) Miscible Unavailable
Isopropylbenzene 120.19 1.47 × 10−2 (25°C) 4.6 (25°C) 48.3 (25°C) 3.45
Isopropyl ether 102.18 9.97 × 10−3 (25°C) 150 (25°C) 0.65 wt.% (25°C) Unavailable
K
Kepone 490.68 3.11 × 10−2 (25°C) 2.25 (25°C) 2.7 (20°C–25°C) 4.74
L
Lindane 290.83 4.8 × 10−7 6.7 × 10−5 (25°C) 7.52 (25°C) 3.03
M
Malathion 330.36 4.89 × 10−9 (25°C) 7.95 × 10−6 (25°C) 330 (30°C) 2.46
(Continued)
588 Appendix: Physical Properties of Common Environmental Contaminants

Molecular Henry’s Law Vapor Pressure

Compound Weight Constant (atm m3/mol) (mm Hg) Solubility (mg/L) Log koc
Maleic anhydride  98.06 Not applicable, reacts with 5 × 10 (20°C)
−5 — Not applicable,
water reacts with water
Mesityl oxide  98.14 4.01 × 10−6 (20°C) 8.7 (20°C) 3 wt.% (20°C) Unavailable
Methoxychlor 345.66 Insufficient vapor pressure data No data found 0.1 (25°C) 4.9
for calculation at 25°C
Methyl acetate  74.08 9.09 × 10−5 (25°C) 235 (25°C) 240,000 (20°C) Unavailable
Methyl acrylate  86.09 1.23–1.44 × 10−4 (20°C) 70 (20°C) 52,000 Unavailable
Methylal  76.10 1.73 × 10−4 (25°C) 400 (25°C) 33 wt.% (20°C) Unavailable
Methyl alcohol  32.04 4.66 × 10−6 (25°C) 127.2 (25°C) Miscible Unavailable
Methylamine  31.06 1.81 × 10−2 (25°C) 3.1 atm (20°C) 9.590 (25°C) Unavailable
Methylaniline 107.16 1.19 × 10−5 (25°C) <1.0 (20°C) 5.624 g/L (25°C) Unavailable
2-Methylanthracene 192.96 — — 0.039 (25°C) 5.12
Methyl bromide  94.94 0.2 1633 (25°C) 13,000 (25°C) 1.92
2-Methyl-1,3-butadiene  68.12 7.7 × 10−2 (25°C) 550.1 (25°C) 642 (25°C) Unavailable
2-Methylbutane  72.15 1.35 (25°C) 687.4 (25°C) 49.6 (25°C) Unavailable
3-Methyl-1-butene  70.13 5.35 × 10−1 (25°C) 902.1 (25°C) 130 (25°C) Unavailable
Methyl cellosolve  76.10 — 6 (20°C) Miscible Unavailable
Methyl cellosolve acetate 118.13 — 7 (20°C) Miscible Unavailable
Methyl chloride  50.48 0.010 (25°C) 3789 (20°C) 7,400 (25°C) 1.4
Methylene chloride  84.93 0.00269 (25°C) 455 (25°C) 13,000 (25°C) 0.94
Methylcyclohexane  98.19 4.35 × 10−1 (25°C) 46.3 (25°C) 16.0 (25°C) Unavailable
o-Methylcyclohexanone 112.17 — ≈1 (20°C) — —
1-Methylcyclohexene  96.17 — — 52 (25°C) Unavailable
Methylcyclopentane  84.16 3.62 × 10−1 (25°C) 137.5 (25°C) 41.8 (25°C) Unavailable
Methyl formate  60.05 2.23 × 10−4 (25°C) 625 (25°C) 30 wt.% (20°C) Unavailable
3-Methylheptane 114.23 3.70 (25°C) 19.5 (25°C) 0.792 (25°C) Unavailable
5-Methyl-3-heptanone 128.21 1.30 × 10−4 (20°C) 2 (25°C) 0.26 wt.% (20°C) Unavailable
2-Methylhexane 100.20 3.42 (25°C) 65.9 (25°C) 2.54 (25°C) Unavailable
3-Methylhexane 100.20 1.55–1.64 (25°C) 61.6 (25°C) 4.95 (25°C) Unavailable
Methylhydrazine  46.07 — 49.6 (25°C) Miscible Unavailable
Methyl iodide 141.94 5.87 × 10−3 (25°C) 405 (25°C) 2 wt.% (20°C) 1.36
Methyl isocyanate  57.05 3.89 × 10−4 (20°C) 348 (20°C) 6.7 wt.% (20°C) Unavailable
Methyl mercaptan  48.10 3.01 × 10−3 (25°C) 1,516 (25°C) 23.30 g/L (20°C) Unavailable
Methyl methacrylate 100.12 2.46 × 10−4 (20°C) 40 (26°C) 1.5 wt.% (20°C) Unavailable
2-Methylnaphthalene 142.20 Insufficient vapor pressure data No data found 25.4 (25°C) 3.93
for calculation
4-Methyloctane 128.26 10.27 (25°C) 7 (25°C) 0.115 (25°C) Unavailable
2-Methylpentane  86.18 1.732 (25°C) 211.8 (25°C) 13.8 (25°C) Unavailable
3-Methylpentane  86.18 1.693 (25°C) 189.8 (25°C) 17.9 (25°C) Unavailable
4-Methyl-2-pentanone 100.16 1.49 × 10−5 (25°C) 15 (20°C) 1.91 wt.% (25°C) 0.79
2-Methyl-1-pentene  84.16 2.77 × 10−1 (25°C) 195.4 (25°C) 78 (25°C) Unavailable
4-Methyl-1-pentene  84.16 6.15 × 10−1 (25°C) 270.8 (25°C) 48 (25°C) Unavailable
1-Methylphenanthrene 192.26 — — 269 ppb (25°C) 4.56
2-Methylphenol 108.14 1.23 × 10−6 (25°C) 0.24 (25°C) 25,000 (25°C) 1.34
4-Methylphenol 108.14 7.92 × 10−7 (25°C) 0.108 (25°C) 23,000 (25°C) 1.69
2-Methylpropane  58.12 1.171 (25°C) 10 atm (66.8°C) 48.9 (25°C) Unavailable
2-Methylpropene  56.11 2.1 × 10−1 (25°C) 2.270 (25°C) 263 (25°C) Unavailable
α-Methylstyrene 118.18 — 1.9 (20°C) — —
Mevinphos 224.16 — 0.003 (20°C) Miscible Unavailable
Morpholine  87.12 — 13.4 (25°C) Miscible Unavailable
N
Naled 380.79 — 2 × 10−4 (20°C) — Not applicable,
reacts with water
Naphthalene 128.18 4.6 × 10−4 0.23 (25°C) 30 (25°C) 2.74
(Continued)
Appendix: Physical Properties of Common Environmental Contaminants 589

Molecular Henry’s Law Vapor Pressure

Compound Weight Constant (atm m3/mol) (mm Hg) Solubility (mg/L) Log koc
1-Naphthylamine 143.19 1.27 × 10−10 (25°C) 6.5 × 10−5 1,700 3.51
(20°C–30°C)
2-Naphthylamine 143.19 2.01 × 10−9 (25°C) 2.56 × 10−4 586 (20°C–30°C) 2.11
(20°C–30°C)
Nitrapyrin 230.90 2.13 × 10−3 0.0028 (20°C) 40 2.64
2-Nitroaniline 138.13 9.72 × 10−5 (25°C) 8.1 (25°C) 1,260 (25°C) 1.23–1.62
3-Nitroaniline 138.13 Insufficient vapor pressure data 1 (119.3°C) 890 (25°C) 1.26
for calculation
4-Nitroaniline 138.13 1.14 × 10−8 (25°C) 0.0015 (20°C) 800 (18.5°C) 1.08
Nitrobenzene 123.11 2.45 × 10−5 0.28 (25°C) 2,000 (25°C) 2.36
4-Nitrobiphenyl 199.21 — — — —
Nitroethane  75.07 4.66 × 10−5 (25°C) 15.6 (20°C) 45 mL/L (20°C) Unavailable
Nitromethane  61.04 2.86 × 10−5 27.8 (20°C) 22 mL/L (20°C) Unavailable
2-Nitrophenol 139.11 3.5 × 10−6 0.20 (25°C) 2,000 (25°C) 1.57
4-Nitrophenol 139.11 3.0 × 10−5 (20°C) 10−4 (20°C) 16,000 (25°C) 2.33
1-Nitropropane  89.09 8.68 × 10−5 (25°C) 7.5 (20°C) 1.4 wt.% (20°C) Unavailable
2-Nitropropane  89.09 1.23 × 10−4 (25°C) 12.9 (20°C) 1.7 wt.% (20°C) Unavailable
N-Nitrosodimethylamine  74.09 0.143 (25°C) 8.1 (25°C) Miscible 1.41
N-Nitrosodiphenylamine 198.22 2.33 × 10−8 (25°C) No data found 35.1 (25°C) 2.76
N-Nitrosodi-n-propylamine 130.19 Insufficient vapor pressure data No data found 9,900 (25°C) 1.01
for calculation
2-Nitrotoluene 137.14 4.51 × 10−5 (20°C) 0.15 (20°C) 0.06 wt.% (20°C) Unavailable
3-Nitrotoluene 137.14 5.41 × 10−5 (20°C) 0.25 (25°C) 0.05 wt.% (20°C) Unavailable
4-Nitrotoluene 137.14 5.0 × 10−5 (25°C) 5.484 (26.0°C) 0.005 wt.% (20°C) Unavailable
n-Nonane 128.26 5.95 (25°C) 4.3 (25°C) 0.122 (25°C) Unavailable
O
Octachloronaphthalene 403.73 — <1 (20°C) — —
n-Octane 114.23 3.225 (25°C) 14.14 (25°C) 0.431 (25°C) Unavailable
1-Octene 112.22 9.52 × 10−1 (25°C) 17.4 (25°C) 2.7 (25°C) Unavailable
Oxalic acid  90.04 1.43 × 10−10 (pH 4) <0.001 (20°C) 9.81 wt.% (25°C) 0.89
P
Parathion 291.27 8.56 × 10−8 (25°C) 9.8 × 10−6 (25°C) 24 (25°C) 3.68
PCB-1016 257.90 750 4 × 10−4 (25°C) 0.22–0.25 4.7
PCB-1221 192.00 3.24 × 10−4 0.0067 (25°C) 1.5 (25°C) 2.44
PCB-1232 221.00 8.64 × 10−4 0.0046 (25°C) 1.45 (25°C) 2.83
PCB-1242 154–358 with 5.6 × 10−4 4.06 × 10−4 (25°C) 0.24 (25°C) 3.71
an average
value of 261
PCB-1248 222–358 with 0.0035 4.94 × 10−4 (25°C) 0.054 5.64
an average
value of 288
PCB-1254 327 (average) 0.0027 7.71 × 10−5 (25°C) 0.012 (25°C) 5.61
PCB-1260 324–460 with 0.0071 4.05 × 10−5 (25°C) 0.080 (24°C) 6.42
an average
value of 370
Pentachlorobenzene 250.34 0.0071 (20°C) 6.0 × 10−3 2.24 × 10−6 M (25°C) 6.3
(20°C–30°C)
Pentachloroethane 202.28 2.45 × 10−3 (25°C) 4.5 (25°C) 7.69 and 500 were 3.28
reported at 25°C
and 20°C
Pentachlorophenol 266.34 3.4 × 10−6 1.7 × 10−4 (20°C) 20–25 (25°C) 2.96
1,4-Pentadiene  68.12 1.20 × 10−1 (25°C) 734.6 (25°C) 558 (25°C) Unavailable
n-Pentane  72.15 1.255 (25°C) 512.8 (25°C) 39.5 (25°C) Unavailable
2-Pentanone  86.13 6.44 × 10−5 (25°C) 16 (25°C) 5.51 wt.% (25°C) Unavailable
(Continued)
590 Appendix: Physical Properties of Common Environmental Contaminants

Molecular Henry’s Law Vapor Pressure

Compound Weight Constant (atm m3/mol) (mm Hg) Solubility (mg/L) Log koc
1-Pentene  70.13 4.06 × 10 (25°C)
−1 637.7 (25°C) 148 (25°C) Unavailable
cis-2-Pentene  70.13 2.25 × 10−1 (25°C) 494.6 (25°C) 203 (25°C) Unavailable
trans-2-Pentene  70.13 2.34 × 10−1 (25°C) 505.5 (25°C) 203 (25°C) Unavailable
Pentycyclopentane 140.28 — — 0.115 (25°C) Unavailable
Phenanthrene 178.24 2.56 × 10−5 (25°C) 6.80 × 10−4 (25°C) 1.18 (25°C) 3.72
Phenol  94.11 3.97 × 10−7 (25°C) 0.34 (25°C) 93,000 (25°C) 1.43
p-Phenylenediamine 108.14 — — 38,000 (24°C) Unavailable
Phenyl ether 170.21 2.13 × 10−4 (20°C) 0.12 (30°C) 21 (25°C) Unavailable
Phenylhydrazine 108.14 — <0.1 (20°C) — Unavailable
Phthalic anhydride 148.12 6.29 × 10−9 (20°C) 2 × 10−4 (20°C) 0.62 wt.% (20°C) 1.9
Picric acid 229.11 <2.15 × 10−5 (20°C) <1 (20°C) 1.4 wt.% (20°C) —
Pindone 230.25 — — 18 (25°C) 2.95
Propane  44.10 7.06 × 10−1 (25°C) 8.6 atm (20°C) 62.4 (25°C) Unavailable
β-Propiolactone  72.06 7.63 × 10−7 (25°C) 3.4 (25°C) 37 vol.% (25°C) Unavailable
n-Propyl acetate 102.12 1.99 × 10−4 (25°C) 35 (25°C) 18,900 (20°C) Unavailable
n-Propyl alcohol  60.10 6.74 × 10−6 (25°C) 20.8 (25°C) Miscible Unavailable
n-Propylbenzene 120.19 1.0 × 10−2 (25°C) 3.43 (25°C) 55 (25°C) 2.87
Propylcyclopentane 112.22 8.90 × 10−1 (25°C) 12.3 (25°C) 2.04 (25°C) Unavailable
Propylene oxide  58.08 8.34 × 10−5 (20°C) 445 (20°C) 41 wt.% (20°C) Not applicable,
reacts with water
n-Propyl nitrate 105.09 — 18 (20°C) — Unavailable
Propyne  40.06 1.1 × 10−1 (25°C) 4310 (25°C) 3,640 (20°C) Unavailable
Pyrene 202.26 1.87 × 10−5 6.85 × 10−7 (25°C) 0.148 (25°C) 4.66
Pyridine  79.10 8.88 × 10−6 (25°C) 20 (25°C) Miscible Unavailable
Q
p-Quinone 108.10 9.48 × 10−7 (20°C) 0.1 (20°C) 1.5 wt.% (20°C) Unavailable
R
Ronnel 321.57 8.46 × 1026 (25°C) 8 × 10−4 (25°C) 40 (25°C) 2.76
S
Styrene 104.15 0.00261 6.45 (25°C) 0.031 wt.% (25°C) 2.87
Strychnine 334.42 — — 0.02 wt.% (20°C) 2.45
Sulfotep 322.30 2.88 × 10−6 (20°C) 0.00017 (20°C) 25 2.87
T
2,4,5-T 255.48 4.87 × 10−8 (25°C) 6.46 × 10−26 (25°C) 278 (25°C) 1.72
TCDD 321.98 5.40 × 10−23 (18°C–22°C) 7.2 × 10−10 (25°C) 0.0193 ppb (22°C) 6.66
1,2,4,5-Tetrabromobenzene 393.70 — — 0.040 4.82
1,1,2,2-Tetrabromoethane 345.65 6.40 × 10−5 (20°C) 0.1 (20°C) 0.07 wt.% (20°C) 2.45
1,2,3,4-Tetrachlorobenzene 215.89 6.9 × 10−23 (20°C) 2.6 × 10−2 (25°C) 5.92 (25°C) 5.4 average value
1,2,3,5-Tetrachlorobenzene 215.89 1.58 × 10−3 (25°C) 1 (58.2°C) 5.19 (25°C) 6.0 average value
1,2,4,5-Tetrachlorobenzene 215.89 1.0 × 10−2 (20°C) <0.1 (25°C) 0.465 (25°C) 6.1 average value
1,1,2,2-Tetrachloroethane 167.85 4.56 × 10−4 (25°C) 6 (25°C) 2,970 (25°C) 2.07
Tetrachloroethylene 165.83 0.0153 20 (25°C) 150 (25°C) 2.42
Tetraethyl pyrophosphate 290.20 — 1.55 × 10−4 (20°C) Miscible Not applicable,
reacts with water
Tetrahydrofuran  72.11 7.06 × 10−5 (25°C) 145 (20°C) Miscible Unavailable
1,2,4,5-Tetramethylbenzene 134.22 2.49 × 10−2 (25°C) 0.49 (25°C) 3.48 (25°C) 3.79
Tetranitromethane 196.03 — 13 (25°C) — —
Tetryl 287.15 <1.89 × 10−3 (20°C) <1 (20°C) 0.02 wt.% (20°C) 2.37
Thiophene  84.14 2.93 × 10−3 (25°C) 79.7 (25°C) 3,015 (25°C) 1.73
Thiram 269.35 — — 30 —
Toluene  92.14 0.00674 (25°C) 22 (20°C) 490 (25°C) 2.06
2,4-Toluene diisocyanate 174.15 — 0.01 (20°C) Not applicable, reacts Not applicable,
with water reacts with water
o-Toluidine 107.16 1.88 × 10−6 (25°C) 0.1 (20°C) 15,0000 (25°C) 2.61
(Continued)
Appendix: Physical Properties of Common Environmental Contaminants 591

Molecular Henry’s Law Vapor Pressure

Compound Weight Constant (atm m3/mol) (mm Hg) Solubility (mg/L) Log koc
Toxaphene 413.82 0.063 0.2–0.4 (25°C) 0.2–0.4 (25°C) 3.18
1,3,5-Tribromobenzene 314.80 — — 2.51 × 10−6 (25°C) 4.05
Tributyl phosphate 266.32 — — 0.1 wt.% (20°C) 2.29
1,2,3-Trichlorobenzene 181.45 8.9 × 10−3 (20°C) 1 (40°C) 18.0 (25°C) 3.87
1,2,4-Trichlorobenzene 181.45 0.00232 0.29 (25°C) 31.3 (25°C) 2.7
1,3,5 Trichlorobenzene 181.45 1.9 × 10−3 (20°C) 0.58 (25°C) 6.01 (25°C) 5.7 (average)
1,1,1-Trichloroethane 133.40 0.0162 (25°C) 124 (25°C) 950 (25°C) 2.18
1,1,2-Trichloroethane 133.40 9.09 × 10−4 (25°C) 19 (20°C) 4,500 (20°C) 1.75
Trichloroethylene 131.39 0.0091 72.6 (25°C) 1,100 (25°C) 1.81
Trichlorofluoromethane 137.37 1.73 (25°C) 792 (25°C) 1,240 (25°C) 2.2
2,4,5-Trichlorophenol 197.45 1.76 × 10−7 (25°C) 0.022 (25°C) 1.2 g L−1 (25°C) 2.85
2,4,6-Trichlorophenol 197.45 9.07 × 10−8 (25°C) 0.017 (25°C) 800 (25°C) 3.03
1,2,3-Trichloropropane 147.43 3.18 × 10−4 (25°C) 3.4 (20°C) — —
1,1,2-Trichlorotrifluoroethane 187.38 3.33 × 10−1 (20°C) 270 (20°C) 0.02 wt.% (20°C) 2.59
Tri-o-cresyl phosphate 368.37 — — 3.1 (25°C) 3.37
Triethylamine 101.19 4.79 × 10−4 (20°C) 54 (20°C) 15,000 (20°C) Unavailable
Trifluralin 335.29 4.84 × 10−5 (23°C) 1.1 × 10−4 (25°C) 240 3.73
1,2,3-Trimethylbenzene 120.19 3.18 × 10−3 (25°C) 1.51 (25°C) 75.2 (25°C) 3.34
1,2,4-Trimethylbenzene 120.19 5.7 × 10−3 (25°C) 2.03 (25°C) 51.9 (25°C) 3.57
1,3,5-Trimethylbenzene 120.19 3.93 × 10−3 (25°C) 2.42 (25°C) 48.2 (25°C) 3.21
1,1,3-Trimethylcyclohexane 126.24 — — 1.77 (25°C) Unavailable
1,1,3-Trimethylcyclopentane 112.22 1.57 (25°C) 39.7 (25°C) 3.73 (25°C) Unavailable
2,2,5-Trimethylhexane 128.26 2.42 (25°C) 16.5 (25°C) 1.15 (25°C) Unavailable
2,2,4-Trimethylpentane 114.23 3.01 (25°C) 49.3 (25°C) 2.05 (25°C) Unavailable
2,3,4-Trimethylpentane 114.23 2.98 (25°C) 27.0 (25°C) 1.36 (25°C) Unavailable
2,4,6-Trinitrotoluene 227.13 — 4.26 × 10−3 (54.8°C) 0.013 wt.% (20°C) 2.48
Triphenyl phosphate 326.29 5.88 × 10−2 (20°C–25°C) <0.1 (20°C) 0.001 wt.% (20°C) 3.72
V
Vinyl acetate  86.09 4.81 × 10−4 115 (25°C) 25,000 (25°C) 0.45
Vinyl chloride  62.50 2.78 2660 (25°C) 1,100 (25°C) 0.39
W
Warfarin 308.33 — — 17 (20°C) 2.96
X
o-Xylene 106.17 0.00535 (25°C) 6.6 (25°C) 213 (25°C) 2.11
m-Xylene 106.17 0.0063 (25°C) 8.287 (25°C) 173 (25°C) 3.2
p-Xylene 106.17 0.0063 (25°C) 8.763 (25°C) 200 (25°C) 2.31

Sources: Montgomery, J.H. and Welkom, L.M., Groundwater Chemicals Desk Reference, Vol. 1, Lewis Publishers, Chelsea, MI, 1990; Montgomery, J.H.,
Groundwater Chemicals Desk Reference, Vol. 2, Lewis Publishers, Chelsea, MI, 1991.
Index
A Anaerobic processes, in situ bioremediation
Abiotic transformation processes
hydrolysis, 62–63
oxidation and reduction reactions, 62
physicochemical properties, 61
precipitation and solubilization, 62
ABOx systems, see Anaerobic biological
oxidation systems
Absorption, 51–52, 416–417, 462
Acidity neutralization capacity (ANC), 335
Acid mine drainage (AMD), 28
Adsorption
adsorption zone, 442
carbon adsorption, 443
carbon regeneration, 442
definition, 416, 440
equilibrium sorption, 50
exothermic process, 51
fixed regenerative carbon bed
adsorber, 442
granular activated carbon, 440–441
hysteresis, 418
ionic adsorption, 50
kinetic sorption, 50
Langmuir and Freundlich isotherms, 50
octanol–water partitioning coefficient, 418
organic adsorption, 50
relative humidity and moisture content, 442
soil adsorption coefficient, 417–418
soil treatment, 462–463
solvent-induced adsorption, 417
sorbent-induced adsorption, 417
volatile organic compound adsorption,
417–418
Advanced profiling system (APS), 122
Aerobic bacteria, 88
Air entry pressure, 452–453
Aluminum hydroxide (Al(OH)3) solubility, 361
Amorphous (finely divided) crystalline
masses, 351
Anaerobic biological oxidation (ABOx) systems
advantages, 249
benzene mass mineralized per unit
mass, 249
biogeochemistry, 250–251
electron acceptors, 249
fuel oxygenates, 255
nitrate-/sulfate-reducing bacteria, 250
oxic, suboxic, and anoxic conditions, 249
petroleum hydrocarbons
degradation pathways, 252–253
dissolved-phase delivery
mechanisms, 252
DNAPLs, 252
LNAPL, 252
microorganisms, 253–254
nitrate-based products, 252
performance monitoring programs,
254–255
residual mass within smear zone, 251
sulfate-based treatment applications, 252
rate-limiting substrate concentration vs.
overall reaction rate, 249–250
source zones with organic contaminants, 249
anaerobic oxidation
advantages, 249
benzene mass mineralized per unit
mass, 249
biogeochemistry, 250–251
electron acceptors, 249
fuel oxygenates, 255
nitrate-/sulfate-reducing bacteria, 250
oxic, suboxic, and anoxic
conditions, 249
petroleum hydrocarbons, 251–255
rate-limiting substrate concentration vs.
overall reaction rate, 249–250
source zones with organic
contaminants, 249
facultative organisms, 221–222
microbial reduction
aerobic carbohydrate metabolism, 222
aerobic glycolysis, 222
aliphatic and aromatic organic
compounds dechlorination, 222
biogeochemistry, 222–224
carbohydrate fermentation, 222
denitrification, 247–249
disproportionation, 222
ERD, 229–240
explosives degradation, 239–244
nitroaromatic compounds reduction, 222
perchlorate degradation, 244–247
substrates, 223–229
reduction potential, alternative electron
acceptors, 221
Anisotropy, 149
Aquifer
aquitard, 108
average linear groundwater flow velocity, 110
building processes, heterogeneity, and
anisotropy, 110–112
definition, 107–108
hydraulic conductivity, 109
hydraulic gradient, 109
total hydraulic head, 109
total porosity, 108–109
unconfined aquifer, 108
volumetric groundwater flow, 110
B
Back-diffusion models, 156–158
Batch flush/batch reactor models, 160
Bench-scale treatability testing, 277
Big data, environmental remediation, see
Environmental remediation
Bimetallic nanoscale particles (BNPs), 310
Biofouling
aerobic bacteria, 88
algae, 88
fungi, 88
iron-and manganese-oxidizing bacteria, 88
SRB, 88
Biogeochemical considerations, design
fouling of wells and equipment
corrosion, 90–92
microbially induced fouling, 88
mineral scaling, 88–89
particulate fouling, 92
safe system function, 87
material compatibility, 101–102
porosity reductions in aquifer
biomass accumulation, 93–94
dispersion of fine particles, 93
gas formation and accumulation, 92–93
Kozeny–Carman equation, 92
mineral precipitation, 94–95
relative permeability, 92
SWQIs
cycling of metals, aquifer matrix,
95–100
degradation intermediates, organic
contaminants, 101
design implications, 101
ISCO, 95
microbial metabolic by-products, 100
nonmetal inorganic reaction
by-products, 100–101
reactant-related by-products, 95
Biological transformation
biocatalysis, 63
bioremediation, 63–64
cometabolic biodegradation, 65
direct biodegradation, 63
metabolic process, 63
microbial oxidation, 64
microbial reduction, 64–65
Biosparging, 217–219, 457–458
Bioventing, 413
aerobic biodegradation process, 433
airflow rates, 434
benzene degradation, 434
in situ respiration test, 436–437
laboratory testing, 434–435
system design, 435–436
vadose zone, 433
volatilization, 433
Borderline cations, 326
Borehole heat exchangers (BHEs), 480
Bulk retention capacity, 55
C
Calcium polysulfide (CaSx)
injection, 340
treatability test data, 338–339
Cancer slope factors (CSFs), 18
Capillary entry resistance, 452
Carbonate interference
acid–base equilibrium, 281
bicarbonate ion, 281
carbonate ion, 281
carbonic acid, 281
competitive interaction, calculation of,
283–284
two-step dissociations, 281–283
Carbon dioxide propagation, 296
Catalytic oxidation
average catalyst lifetime, 440
conventional-type heat exchanger
with catalyst, 439
design criteria, 440
593
594 Index

piping and instrumentation PCE, 18–19 dissolved phase, 33

diagram, 440–441 regulatory guidance models, 18 hydrodynamic transport processes
supplemental fuel costs, 439 RFD, 18 advection, 57–58
VOC concentrations, 440 RGVs, 18 diffusive mass transport, 58
Catalyzed hydrogen peroxide (CHP), 272 setting up, 18 dispersion, 58
by-product formation, 296 surface soil contamination, 18 groundwater plumes, 58–59
competitive inhibitors TCE, 18 remediation hydrogeology, 57
bicarbonate, 295 Clean water front, 194 solute-based transport, 58–60
biological enzymes, 296 Coal combustion residuals (CCRs) volatilization and transport, unsaturated
carbonate, 295 by-products, 577 zone, 60–61
chloride, 295 coal ash, 577 inorganic contaminants
sulfate, 295 pond closure, 578 metals, 43–44
ex situ treatment applications, 291 recycling, 578 nitrogen compounds, 44–45
future innovation and current regulations, 577–578 perchlorate, 45
research, 296 Cometabolic biodegradation, 65 molecular structure of compounds
hydroxyl radical (OH•), 291 Command and control phase, 17 covalent bonds, 34–35
iron catalysis strategies Common environmental contaminants, physical definition, 33
aquifer mineral strategies, 293–294 properties, 583–591 dispersion forces, 39–40
conventional Fenton’s process, 293 Complexation reactions, 346 electrons, 33–34
iron chelation strategies, 293–294 Compound-specific isotopic analysis, 10 elemental composition, 33
kinetics Compound stable isotope analysis hydrogen bonds, 37–38
competition kinetic analysis, 295 (CSIA), 536 hydrophobic bonds, 39
fundamental chemistry models, 295 Comprehensive Environmental Response, ionic bonds, 38–39
second-order rate kinetics, 294 Compensation, and Liability Act polar covalent bonds, 35–37
simplified pseudo-first order, 295 (CERCLA), 1, 20 van der Waals interactions, 39
large-scale gas production, 291 Conceptual site models (CSMs), 7, 18, 107 NAPLs, 33
performance monitoring, 296 development process, 130–131 architecture, 54–55
pH adjustment limitations, 291 digital CSM, 132 DNAPL, 54
reaction mechanisms elements LNAPL, 54
direct oxidation, 292 geology, 131 saturation and mobility, 55–56
initiation, propagation, and termination hydrogeology, 131–132 weathering, 56–57
reactions, 292 potential contaminants, 130–131 nonreactive/recalcitrant chemicals, 33
primary regeneration reaction, 292 site history and operations, 130 organic contaminants
radical chain reactions, 291–292 investigation and design and optimize fuel oxygenates, 43
radical oxidation, 292–293 remediation systems, 132–135 halogenated organics, 41–42
short-duration reactions, 291 refinement, 149–151 ketones, 42
Cation exchange capacity (CEC), 53–54 Concerted reaction, 268 NAPL, 40
CCRs, see Coal combustion residuals Cone penetrometer testing (CPT) PAHs, 43
Chemical oxidation, 258; see also In situ methods, 120–122 partitioning in subsurface
chemical oxidation Contaminant characteristics environment, 40
Chemical reactivity abiotic transformation processes petroleum hydrocarbons, 42–43
enzyme participation, 259 hydrolysis, 62–63 physicochemical and biological
geochemical considerations oxidation and reduction reactions, 62 properties, 33
ionic strength effects, 271–272 physicochemical properties, 61 reactive contaminants, 33
pH effects, 271 precipitation and solubilization, 62 sorbed phase, 33
temperature effects, 270–271 biological transformation vapor phase, 33
objective, 259 biocatalysis, 63 Contaminant of emerging concern (CECs), 566
oxidation states, 259–260 bioremediation, 63–64 Core electrons, 34
reaction mechanisms cometabolic biodegradation, 65 Corrosion fouling
electron transfer reactions, 267–268 direct biodegradation, 63 acids, 91–92
nucleophilicity, 269–270 metabolic process, 63 anodic and cathodic reaction balance, 90
nucleophilic substitution and elimination microbial oxidation, 64 carbon dioxide (CO2), 91
reactions, 268–269 microbial reduction, 64–65 chloride, 90–91
thermodynamics vs. kinetics bulk parameters hydrogen sulfide, 91
bond energies, 260–261 TDS, 46 iron metal oxidation, 90
Gibbs free energy, 260–263 TOC, 46 oxygen, 90
kinetic control of reaction TPH, 45–46 water velocity, 92
rates, 263–267 contaminant distribution, 33–34 Covalent bonds
Nernst equation, 263 contaminant properties bond angles, 35
Chlorinated volatile organic compounds absorption, 51–52 ethene, 35
(CVOCs), 467–468 adsorption, 50–51 ethyne, 35
Chlorofluorocarbons (CFCs), 42 cation exchange capacity, 53–54 hydrogen atom, 34–35
CHP, see Catalyzed hydrogen peroxide density, 48 methane, 35
Chromite ore processing residue (COPR), 377 fluid properties, 49–50 nitrogen and phosphorus, 34–35
Chromium hydroxide (Cr(OH)3) Henry’s law constant, 48 oxygen and sulfur, 34–35
solubility, 362–363 liquid viscosity, 48–49 polar covalent bonds
Cleanup standards multicompartment sorption C–C and C–H bonds, 36
cleanup levels, 17–18 models, 51–53 dipole–dipole forces, 37
CSFs, 18 solubility, 46–47 electronegativity, 35–36
CSM, 18 sorption, 50 ion–ion forces, 37
HHRA, 18 vapor pressure, 47–48 net dipole moment, 35–37
Index
nonpolar molecules, 36–37
O–H bond, 36
polarizability, 36
CPT methods, see Cone penetrometer testing
methods
Critical failure analysis worksheet
causes and probability of occurrence, 74, 76
current controls and likelihood of
detection, 74, 76
effects and severity, 74–76
failure mode, 74–75
follow through, 77
recommended action, 76
RPN, 74
system element, 74
CSMs, see Conceptual site models
CVOC-based DNAPLs, 472–473
D performance, conventional approach,
Darcy’s law, 109, 113
Denitrification, anaerobic processes
ammonification, 247–248
in situ microbial denitrification, 248–249
molecular ammonia, 247
nitrification, 248
nitrogen forms, 247–248
by organisms, 248
redox potential, 249
Dense nonaqueous phase liquids (DNAPLs),
20, 54, 513
chlorinated DNAPL mapping, 127–128
ISCO, 287
petroleum hydrocarbons, 252
source zones, IRZs, 196
DGR, see Dynamic groundwater recirculation
Digital CSMs, 132
1,4-Dioxane
AFFFs, 568
biological degradation, 573–574
biological funneling, 568
DGR, 573
EPA, 569
in situ chemical oxidation, 571–573
LCMSMS, 569
PFAAs, 568
PFOS and PFOA, 568
polytetrafluorethylene, 567–568
smart characterization, 569–571
Direct-push injection logging (DPIL) tools, 122
Dispersion forces, 39–40
DNAPLs, see Dense nonaqueous phase liquids
Dose-response wells, 186–187
Drift phase monitoring, 187
Drift wells, 186–187
Dual-direction diffusion, 157–158
Dual-domain model (DDM), 137
Dual-equilibrium desorption (DED)
model, 52–53
Dye-enhanced laser-induced fluorescence
(DyeLIF), 128–129
Dynamic groundwater recirculation (DGR), 573
commercial property and metropolitan
setting
CSM, 161–163
design considerations, 163–165
plume adaptive approach and
performance tracking, 165–166
site closure and lessons learned, 166
complex heterogeneous systems, 147–148
contaminant transport, 137–139
design concepts, 159–161
former Reese Air Force Base
background, 149
cleanup objectives, 155–158
complete cleanup demonstration, 158
CSM refinement, 149–151
optimization, remedy strategy, 151–152
revised remedy strategy implementation,
151–155
TCE plume reduction, 8-year remediation
period, 158–159
pump and treat
critical elements, 147
enhanced flushing-based solution, 147
groundwater TCE plume development,
140–141
performance at manufacturing site,
139–140
140, 142–144
TCE plume, three hydrostratigraphic
units, 144–146
refueling pad
cross section A–A′, 168–169
design elements, 169–170
DGR performance and results, 170–172
geology and hydrogeology, 167–168
groundwater extraction and
reinjection, 170
injection wells, extraction wells and areas
A, B, C, 168–169
soil and groundwater impacts, 167–168
REV, 137
E Environmental microbiology, 8–9
Ecological risk assessments (ERA), 19
Electrical resistance heating (ERH)
electrical power, 470
electrodes and vapor extraction wells, 474
ET-DSP™, 476
in situ boiling temperature, 475
Joule’s law, 469
Ohm’s law, 470
resistive losses, 469
SI unit, 469–470
six-phase ERH, 474–475
steam and contaminant vapors, 475
steam stripping, 476
three-phase ERH, 474
unsaturated soil zone, 476
using continuous long electrode, 474–475
Electrical resistivity tomography (ERT)
method, 452
Electronegativity, 35–36
Electron transfer reactions, 267–268
Electro-thermal dynamic stripping process™
(ET-DSP™), 476
Elimination reaction, 268–269
Emerging contaminants, 26–27
Energy dispersive x-ray spectrometers
(EDS), 390
Enhanced reductive dechlorination (ERD)
carbon–chlorine bond, 229, 231
chlorinated hydrocarbon as electron
acceptor, 229
cis-DCE, 230
dechlorinating organisms
chlorinated alkenes and alkanes, 233
chlorinated benzoates, 233
chlorinated ethenes, 235
595
Dehalococcoides, 234
dihaloelimination reaction, 234
hexachlorocyclohexanes, 234
iron sulfide minerals, 235
methanogens, 234–235
sulfate-reducing bacteria, 235
degradation pathways
biological and abiotic, 231–232
common pathways, 231–232
dechlorination processes, 231
Dehalococcoides, 233
ecological selection pressures, 231
Gibbs free energy, 232–233
metabolic functions, 232
RDase genes, 233
tceA reductase enzyme, 233
thermodynamic analysis, 232
dissolved hydrogen as electron donor, 229
metabolic mechanisms, 229
metabolic processes, 229, 231
monitoring
daughter and end products, 239–240
geochemical conditions, 236–239
injection wells, 235
organic carbon donor, 236–237
primary decision-making steps, 235
sampling program, 235
PCE and TCE, 229
site hydrogeologic characteristics, 231
solvent molecules, 229
well-based configurations, 230
Enhanced resistivity heating (ERH) remedy, 163
Environmental biotechnology, 15
Environmental geochemistry, 9–10
Environmental remediation
CCRs, 577–578
conceptual site model, 559
data analysis, 551
data fusion, 560
data sets, 549–550
developing and validating benchmarks,
555–556
1,4-dioxane, 556
emerging contaminants
CECs, 566
1,4-dioxane, 565, 567
history, 564
perfluoroalkyl substances, 568–574
PFCs, 565
pharmaceuticals, hormones, and EDCs,
565–566
pump-and-treat systems, 566
1,2,3-TCP, 566
evaluations, 551–553
E-waste, 580–581
influence of, 549
large contaminated groundwater
advective scale, 560
cleaning up, 562–563
diffusion, 561–562
multiple technologies, 560
physical scale, 560
trichloroethene, 563–564
large plume management, 557–559
LNAPL management, 556–557
nanomaterials, 578–580
porosities, realistic values, 557–558
sensors, 554
smart investigations, 553
stratigraphic flux, 554–555
596
sustainability, 553
tracer testing data, 553–554
vapor intrusion, 575–577
Environmental security technology certification
program (ESTCP), 95
Equilibrium partitioning process,
see Absorption
Equilibrium solubility, 346
ERD, see Enhanced reductive dechlorination
ERH, see Electrical resistance heating
Excavation-based installation methods,
516, 518–521
Experimentation and coeducation phase, 17
Explosives
gaseous products in, 239
history, 239–240
HMX
anaerobic degradation, 242
biodegradation, 242
mineralization, 242
molecular structure, 240
threshold concentrations, 242
RDX
anaerobic degradation, 242
biodegradation, 242
capacity constant, sorption, 242
cometabolic process, 244
mineralization, 242
molecular structure, 240
second putative pathway, 242–243
threshold concentrations, 242
soils and groundwater contamination, 240
TNT
attenuation, 241
biodegradation, 241–242
diamino products, 240
microbial transformation, 241
molecular structure, 240
reductive transformation products, 240
threshold concentrations, 242
triamino product, 241
triaminotoluene (TAT), 241–242
two-stage reductive/oxidative
process, 241–242
Ex situ soil treatment
design considerations
soil stability, 467
soil volume, 467
disposal, 464–465
incineration, 465
land farming and biopiles, 466
thermal desorption, 465–466
Extracellular polymeric substance (EPS), 88
F contaminant properties, 48, 415–416
Faster groundwater velocity, 228
Fenton’s chemistry, see Catalyzed hydrogen
peroxide
Fick’s laws of diffusion, 113
Field design test, see Pilot testing, SVE
Flame ionization detector (FID), 485
Fluorescent dyes, 185
Former Reese Air Force Base
background, 149
cleanup objectives, 155–158
complete cleanup demonstration, 158
CSM refinement, 149–151
optimization, remedy strategy, 151–152
revised remedy strategy
implementation, 151–155
TCE plume reduction, 8-year remediation
period, 158–159
Freundlich isotherm, 386
Fuel oxygenates, 43, 255
G dispersion, 58
Geochemical strategies
biological methods, 344
chemical precipitation
development, 331
insoluble metallic sulfide
precipitates, 331
pH adjustment, 331–332
reduction, 332–333
sulfide precipitation, 332–335
sorption/coprecipitation, 344–345
Geophysical methods, 10–11
Geoprobe Systems, 127
Gibbs free energy, thermodynamics vs. kinetics
endergonic reactions, 261
enthalpy consideration, 261–263
entropy consideration, 263
exergonic reactions, 261
of products and reactants, 260
spontaneous reactions, 260
van’t Hoff equation, 260
Grain size analysis, 123
Gravity feed delivery, 180–181
Green liver model, 505
Groundwater extraction and treatment system
(GETS), 511, 538–539
Groundwater remediation technology
analysis, 95
H horizontal hydraulic conductivity, 180
Hard cations, 326
Health and safety (H&S) in design
behavior-based safety programs, 73
HASP, 73
hazard control hierarchy
engineering controls, 77
PPE, 77–78
work practices and administrative
controls, 77–78
hazard identification and critical failure
analysis
analysis worksheet, 74–77
block diagram creation, 74
process/task-related hazards, 73–74
system reliability–related hazards, 73–74
response planning, 78–79
Henry’s law constants
CVOCs, 467
VOCs, 467
Hexahydro-1,3,5-trinitro-1,3,5-triazine,
see Royal demolition explosive
Hexavalent chromium (Cr6+) precipitation
reaction, 336
High melting explosive (HMX)
anaerobic degradation, 242
biodegradation, 242
mineralization, 242
molecular structure, 240
threshold concentrations, 242
High-resolution direct-push slug testing,
122–123
HMX, see High melting explosive
H&S plan (HASP), 73
Index
Human health risk assessments (HHRA), 18–19
Hydraulic profiling tool (HPT), 122
Hydrodynamic transport processes
advection, 57–58
diffusive mass transport, 58
groundwater plumes, 58–59
remediation hydrogeology, 57
solute-based transport, 58–60
volatilization and transport, unsaturated
zone, 60–61
Hydrogen bonds, 37–38, 50
Hydrolytic dechlorination, 65
Hydrophobic bonds, 39
Hydroxyl radical (OH•), 273, 275
Hyperaccumulators, 505
I
Injection-based installation method, 521–522
Injection delivery methods
fracture-based injection tooling, 178, 180
hydraulic/pneumatic fracturing applications,
178–179
injection well, 178–179
reagent distribution, 179
selection, 178
well-based applications, 180
Injection phase monitoring, 187
Injection pressure considerations
allowable gauge pressure, 182
fluid injection, 180
grain-to-grain contact pressures, 181
gravity feed delivery, 180–181
horizontal effective stress, 181
hydraulic fracturing, 181
initial vertical effective stress, 182
injection flow rates, 180
low-pressure application, 182
maximum allowable injection pressure, 182
pressure relief, 182
saturated pore pressure, 181
theoretical injection pressure calculation, 181
total vertical stress, 181
Inorganic contaminants
metals, 43–44
nitrogen compounds, 44–45
perchlorate, 45
In situ air sparging process
airflow pathways distribution, 449
air injection into water-saturated soils,
447–448
applicability
contaminant applicability, 446–447
geologic characteristics, 447
biodegradation, 444–445
biosparging, 457–458
contaminant mass removal processes, 444
degree of channeling, 444
direct volatilization, 446
groundwater mixing, 449–450
in situ air stripping, 445–446
performance monitoring, 456
pilot testing
air distribution zone, 455
contaminant removal efficiencies,
455–456
full-scale air sparging systems, 454–455
injection air pressure, 455
injection flow rate, 455
Index
mass removal efficiency, 455–456
preliminary screening tool, 455
site-specific parameters, 455
primary components
air compressor/air blower, 456–457
vacuum blower, 457
valves and control devices, 457
saturated zone, 444
schematic diagram, 444
system design parameters
air distribution (zone of influence),
450–452
air injection pressure and flow rate,
452–453
contaminant type and distribution, 454
depth of air injection, 452
injection mode (pulsing and
continuous), 453
injection well construction, 453–454
volatile and aerobically biodegradable
organic contaminants, 444
water table mounding, 448–449
In situ biogeochemical processes, 9
In situ bioremediation
aerobic processes
aerobic biodegradation, 212–213
aerobic oxidation, 215–216
aromatic organic compounds, 214–215
catabolic pathway, naphthalene
degradation, 215–216
chlorinated aliphatic compounds,
215–217
contaminant types, 213
gasoline, 211
hydrocarbon degraders, 214
isolated bacterial genera, 213–214
methane compounds, 216
monitoring, 221–222
nutrient addition, 220–221
oxygen concentrations, 212–213
oxygen delivery mechanisms, 217–220
petroleum compounds, 211–212
pseudomonads, 213
anaerobic processes
anaerobic oxidation, 249–255
facultative organisms, 221–222
microbial reduction, 222–249
reduction potential, alternative electron
acceptors, 221
In situ chemical oxidation (ISCO), 95
1,4-dioxane, 571–573
oxidant characteristics, 272
radical reactions
chain reactions, 273–275
chemical reactive zone mechanisms, 273
kinetic rate constants, 273–274
radical chemistry, 273, 275
reagent loading and geochemistry
amount of oxidant, 275
bench testing, 277
carbonate interference, 281–284
contaminant concentrations, 275
health and safety considerations,
284–285
matrix oxidant demand, 275–277
oxidant quenching, 284
secondary water quality, 277–281
reagent selection/types
adsorbed mass/NAPL, 286–287
CHP, 272, 291–296
contaminant applicability, 285–286
dissolved-phase contamination, 286
DNAPL, 287
oxygen gas buildup, 287
ozone (O3), 272, 286, 301–304
permanganate (MnO4−), 272–273, 285,
287–291
persulfate (S2O82−), 272, 286, 296–301
pore water displacement, 287
volatile organic carbon stripping, 287
remedy designs, 186
resultant reactive species and parent
compounds, 272
In situ chemical reduction (ISCR)
abiotic reductants, 305
anaerobic biological strategies, 305
contaminants and metal precipitation, 305
naturally occurring chemical reductants, 305
reagent selection/types
applications, 305
chemical reductants and recent
pricing, 305
polysulfide, 306–307
sulfur oxyanions, 306
ZVI, 305, 307–311
reductive dechlorination and precipitation
processes, 304
In situ chemical remediation
chemical oxidation, 258
CHP, 272
combined reagents, 304
oxidant characteristics, 272
ozone, 272
permanganate, 272–273
persulfate, 272
radical reactions, 273–275
reagent loading and geochemistry,
275–285
reagent selection/types, 285–304
resultant reactive species and parent
compounds, 272
chemical reactive zone treatments, 258
chemical reactivity
enzyme participation, 259
geochemical considerations, 270–272
objective, 259
oxidation states, 259–260
reaction mechanisms, 267–270
thermodynamics vs. kinetics, 260–267
chemical reduction
abiotic reductants, 305
anaerobic biological strategies, 305
contaminants and metal
precipitation, 305
naturally occurring chemical
reductants, 305
reagent selection/types, 305–311
reductive dechlorination and precipitation
processes, 304
chemical remediation kinetics vs. biological
remediation kinetics, 258
contaminant destruction and immobilization
mechanisms, 257
nontarget compounds and nontarget reaction
losses, 258
thermodynamic feasibility, 259
In situ engineered reductive dechlorination,
153–155
In situ extractive techniques, 173
In situ metals treatment
acid dissociation constant, 323
alkali metals, 323
597
alkaline earth metals:, 323–324
anion, 324
arsenic, 398–401
buffering capacity, 324
cation and colloidal particle, 324
chromium, 397–398
common ion effect, 324
co-precipitation, 324
dissolved metal analysis, 388
durability/permanence, 323
element re-oxidation, 405–407
equilibrium constants, 329–331
equilibrium solubility, 323
geochemical strategies
biological methods, 344
chemical precipitation, 331–344
sorption/coprecipitation, 344–345
geochemistry
analytical results, nickel and measured
pH, 364–365
biological reactive zone, 365, 367
hydration, 368
matrix effect, 367–368
metal hydroxides and carbonates
solubility, 358, 360
metal hydroxide vs. metal carbonate
solubility products, 358, 360
nickel-containing plating solution, 365
nickel sulfide formation, 365–367
oxides and hydroxides, 358–363
precipitate formation and inhibition,
346–358
solubility, targeted mineral, 345–346
sulfides, 363–364
heavy metal, 326
heterogeneous and homogenous
reactions, 324
ionic strength, 324
kinetics, 323
Lewis acid and base, 324
metal bonding characteristics, 325–326
metal characteristics, transport and
toxicity, 327
metal sulfides (MeS), 405
operational (functional) analysis, 396–397
oxidation–reduction potential, 324–325
pE–pH diagrams, 328–329
point of zero charge, 324
radionuclides
plutonium, 403–404
technetium-99, 402–403
uranium, 401–402
regulatory considerations, 327–328
solid metal analysis
data acquisition, 388
elemental analysis, 388–389
QEMSCAN system, 390–395
structural analysis, 389
XAS, 394–397
XRD, 389
solubility product, 324
technology type
extraction, 384–387
PRBs, 373–375
reactive zones, 369–373
stabilization, 375–384
transition elements, 325–327
In situ nonextractive techniques, 173
In situ reactive zones (IRZs), 15–16
concept of, 173–174
contaminant considerations
598
biodegradable contaminants, 176
kinetic-based oxidation–reduction
remedies, 175
metabolism, 175
MNA, 176
organic contaminants, 175
physicochemical properties, 175
relative susceptibility, 175
design parameters
injection delivery methods, 178–180
injection frequency, 183–184
injection pressure considerations,
180–182
reagent types and selection
considerations, 182–183
reevaluation of hydrogeology, 176
volume–radius relationship, 176–178
enhanced NAPL dissolution
benzene concentrations, 198–199
chlorinated solvent source zone
applications, 197
concentration gradient, 196
design decision making, 198
dissolved-phase treatment
remedies, 196
DNAPL source zones, 196
field data set, source zone monitoring,
197–198
hydrophobic organics distribution,
196–197
LNAPL treatment, 196
mass transfer coefficient, 196–197
mechanisms, 197
short-term physical removal
techniques, 198
solubility and degradability, 198
Suntech method, 196
fundamental requirements, 173
injection configurations
batch mixing injection setup, 192
fully automated mixing system, 192
geology and groundwater transport
velocity, 192
injection-based applications, 190–191
large plume treatment, 193–195
plume cutoff barrier transects, 191
plume-wide reactive zones, 191
pulse and drift vs. recirculation, 192–193
reagent distribution, 190, 192
semisoluble/sparingly soluble
reagents, 192
source area reactive zones, 191
water-soluble reagents, 192
injection tests and tracer studies
feasibility and selection criteria, 184
field demonstration, 184
injection duration, 185
mobile porosity and velocity
interpretation, 187–190
multiple well pilot tests, 185
multiple well tracer tests, 184–185
pilot test, 184
reagent-based injection tests, 184
single-well tests, 184
test layout and monitoring programs,
186–187
tracer test, 184
tracer types, 185–186
in situ mass destruction techniques, 173
performance monitoring, 195–196
types of reactions
chemical and biological reactions,
174–175
equilibrium, 175
heterogeneous, 174
homogeneous, 174
kinetics, 175
mineralization, 174
oxidation–reduction (redox)
reactions, 175
reversible reactions, 175
steady-state condition, 175
substitution, elimination, and
configuration reactions, 174
system, 175
In situ soil mixing (ISM), 375
advantages, 487
bench-scale treatability testing, 487
design goals, 489–490
field pilot testing, 487
geotechnical and earth retention
applications, 486
implementation challenges, 492–493
implementation methods
deep soil mixing, 490–491
jet mixing/grouting, 491
shallow soil mixing, 490–492
ISS, 486
former creosote facility, 494–495
former MGP site, 493–494
treatability challenges, 490
treatability test, 488
IST, 487
chemical oxidants, 496
contaminant flux, 495–496
homogenization, 495–496
reactive materials, 495
ZVI and clay, 496–497
reagent selection, 488–489
soil characterization, 487
soil sampling, 487–488
In situ soil stabilization/solidification
(ISSS), 309
In situ solidification/stabilization (ISS), 486
former creosote facility, 494–495
former MGP site, 493–494
treatability challenges, 490
treatability test, 488
In situ thermal remediation
aquifer minerals and metals, 467
CVOCs, 467–468
energy input and heating mechanisms
combustion/smoldering, 470
conduction, 469
convection, 469
Joule (electrical resistance) heating,
469–470
radio frequency/microwave heating, 470
energy transport and storage mechanisms
advection, 470
convection, 470
heat capacity, 471
heat of condensation, 471
heat of vaporization, 471
thermal conductivity and thermal
diffusivity, 470–471
performance monitoring
process monitoring, 485–486
remote monitoring, 485
thermal well field monitoring, 485
pore volumes, 468
thermal treatment technologies
Index
COCs, 481–482
design considerations, 483–485
ERH, 474–476
geologic settings, 481, 483
groundwater flow conditions, 481, 483
hydraulic and pneumatic control, 483
identification and selection, 481–482
low-temperature in situ thermal
treatment, 479–480
mass and energy balance, 483–484
in North America, 480–481
SEE, 477–479
smoldering combustion, 479
target treatment temperature, 482–483
TCH, 476–477
technical aspects, 481
treatment and removal mechanisms
fluid property changes, 473–474
low-boiling point azeotropes formation,
472–473
preferential partitioning, vapor
phase, 472
TAADR, 473–475
vaporization and volatilization, 472
treatment zone, 468
vaporization, 467
VOCs, 467–468
In situ treatment (IST), 487
chemical oxidants, 496
contaminant flux, 495–496
homogenization, 495–496
reactive materials, 495
ZVI and clay, 496–497
Interspecies hydrogen transfer, 226
Interstate technology and regulatory council
(ITRC), 95
Intrinsic solubility, 346
Ionic bonds, 38–39
Iron-and manganese-oxidizing bacteria, 88
Iron hydroxide (Fe(OH)3) solubility, 361–362
IRZs, see In situ reactive zones
ISCO, see In situ chemical oxidation
ISCR, see In situ chemical reduction
ISM, see In situ soil mixing
ISS, see In situ solidification/stabilization
IST, see In situ treatment
K
Kinetic control of reaction rates
collisions between reactants frequency, 263
first-order reactions, 264
kinetic feasibility
elements of kinetic analysis, 267
energy-yielding reactions, 266
potential kinetic limitations, 266–267
principle of, 266
likelihood of reaction, 263
probability of reaction, 263
pseudo-first-order reaction kinetics, 265–266
rate equations, 264
reaction order, 264
second-order reactions, 264–265
zero-order reactions, 264
L
Laser-induced fluorescence (LIF)
for chlorinated DNAPL mapping, 127–128
DyeLIF, 128–129
fluorescent molecules, 126
Index
for LNAPL characterization, 127–128
log, 127
sapphire-windowed probe, 126
versions, 126
Light nonaqueous phase liquids (LNAPLs),
28–29, 54
IRZs, 196
LIF, 127–128
petroleum hydrocarbons, 252
Liquid chromatography with tandem mass
spectrometry (LCMSMS), 569
Longitudinal dispersion, 58
M (OSHA), 21–22
Mass transfer zone (MTZ), 442
Matrix oxidant demand, 275–277
Maximum contaminant levels (MCLs), 327–328
Membrane interface probe (MIP), 124–125
Metal partitioning coefficients, 386–387
Methane monooxygenase (MMO), 65
Methyl tert-butyl ether (MTBE), 213, 255
Microbially induced/influenced corrosion
(MIC), 91
Microbial oxidation, 64
Microbial reduction, 64–65
aerobic carbohydrate metabolism, 222
aerobic glycolysis, 222
aliphatic and aromatic organic compounds
dechlorination, 222
biogeochemistry, 222–224
carbohydrate fermentation, 222
denitrification, 247–249
disproportionation, 222
ERD, 229–240
explosives degradation, 239–244
nitroaromatic compounds reduction, 222
perchlorate degradation, 244–247
substrates, 223–229
Mine reclamation
AMD, 28
mine closure, 27
mine tailings, 27–28
mining habitats, 28
Mobile porosity and velocity interpretation
bulk velocity, 188–189
center of mass, 188
dose-response wells, 187
downgradient drift wells, 188
first temporal moment, 188
groundwater velocity, 188
method of moments, 188–189
minimal nonideal transport, 189–190
moderate nonideal transport, 189–190
normalized concentration, 188
normalized tracer responses, 188
projected tail moments, 189
second temporal moment, 188–189
significant nonideal transport, 189–190
transport velocity, 188–189
volume to distribution ratio, 188
Monitored natural attenuation (MNA), 176
N anion perchlorate, 244
Nanoscale ZVI (nZVI), 310–311
NAPLs, see Nonaqueous-phase liquids
Natural oxidant demand (NOD), see Matrix
oxidant demand
Natural source zone depletion (NSZD), 556
Nonaqueous-phase liquids (NAPLs), 33
599
architecture, 54–55 denitrifying microorganisms, 245
DNAPL, 20, 54 IRZ deployment, 245–246
LNAPL, 54 microbial transformation, 245
saturation and mobility, 55–56 oxidation poise setting, 244
source zone, 55 permissive geological units, 244
weathering, 56–57 postulated chemical mechanisms, 244
Nucleophilicity, 269–270 reduction, 245, 247
Nucleophilic substitution reaction, 268–269 in soil, 247–248
Perfluoroalkyl acids (PFAAs), 568
O Perfluoroalkyl substances (PFASs), 42
AFFFs, 568
Obligate proton reducers, 225 biological degradation, 573–574
Occupational Safety and Health Administration biological funneling, 568
DGR, 573
Octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine, EPA, 569
see High melting explosive in situ chemical oxidation, 571–573
Optical image profiler (OIP), 127 LCMSMS, 569
Organic absorption, 50 PFAAs, 568
Organic contaminants PFOS and PFOA, 568
fuel oxygenates, 43 polytetrafluorethylene, 567–568
halogenated organics smart characterization, 569–571
chlorinated alkenes and alkanes, 41 Permanganate (MnO4−), 272–273
chlorinated aromatics, 41–42 chlorinated alkenes treatment, 285
fluorinated organics, 42 potassium permanganate (KMnO4), 285,
ketones, 42 287–288
NAPL, 40 potential trace chromium concentration, 288
PAHs, 43 reaction mechanisms, 288–289
partitioning in subsurface environment, 40 by-product formation, 289–291
petroleum hydrocarbons, 42–43 future innovation and current
Oxygenated water recirculation system, 220 research, 290
Oxygen delivery mechanisms kinetics, 289–290
aqueous oxygen delivery, 219–220 performance monitoring, 290
automated delivery systems, 217 sodium permanganate (NaMnO4), 285,
biosparging, 217–219 287–288
comparative costs, 217 stability, 285
solid (oxygen release compounds), 220 Permeable reactive barriers (PRBs), 373–375
solid-phase materials, 217 biological reactive mechanism
Oxygenolytic dechlorination, 65 aerobic, 529
Oxygen propagation, 296 anaerobic, 528–529
Oxygen-releasing materials (ORMs), 217, 220 chemical reaction mechanism
Ozone (O3), 272, 286 abiotic reduction, 526–527
applications, 301 chemical oxidation, 527–528
aqueous-phase solubility, 301–302 precipitation, 526
by-product formation, 304 components, 533
cost–benefit analysis, 301 configuration, 511–512
performance monitoring, 304 constructability
production, 301 continuous PRB, 516–517
reaction mechanisms excavation-based installation methods,
direct oxidation, 302–303 516, 518–521
dissolution, 302 funnel walls, 517
radical chain reactions, 301 injection-based installation method,
radical oxidation, 303–304 521–522
unstable nature, 301 limitations, 522
second-order rate kinetics, 304 sheet pile walls, 518
slurry walls, 517–518
P contaminant distribution and mass flux, 535
continuous PRB, 512–513
Particle tracking methods, 160–161 funnel and gate
Passivation, 374–375 advantage, 513
Passive flux meters (PFMs), 128–129 cross-sectional views, 513–514
Perchlorate degradation DNAPL, 513
ammonium perchlorate, 244–245 funnel width and angle, 514–515
anaerobic reduction, 246 physical, chemical, and biological
mechanisms, 514
anthropogenic perchlorate reactive gate length, 515
contamination, 245 reactive gate permeability, 515
in aquifers, 245 single reactive gate, 514
biogeochemical inhibitor setting, 244 trichloroethylene, 514
biogeochemical operating principles, hydraulic capture, 522
245, 247 hydraulics, 533–534
chlorate reductase, 245 longevity, 535
600 Index

O&M, 530 contaminant levels, 508–509 Precipitate formation and inhibition

performance monitoring irrigation, agronomic inputs, and biological interferences, 355–357
demonstration, 536–537 maintenance, 509 chemical interferences, 357–358
in Elizabeth City, 543–544 physical/mechanical impedance, 508 colloidal particles, 353
GETS replacement, 538–539 plant selection process, 509 crystallinity maturation, 350–351
perchlorate, 539–543 site characterization data, 508 dissolution control, 347
potential arrangements, 536 soil air, 508 dissolved-phase concentration, 347, 349
secondary water-quality, 537 soil pH, 508 in situ remediation, 354
physical reaction mechanism soil temperature, 508 ionic strength, 354
air sparging, 523–524 soil water, 508 mixed mineral phases, 351–352
ion exchange resins, 524–525 topography, 508 nickel carbonate (NiCO3) solubility, 348
liquid-phase granular activated treatability/plant screening, 509 nickel concentration, 347–348
carbon, 524 history, 497 nickel hydroxide (Ni(OH)2) solubility, 349
reactivity, 523 Meinzer’s observations, 497 nucleation, 350
residence time, 523 soil–plant system, chemicals in point of zero charge (pHpzc), 354
treatment kinetics and minimum residence inorganic macronutrients, 498 potential fouling, 358
time, 534–535 inorganic micronutrients, 498 precipitation, definition, 346
treatment reagent metals, 498–499 predicted nickel solubility, 348
apatite, 531 organic compounds, 499–500 solubility product, 347, 349
availability, 530–531 transpiration process, 497 stability, oxidation–reduction sensitive
compatibility, 531 types metals, 354–355
gypsum, 532 hazardous waste remediation, 500 thermodynamic control, 346–347
limestone, 532 phytodegradation, 500, 505–507 TSSs, 352–353
organic, 532 phytoextraction, 500, 504–506 Predesign characterization, 79, 87
organophilic clays, 531 phytohydraulics, 500, 503–504 Predesign experimentation
reactivity, 530 phytosequestration, 500–501 real experiments, 79
zeolites, 531 phytovolatilization, 500, 505–508 amendments, 85
ZVI, 531 rhizodegradation, 500–503 analysis and interpretation, 83
Personal protective equipment (PPE), 21–22, water table, daily fluctuations, 497–498 control, 82–83
77, 284 White’s observations, 497 1,2-DCA degradation, 84–86
Persulfate chemistry, 272, 286 Phytotransformation, see Phytodegradation factors, 82
by-product formation, 300 Phytovolatilization, 500, 505–508 field experiments, 84
competitive inhibitors Pilot testing findings, 85
aquifer minerals, 300 in situ air sparging process, 454–456 focus and goals, 82
chloride, 299–300 SVE framework, 82
engineered activation, 297 air samples, 425–426 in situ bioremediation, 84
future innovation and current research, components, 425–426 methods, 83
300–301 extraction well location, 426–427 microcosm preparation, 85
kinetics, 299 nested probe monitoring well, 427–428 preliminary soil analysis, 85
performance monitoring, 301 pneumatic conductivity, 428 preliminary water analysis, 85
peroxydisulfate, 296 regenerative vacuum pump models, replication, 83
peroxymonosulfate, 296 operational ranges, 427, 429 sample collection and processing, 85
physical and chemical properties, 296–297 turbine vacuum pump models, scope and scale, 82
reaction mechanisms operational ranges, 427, 429 treatability testing, 82, 84
direct oxidation, 297 vacuum monitoring points, 427 thought experiment, 79
radical oxidation, 297–299 well, 427 dispersion patterns, 80
Petroleum hydrocarbons (PHCs), 42–43 Polychlorinated biphenyls (PCBs), 41–42 NAPL encrustation, 80–81
ABOx systems, 251–253 Polyfluoroalkyl substances (PFASs), 42 oxidant-target compatibility, 81
permanganate, 81 Polynuclear aromatic hydrocarbons screening technology applications, 80
PFASs, see Perfluoroalkyl substances (PAHs), 43 secondary water quality effects, 81–82
PHCs, see Petroleum hydrocarbons Polysulfide theories testing, 80
Photoionization detector (PID), 485 chemical reduction reagent, 306–307 uniformity of coverage, 82
Phytoaccumulation, see Phytoextraction metal precipitation Primary fermentation, 225
Phytoaccumulators, 505 arsenic precipitation, 341–342 Pseudo-first-order reaction rates, 289–290
Phytodegradation, 500 bench-scale treatability test, 337–338 Pump-and-treat (P&T) systems, 6, 15–16
current state of science, 507 CaSx injection, 340
green liver model, 505 CaSx treatability test data, 338–339 Q
parrot feather,507 in situ field treatability test, 338–340
and phytovolatilization, 505–507 metal oxides vs. metal sulfides, 331, 342 Quantitative evaluation of minerals by
plant enzyme systems, 505 metal sulfides vs. metal hydroxides, 338 SCANning (QEMSCAN) electron
reduction, oxidation, conjugation, and pE–pH stability diagram, sulfur microscopy system
sequestration, 505 system, 335, 337 COPR, 390
TCE degradation, 507 pH neutralization, 341 data visualization, 393
TNT degradation, 507 pseudo-first-order reaction electron beam, 390
Phytoextraction, 500, 504–505 kinetics, 337 outputs, 394
Phytoextractors, 505 selenium, 341 posttreatment homogenate SEM-EDS image,
Phytohydraulics, 500, 503–504 solubility products, 331, 342 390–392
Phytosequestration, 500–501 Pore flushing approximation, 385–387 pre-treatment homogenate SEM-EDS image,
Phytotechnologies Pore volume exchange rate (PVER), 431–432 390–391
application, 497, 501 PPE, see Personal protective equipment quantitative evaluation of minerals, 392–394
design PRBs, see Permeable reactive barriers TEM image resolution, 394–395
Index 601

R incremental implementation, 73 remediation engineer

Radical chain reactions
initiation, 273
promotion, 273–274
termination, 275
RCRA, see Resource Conservation and
Recovery Act
RDX, see Royal demolition explosive
Reaction kinetic effects, 351
Reactive zones
bedrock formation, 370–371
biological IRZs, 370
chemical, 369–370
definition, 369
hexavalent chromium plume progression, 371
hexavalent chromium (Cr6+) reduction,
370–374
intrinsic biological reduction, 370
IRZ, 369
off-site geochemical response, 371, 373
Reagent handling, 183
Reagent injectability, 182
Reagent longevity, 183
Reagent-related by-products, 183
Reagent solubility, 182
Record of decision (ROD), 14
Redox reactions, see Electron transfer reactions
Redox recovery zone, 195
Reductionistic progression, 9
Reductive dechlorination, 65
Reductive dehalogenase (RDase) genes, 233
Reference dose (RFD), 18
Refueling pad
cross section A–A′, 168–169
design elements, 169–170
DGR performance and results, 170–172
geology and hydrogeology, 167–168
groundwater extraction and reinjection, 170
injection wells, extraction wells and areas
A, B, C, 168–169
soil and groundwater impacts, 167–168
Regulatory guidance values (RGVs), 18
Relative mass flux, 138–139
Remediation design
biogeochemical considerations
fouling of wells and equipment, 87–92
material compatibility, 101–102
porosity reductions in aquifer, 92–95
secondary water quality impacts, 95–101
environmental considerations
dust/particulate emissions, 102
Green and Sustainable Remediation, 103
noise, 102
security, 103
surface water protection, 103
traffic, 102
vibration and subsidence, 102
volatile emissions and odors, 102
web-accessible best management
practices, 103
health and safety
behavior-based safety programs, 73
HASP, 73
hazard control hierarchy, 77–78
hazard identification and critical failure
analysis, 73–77
response planning, 78–79
integrated design
adaptive vs. fixed practice, 72
holistic/whole-system viewpoint, 72
integrated development, 72–73
long-term stewardship, 72
restoration solutions, 72
watershed functions, 72
predesign efforts
characterization, 79, 87
concepts and definitions, 79–80
experimentation, 79–86
process elements, 69–70
brainstorm, 70
define, 69
deploy, 71–72
plan, 70–71
refine, 71
test, 71
Remediation engineering
complementary disciplines, advances in
emerging engineering, 5
environmental geochemistry, 9–10
environmental microbiology, 8–9
foundational knowledge base, 5–6
geophysical methods, 10–11
key events, 5
remediation hydrogeology, 5–8
current trends
emerging contaminants, 26–27
evolutionary developments, 23–24
LNAPL management, 28–29
mine reclamation, 27–28
potential barriers, 23–24
sustainable (green) remediation, 24–26
water resources protection, 29–31
health and safety
awareness and current trends, 21–22
in design process, 22–23
hazardous waste remediation
projects, 21
occupational considerations, 20–21
operations and maintenance, 21
potential hazards, 22
industry growth
ecological management, 3
federal government collaboration, 3
funding source, remediation project
implementation, 2
growth rates, 1
long-term stewardship, 3
regulation-driven markets, 2
regulatory programs, 1
restoration, 3
site closure, 2
standards, 3
technology development, 3
knowledge management continuum, 1–2
regulatory framework
CERCLA (1980), 17
cleanup standards, 17–19
Federal Water Pollution Control Act of
1948, 16
National Environmental Policy Act
(1969), 17
Oil Pollution Act of 1924, 16
regulatory influence, 17
risk-based approaches, 19–20
River and Harbor Act of 1899, 16
Solid Waste Disposal Act of 1965, 17
technical impracticability
considerations, 20
USEPA, 16–17
UST systems, 17
best-value remediation design, 12–13
characteristics, 11–12
financial performance, 13
ill-defined terminology, 12
interdisciplinary nature, 12
leadership role, 12
long-standing cleanup standards, 12
site closure, 12
technical discipline
advancement, 4
analytical chemistry techniques, 4
civil/sanitary engineers, 1970s, 3
direct push drilling technologies, 4
environmental engineers, 1980s, 3
environmetrics, 4–5
evolutionary growth, 4
history, 3–4
organic and inorganic compounds, 4
source-zone mass removal, 4
subsurface environment, 3–4
subsurface media, 4
technologies evolution and maturation
contaminants type and chemical
characteristics, 13
contaminant treatment pathways, 13
cost-effective technologies, 13
emerging technologies, 13
operational efficiencies, 13
P&T systems, 15–16
regulatory influences, 14–15
Remediation hydrogeology
contaminant mass flux, 8
contaminant transport processes
advection, 112–113
advection–diffusion model, 113
advection–dispersion model, 113
diffusion, 112–113
dispersion, 112–113
nonpoint sources, 112
point sources, 112
CSMs, 7
early developments, 1950s–1980s, 114
first generation, 1980s–2000s, 114
flux-informed remediation decision
making, 8
groundwater and mineral resources
development, 5
groundwater flow
aquifer and characteristics, 107–110
aquifer building processes, heterogeneity,
and anisotropy, 110–112
groundwater hydrogeology, 6
high-resolution site characterization
techniques, 7
injection-based in situ systems, 7
large dissolved plumes, 8
large-scale averaging, 6
macroscale hydrogeologic and hydrodynamic
principles, 6
mass discharge measurement techniques, 8
mass flux, 107
observation vs. utilization, 6
P&T systems, 6
remediation hydraulics, 2000s–present, 113
flux-focused investigation and
remediation strategies, 117–118
heterogeneous advection and
diffusion, 115
hydrostratigraphy, 114
mass storage zones, 114
602
mass transport zones, 114
stratigraphic flux, 115–117
site characterization
CSMs, 107, 130–135
mass flux–based perspective, 118
Smart Characterization, 107, 120–130
traditional site investigation methods,
limitations, 118–120
smart investigation tools, 7–8
volumes, 107–108
water supply origins, pre-1950s, 113–114
Remediation industry
CERCLA, 1
hazardous waste cleanup sites, 1
hazardous waste handling, transport, and
disposal, 1
UST regulations, 1
Representative elemental volume (REV), 137
Resource Conservation and Recovery Act
(RCRA), 1, 17, 20, 464, 578
Retardation factor (Rf), 160
Return on investigation (ROI), 120
Rhizodegradation, 500–503
Risk-based corrective action (RBCA), 14–15
Royal demolition explosive (RDX)
anaerobic degradation, 242
biodegradation, 242
capacity constant, sorption, 242
cometabolic process, 244
mineralization, 242
molecular structure, 240
second putative pathway, 242–243
threshold concentrations, 242
S aquifer minerals and metals, 467
Safe Drinking Water Act, 26
Safety data sheet (SDS), 284
Secondary/coupled fermentation, 225–226
Secondary water quality impacts (SWQIs)
cycling of metals, aquifer matrix
anaerobic systems, metals mobilization
in, 97, 99–100
high-/low-pH extremes development, 96
ionic strength/specific dissolved ion
concentration, 96
oxidation/reduction reactions, 96
oxidizing systems, metals mobilization
in, 96–98
degradation intermediates, organic
contaminants, 101
design implications, 101
ISCO, 95
microbial metabolic by-products, 100
nonmetal inorganic reaction by-products,
100–101
reactant-related by-products, 95
SEE, see Steam-enhanced extraction
Shelby tube sampling, 123
Slower groundwater velocity, 229
Smart Characterization, 107
concentration mapping tools
laser-induced fluorescence NAPL
mapping tools, 126–128
MIP, 124–125
vertical aquifer profile sampling,
123–124
WCSS, 125–126
direct flux mapping, 128–129
measurement methods, 120
permeability characterization
geologic logging and soil
classification, 120
permeability profiling methods, 120–122
point permeability methods, 122–123
USCS approach, 120
quantitative sampling, 120
ROI, 120
screening level tools, 120
3D visualization, 129–130
Soft cations, 326
Soil excavation
cleaning, mobile treatment, 464
construction equipment, 463
ex situ soil treatment
design considerations, 467
disposal, 464–465
incineration, 465
land farming and biopiles, 466
thermal desorption, 465–466
logistical challenges, 464
past site history and activities, 463
site workers, 464
Soil remediation, see Soil treatment
Soil treatment
in situ soil mixing
advantages, 487
geotechnical and earth retention
applications, 486
implementation challenges, 492–493
implementation methods, 490–492
implementation plan, 487–490
ISS, 486, 493–495
IST, 487, 495–497
in situ thermal remediation
CVOCs, 467–468
energy input and heating mechanisms,
469–470
energy transport and storage
mechanisms, 470–471
performance monitoring, 485–486
pore volumes, 468
thermal treatment technologies, 474–485
treatment and removal mechanisms,
472–475
treatment zone, 468
vaporization, 467
VOCs, 467–468
phytotechnologies, 461, 497–498
design, 508–509
soil–plant system, chemicals in,
498–500
types, 500–508
predesign investigation (PDI), 461
residual soil contaminants, 461
screening criteria, 461–462
soil excavation
cleaning, mobile treatment, 464
construction equipment, 463
ex situ soil treatment, 464–467
logistical challenges, 464
past site history and activities, 463
site workers, 464
sorptive processes, 462–463
thermal remediation, 461
Soil vapor extraction (SVE)
advantages, 413
airflow characteristics
airflow in permeable media, 421
airflow patterns and vacuum
distribution, 421
Index
Darcian equation for radial flow,
423–424
Darcian flow through constant cross
section, 422–423
surface seals, 421
applicability
contaminant applicability, 424
site characterization, 424–425
bioventing, 413
aerobic biodegradation process, 433
airflow rates, 434
benzene degradation, 434
in situ respiration test, 436–437
laboratory testing, 434–435
system design, 435–436
vadose zone, 433
volatilization, 433
contaminant partitioning characteristics
direct volatilization, 414, 419
dissolved contaminant extraction, 414
equilibrium disruption, 414
equilibrium dissolved concentration and
adsorbed concentration, 419
NAPL, 419
organic contaminant phases, soil matrix,
413–414
pore volume exchange, 414
vadose zone, 419
vapor concentrations decline, 413, 415
contaminant properties
biodegradability, 418
four phase diagram, 414
Henry’s law constant, 415–416
molecular structure, 418
molecular weight, 418
octanol–water partitioning
coefficient, 418
polarity, 418
soil adsorption coefficient, 417–418
three phase diagram, 414
vapor pressure, 414–415
water solubility, 415
weathering, 418
in situ SVE system components, 413–414
performance monitoring requirements,
437–438
soil properties
soil heterogeneity, 420
soil porosity, 419
water content, 419
water table, 420
system design
airflow models, 432
categories, 425
computer simulation modeling, 432
criteria, 425–426
empirical approach, 428–429
goals, 425
multiphase transport models, 432
operational considerations, 432–434
pilot testing, 425–429
pore volume exchange approach,
430–432
radius of influence approach, 429–431
vapor treatment technologies
adsorption, 440–443
catalytic oxidation, 439–441
condensation, 443
cost considerations, 443–444
thermal oxidation, 437–439
VOC types, 437–438
Index
Soluble salts, 185
Solute-based transport
hydraulic conductivity and flux, 59–60
mass discharge, 58–59
mass flux, 58–59
risk-based decision-making, 60
Solvent–solute equilibrium system, 46
Sorption, 417
Sorption-based retardation, 386
Source mass approximation, 385
Stabilization
baseline pH, 382–383
bench-scale treatability study, 377–378
cell division, 379
COPR, 377
Cr6+ concentration, 380–381
facility, 375
field-scale pilot study, 378
innovative approach, 377
ISM, 375
performance monitoring, 380
phased treatability study, 375–377
pH measurements, sulfuric acid addition, 379
small field-scale pilot study, 378
targeted dosage, 378
temperature measurements, sulfuric acid
addition, 379–380
total chromium (Crtot), 380–382
total iron concentrations, 383
total organic carbon, 383–384
Stable isotope tracers, 185–186
Steam-enhanced extraction (SEE), 477–479
Stewardship, 3
Strategic environmental research and
development program (SERDP), 95
Substrates, microbial reduction
design considerations, 227–229
fermentation reactions, 222, 225–226
organic carbon, 223–224
selection considerations, 226–227
Sulfate-reducing bacteria (SRB), 88
Sulfide precipitation
acidity consumption, 335–336
broader matrix, 333
distribution of sulfides, 333, 335
dithionite metal precipitation, 336–337
in situ metal precipitation, 332
ionic manipulation, 343–344
metal oxides vs. metal sulfides, 331, 333
metal solubility, 333–334
polysulfide metal precipitation, 337–342
solubility product data, 330, 333
sulfur speciation diagram, 332, 334
ZVI metal precipitation, 342–343
Sulfur oxyanions, 306
Superfund, 1
Sustainable (green) remediation
balancing criteria and metrics, 26
definition, 24
evaluation factors, 25
footprint, 24
governing, macro-level criteria, 26
indicator categories, 25
micro-level, threshold criteria, 26
quantitative models, 25
603
stakeholders, 24 Vapor intrusion (VI), 575–577
sustainability movement, 25 Vaporization of target compounds, 296
sustainable community, 24 Vapor migration, 419
SVE, see Soil vapor extraction Volatile organic compounds (VOCs)
SWQIs, see Secondary water quality impacts in situ thermal remediation,
467–468
T vapor treatment
adsorption, 440–443
Technetium-99 (99Tc), 402–403 catalytic oxidation, 439–441
Temperature-activated autodecomposition condensation, 443
reactions (TAADR), 473–475 cost considerations, 443–444
Thermal conduction heating (TCH), 476–477 thermal oxidation, 437–439
Thermal in situ sustainable remediation types, 437–438
(TISR), 480
Thermal oxidation W
degree of mixing, 438
heat recovery equipment, 438 Waste electrical and electronic equipment
internal combustion (IC) engines, 439 (WEEE), 580–581
operating temperature, combustion Water-table aquifer, 108
chamber, 437 Whole-core saturated soil (WCSS) sampling,
recuperative systems, 439 125–126
regenerative systems, 439
residence time, 438 X
straight-through thermal oxidation systems,
438–439 XAS, see X-ray absorption spectroscopy
unit components, 437 X-ray absorption fine structure (XAFS),
VOC destruction efficiency, 437–438 394–395
Time-domain reflectometry (TDR) X-ray absorption near edge structure (XANES),
technique, 452 394–395
TNT, see 2,4,6-Trinitrotoluene X-ray absorption spectroscopy (XAS)
Total dissolved solids (TDS), 46 binding energy of electrons, 394
Total organic carbon (TOC), 46 biogenic uraninite, 395–396
Total petroleum hydrocarbon (TPH), 45–46 chromium analysis, 395–396
Total suspended solids (TSSs), 352–353 pattern, conceptual depiction, 395
Transmission electron microscopy (TEM) XANES/XAFS, 394–395
image, 394–395 μXRF cross section maps, 396–397
Transverse dispersion, 58
2,4,6-Trinitrotoluene (TNT) Z
attenuation, 241
biodegradation, 241–242 Zero-valent iron (ZVI), 305
diamino products, 240 applications, 307
microbial transformation, 241 granular, 309
molecular structure, 240 in situ soil mixing, 496–497
reductive transformation products, 240 iron type, 310
threshold concentrations, 242 ISSS implementations, 309
triamino product, 241 kinetics, 309
triaminotoluene (TAT), 241–242 metal precipitation, 342–343
two-stage reductive/oxidative process, nanoscale, 310–311
241–242 oxic reaction, 308
physical characteristics, 307
U reaction mechanisms
β-elimination reaction, 308
Udden–Wentworth classification approach, 123 heterogeneous vs. homogeneous
Unconfined aquifer, 108 reactions, 308
Underground storage tank (UST) hydrogenation, 309
regulations, 1, 17 hydrogenolysis
Unified Soil Classification System (USCS), 120 reaction,
Unregulated Compounds Monitoring 308–309
Rule (UCMR), 26 reactive barrier, 307
residence time, 311
V solid-phase reducing agent, 307
Zinc hydroxide (Zn(OH)2)
Valley of death, 14 solubility, 362
van der Waals forces, 50 Zone of influence, 450
van der Waals interactions, 39 ZVI, see Zero-valent iron