بسم الله الرحمن الرحيم
In Situ Chemical Oxidation for Groundwater Remediation
by
Robert L. Siegrist, Michelle Crimi, Thomas J. Simpkin
In Situ Chemical Oxidation for Groundwater Remediation
by
Robert L. Siegrist, Michelle Crimi, Thomas J. Simpkin
BooK description
This volume provides comprehensive up-to-date descriptions of the principles and practices of in situ chemical oxidation (ISCO) for groundwater remediation based on a decade of intensive research, development, and demonstrations, and lessons learned from commercial field applications.
Contents
List of Figures
List of Tables
CHAPTER 1: IN SITU CHEMICAL OXIDATION: TECHNOLOGY DESCRIPTION AND STATUS
1.1 CONTAMINATED SITES AND IN SITU REMEDIATION
1.1.1 Introduction
1.1.2 Characteristics of Contaminated Sites
1.1.3 Site Remediation Approaches
1.1.4 Organization of This Volume on ISCO
1.2 ISCO AS A REMEDIATION TECHNOLOGY
1.3 EVOLUTION OF ISCO
1.3.1 Research and Development Activities
1.3.2 Field Applications
1.4 SYSTEM SELECTION, DESIGN, AND IMPLEMENTATION
1.5 PROJECT PERFORMANCE AND COSTS
1.6 SUMMARY
REFERENCES
CHAPTER 2: FUNDAMENTALS OF ISCO USING HYDROGEN PEROXIDE
2.1 INTRODUCTION
2.2 CHEMISTRY PRINCIPLES
2.2.1 Physical and Chemical Properties
2.2.2 Oxidation Reactions
2.2.2.1 Direct Oxidation
2.2.2.2 Free Radicals and Other Reactive Intermediates
Hydroxyl Radical (OH)
Superoxide Anion (O2-)
Perhydroxyl Radical (HO2)
Hydroperoxide Anion (HO2-)
Ferryl Ion [Fe(IV) FeO2+]
Solvated Electrons [e-(aq)]
Singlet Oxygen (1O2)
Atmospheric Oxygen (O2)
2.2.2.3 Impact of pH on Radical Intermediates
2.2.3 Catalysis of Hydrogen Peroxide
2.2.3.1 Catalysis with Dissolved Iron
2.2.3.2 Catalysis with Natural Minerals
2.2.3.3 Catalysis with Chelated Metals and Impacts of Other Organo-Metallic Complexes
2.2.4 CHP Reaction Kinetics
2.2.4.1 Fundamental Reaction Kinetics and Modeling Approaches
Fundamental Chemistry Models
Competition Kinetics Analysis
Other Approaches
2.2.4.2 Hydrogen Peroxide Decomposition Kinetics in Porous Media (Oxidant Persistence)
Hydrogen Peroxide Stabilization
Oxidant Persistence
2.2.5 Factors Affecting Efficiency and Effectiveness of Oxidation
2.2.5.1 Competing Nonproductive Reactions
Carbonate and Bicarbonate
Chloride
Sulfate
Hydrogen Peroxide
Other Anions
Biologic Enzymes
2.2.5.2 Contaminant Mineralization and Byproduct Formation
2.2.5.3 Natural Organic Matter
2.2.5.4 Temperature
2.2.5.5 Oxygen Gas
2.3 OXIDANT INTERACTIONS IN THE SUBSURFACE
2.3.1 Impact of Oxidant Persistence on Oxidant Transport
2.3.2 Impacts on Metal Mobility
2.3.2.1 Studies of Increased Metal Mobility during CHP treatment
2.3.2.2 Oxidative Alteration or Destruction of NOM
2.3.2.3 Alteration of pH
2.4 CONTAMINANT TREATABILITY
2.4.1 Halogenated Aliphatic Compounds
2.4.1.1 Chloroethenes
2.4.1.2 Chloroethanes
2.4.1.3 Halomethanes
2.4.1.4 Other Halogenated Aliphatic Compounds
2.4.2 Chlorinated Aromatic Compounds
2.4.2.1 Chlorobenzenes and Chlorophenols
2.4.2.2 Polychlorinated Biphenyls, Dioxins, and Furans
2.4.3 Fuel Hydrocarbons
2.4.3.1 Methyl Tert-Butyl Ether
2.4.3.2 Benzene, Toluene, Ethylbenzene, and Total Xylenes
2.4.3.3 Total Petroleum Hydrocarbons and Fuel Mixtures
2.4.4 Polycyclic Aromatic Hydrocarbons
2.4.5 High Explosives, Nitro- and Amino-Organic Compounds
2.4.6 Pesticides
2.4.7 Sorbed or NAPL Contaminants
2.5 SUMMARY
References
CHAPTER 3: FUNDAMENTALS OF ISCO USING PERMANGANATE
3.1 INTRODUCTION
3.2 CHEMISTRY PRINCIPLES
3.2.1 Physical and Chemical Properties
3.2.2 Oxidation Reactions
3.2.3 Reaction Mechanisms and Pathways
3.2.4 Permanganate Reaction Kinetics
3.2.5 Manganese Dioxide Production
3.2.6 Carbon Dioxide Gas Evolution
3.2.7 Oxidation of Natural Organic Matter
3.3 OXIDANT INTERACTIONS IN THE SUBSURFACE
3.3.1 Natural Oxidant Demand
3.3.1.1 Process Description
3.3.1.2 NOD Magnitude
3.3.1.3 NOD Kinetics
Overview of Considerations
Instantaneous NOD Approach
Rate-Limited NOD Approaches
3.3.1.4 Impact of NOD on Permanganate Transport
3.3.2 Permanganate Impacts on Subsurface Transport Processes
3.3.2.1 Impact of MnO2 on Flow and Transport
3.3.2.2 Impact of Gas Evolution on Flow and Transport
3.3.2.3 Impacts on DNAPL Mass Transfer Processes
Dissolution Enhancement by COC Oxidation
Dissolution Inhibition Due to MnO2 Deposition
Encapsulation of DNAPLs by MnO2
Mitigating Efficiency Problems Caused by MnO2 Deposition
3.3.2.4 Oxidation Impacts on Contaminant Sorption
3.3.2.5 Impacts of Permanganate ISCO on Metal Mobility
Alteration of pH and Eh
Formation of MnO2
Alteration of Ionic Content
Destruction or Alteration of NOM
Introduction of Metals as Impurities in Permanganate
Metals Mobilization Observed During Permanganate ISCO
3.3.2.6 Density-Driven Advection
3.4 CONTAMINANT TREATABILITY
3.4.1 Chloroethenes
3.4.2 Chloroethanes and Chloromethanes
3.4.3 BTEX, MTBE, and Saturated Aliphatic Compounds
3.4.4 Phenols
3.4.5 Polycyclic Aromatic Hydrocarbons
3.4.6 High Explosives and Related Compounds
3.4.7 Pesticides
3.5 SUMMARY
References
CHAPTER 4: FUNDAMENTALS OF ISCO USING PERSULFATE
4.1 INTRODUCTION
4.2 CHEMISTRY PRINCIPLES
4.2.1 Physical and Chemical Properties
4.2.2 Oxidation Reactions
4.2.2.1 Direct Oxidation
4.2.2.2 Free Radical Oxidation
4.2.2.3 Impact of pH on Radical Intermediates
4.2.3 Persulfate Activation and Propagation Reactions
4.2.3.1 Activation Methods
Heat Activation
Activation with Dissolved Iron and Other Transition Metals
Activation with Chelated Metals
Activation with Hydrogen Peroxide
Activation with Alkaline pH
4.2.3.2 Propagation Reactions
4.2.4 Persulfate Reaction Kinetics
4.2.4.1 Persulfate Decomposition Kinetics in Porous Media (Oxidant Persistence)
4.2.4.2 Fundamental Reaction Kinetics and Modeling Approaches
4.2.5 Factors Affecting Efficiency and Effectiveness of Oxidation
4.2.5.1 Carbonate and Bicarbonate
4.2.5.2 Chloride
4.2.5.3 Porous Media
4.3 PERSULFATE INTERACTIONS IN THE SUBSURFACE
4.3.1 Impacts on Subsurface Transport Processes
4.3.1.1 Impacts on NAPL
Conceptual Model of NAPLs in the Subsurface During ISCO
Reactions at the NAPL-Water Interface
Potential for Impacts to Persulfate Reaction Chemistry
Potential for Gas Evolution
4.3.1.2 Impacts on Contaminant Sorption
4.3.2 Impacts on Metal Mobility
4.4 CONTAMINANT TREATABILITY
4.4.1 Halogenated Aliphatics
4.4.1.1 Chloroethenes
4.4.1.2 Chloroethanes
4.4.1.3 Halogenated Methanes
4.4.2 Chlorinated Aromatics
4.4.2.1 Chlorobenzenes and Chlorophenols
4.4.2.2 Polychlorinated Biphenyls
4.4.3 Fuel Hydrocarbons
4.4.3.1 Methyl Tert-Butyl Ether
4.4.3.2 BTEX and Other Aromatic Hydrocarbons
4.4.3.3 Aliphatic Hydrocarbons
4.4.4 Polycyclic Aromatic Hydrocarbons
4.4.5 Nitro-Aromatic Compounds
4.4.6 Pesticides
4.5 SUMMARY
References
CHAPTER 5: FUNDAMENTALS OF ISCO USING OZONE
5.1 INTRODUCTION
5.2 CHEMISTRY PRINCIPLES
5.2.1 Physical and Chemical Properties
5.2.2 Oxidation Reactions
5.2.2.1 Gas Phase Reactions
5.2.2.2 Aqueous Phase Reactions
Direct Oxidation Reactions
Free Radical Reactions
Impact of pH on Reaction Pathways
5.2.2.3 Peroxone Reactions
5.2.3 Ozone Reaction Kinetics
5.3 OXIDANT INTERACTIONS IN THE SUBSURFACE
5.3.1 Interactions Affecting Reaction Chemistry
5.3.1.1 Impact of Metal Oxides
5.3.1.2 Impact of Natural Organic Matter
5.3.1.3 Impact of Dissolved Solutes
5.3.2 Interactions Affecting Ozone Transport
5.3.2.1 Ozone Reaction Characteristics
5.3.2.2 Subsurface Conditions Impacting Ozone Transport
Porous Media Water Content
Natural Organic Matter Content
Contaminant Concentrations
Metal Oxides and Other Minerals
5.3.3 Ozone Transport Processes
5.3.3.1 Vadose Zone Processes
5.3.3.2 Saturated Zone Processes
Ozone Sparging and Gas Flow
Ozone Mass Transfer and Reaction
Impact of Ozone on Contaminant Transport
5.3.4 Modeling of ISCO Using Ozone
5.3.5 Ozone Impacts on Metal Mobility
5.3.5.1 Changes in Subsurface Conditions
Alteration of pH and Eh
Alteration or Destruction of NOM
Changes in Water Content
5.3.5.2 Assessing Metal Mobility Under Field Conditions
5.4 CONTAMINANT TREATABILITY
5.4.1 Chlorinated Aliphatics
5.4.2 Chlorinated Aromatics
5.4.3 Fuel Components and Total Petroleum Hydrocarbons
5.4.3.1 Aliphatic Hydrocarbons
5.4.3.2 Aromatic Hydrocarbons
5.4.3.3 Methyl Tert-Butyl Ether
5.4.4 Coal Tars, Creosote, and Hydrocarbon Wastes
5.4.4.1 Polycyclic Aromatic Hydrocarbons
5.4.4.2 Phenolic Compounds
5.4.5 Nitroaromatics and Nitroamine Explosives
5.4.6 Pesticides
5.5 SUMMARY
References
CHAPTER 6: PRINCIPLES OF ISCO RELATED SUBSURFACE TRANSPORT AND MODELING
6.1 INTRODUCTION
6.2 SOURCE ZONE ARCHITECTURE
6.3 CONTAMINANT MASS TRANSFER
6.3.1 NAPL Dissolution
6.3.2 Contaminant Sorption/Desorption
6.4 PRIMARY REAGENT TRANSPORT PROCESSES
6.4.1 Advection
6.4.2 Dispersion
6.4.3 Diffusion
6.4.4 Density-Induced Flow
6.4.5 Sorption
6.4.6 Gas Injection
6.5 PROCESSES IMPACTING HYDRAULIC CONDITIONS
6.5.1 Permeability Reductions Caused by Immobile Components
6.5.1.1 NAPL Content
6.5.1.2 Solids Formation
6.5.2 Gas Formation
6.6 OXIDANT/CONTAMINANT KINETIC REACTION EXPRESSIONS
6.6.1 Permanganate Reaction
6.6.2 Ozone Reaction
6.6.3 Hydrogen Peroxide Reaction
6.6.4 Persulfate Reaction
6.7 OXIDANT CONSUMPTION BY NONPRODUCTIVE REACTIONS
6.7.1 Permanganate Nonproductive Oxidant Demand
6.7.2 Ozone Nonproductive Oxidant Demand
6.7.3 Hydrogen Peroxide Nonproductive Oxidant Demand
6.7.4 Persulfate Nonproductive Oxidant Demand
6.8 PUBLISHED ISCO MODELING STUDIES
6.8.1 Ozone Modeling
6.8.2 Permanganate Modeling
6.9 AVAILABILITY OF ISCO MODELING TOOLS
6.9.1 Model Dimensions (1-D/2-D/3-D)
6.9.2 Analytical Solutions
6.9.3 Conceptual Design for ISCO
6.9.3.1 CDISCO Permanganate Transport Model
6.9.3.2 CDISCO Cost Estimating Procedure
6.9.3.3 Application of CDISCO to Persulfate and CHP
6.9.4 Chemical Oxidation Reactive Transport in Three-Dimensions
6.9.4.1 CORT3D Model Formulation
6.9.4.2 CORT3D Model Code Verification
6.9.4.3 CORT3D Simulation of Navy Training Center Site, Florida
6.10 SUMMARY
REFERENCES
CHAPTER 7: PRINCIPLES OF COMBINING ISCO WITH OTHER IN SITU REMEDIAL APPROACHES
7.1 INTRODUCTION
7.2 IN SITU BIOLOGICAL METHODS
7.2.1 Impacts of Oxidants on Geochemistry and Bioprocesses
7.2.2 Enhanced Biodegradability of Contaminants by Pre-oxidation
7.2.3 Monitored Natural Attenuation
7.2.4 Enhanced In Situ Bioremediation
7.2.4.1 Anaerobic Processes
7.2.4.2 Aerobic Processes
7.3 SURFACTANT/COSOLVENT FLUSHING METHODS
7.3.1 Oxidation in the Presence of Surfactants or Cosolvents
7.3.2 Oxidation Mechanism Shifts in the Presence of Cosolvents
7.3.3 Oxidant Compatibility with Surfactants and Cosolvents
7.3.4 Surfactant Production by Oxidation Reactions
7.4 ABIOTIC REDUCTION METHODS
7.4.1 Zero-Valent Iron
7.4.2 Other In Situ Chemical Reduction Technologies
7.5 AIR SPARGING METHODS
7.6 THERMAL METHODS
7.7 FIELD APPLICATIONS OF COMBINED APPROACHES
7.8 SUMMARY
References
CHAPTER 8: EVALUATION OF ISCO FIELD APPLICATIONS AND PERFORMANCE
8.1 INTRODUCTION
8.2 PREVIOUS CASE STUDY REVIEWS
8.3 DEVELOPMENT OF AN ISCO CASE STUDY DATABASE
8.3.1 Key Database Parameter Definitions
8.3.1.1 Site Geology
8.3.1.2 Oxidants
8.3.1.3 COC Groups
8.3.1.4 Treatability Studies
8.3.1.5 Project Goals
8.3.1.6 Design Parameters
Number of Pore Volumes Delivered
Oxidant Loading Rate
8.3.1.7 Percent Reduction in Maximum Groundwater Concentration
8.3.1.8 Cost
8.3.1.9 Coupling
8.3.1.10 Rebound
8.3.2 Case Study Database Development Construction
8.3.3 Potential Limitations
8.3.3.1 Data Collection Limitations
8.3.3.2 Data Reduction and Analysis Limitations
8.4 OVERVIEW OF ISCO CASE STUDY DATABASE CONTENTS
8.5 ANALYSIS OF CONDITIONS IMPACTING ISCO DESIGNS
8.5.1 COCs Treated
8.5.2 Hydrogeologic Conditions
8.5.3 Oxidant
8.6 ANALYSIS OF CONDITIONS IMPACTING ISCO TREATMENT PERFORMANCE
8.6.1 Use of Performance Metrics
8.6.2 Performance Experiences and Effects of Design and Environmental Conditions
8.7 SECONDARY ISCO IMPACTS
8.8 SUMMARY OF KEY FINDINGS
8.9 SUMMARY
References
CHAPTER 9: SYSTEMATIC APPROACH FOR SITE-SPECIFIC ENGINEERING OF ISCO
9.1 INTRODUCTION
9.2 SCREENING OF ISCO APPLICABILITY
9.2.1 Introduction
9.2.2 Site Characterization Data Needed for CSM Development and Screening of ISCO
9.2.3 Screening ISCO for Site-Specific Contaminants, Site Conditions, and Treatment Goals
9.2.3.1 Determine ISCO Applicability for COCs
9.2.4 The Conceptual Site Model for ISCO Screening
9.2.5 Consideration of Pre-ISCO Remediation
9.2.6 Detailed Screening of ISCO
9.2.7 Consideration of ISCO Coupling
9.2.8 Outcomes of the ISCO Screening Process
9.3 CONCEPTUAL DESIGN OF AN ISCO SYSTEM
9.3.1 Introduction
9.3.2 The Target Treatment Zone
9.3.3 Tier 1 Conceptual Design
9.3.3.1 Design Considerations
9.3.3.2 Tier 1 Design Approaches
Tier 1 Mass Balance Design Approach
Tier 1 Analytical Model Design Approach
9.3.4 Feasibility of Conceptual Design Options
9.3.5 Ranking Oxidant and Delivery Approach Options
9.3.6 Tier 2 Conceptual Design
9.3.6.1 Cost and Performance Confidence
9.3.6.2 Consider Additional Data Needs
9.3.6.3 Consider Additional Modeling Needs
9.3.6.4 Refining the Tier 1 Conceptual Design
9.3.6.5 Cost Estimation
9.4 DETAILED DESIGN AND PLANNING OF AN ISCO SYSTEM
9.4.1 Introduction
9.4.2 Preliminary Design Phase
9.4.2.1 The Preliminary Basis of Design Report
9.4.2.2 Data Adequacy for Design
9.4.2.3 The Operation and Contingency Plan
9.4.3 Final Design Phase
9.4.3.1 Contracting Approaches
9.4.3.2 Constructability Review
9.4.3.3 Value Engineering/Design Optimization Assessment
9.4.3.4 Construction Cost/Engineer´s Estimate
9.4.3.5 Projected Cost Versus Budget
9.4.3.6 Cost Optimization
9.4.4 Planning Phase
9.4.4.1 Procurement Packages, Bidding, and Contractor Selection
9.4.4.2 Quality Assurance, Health and Safety, and Performance Monitoring Plans
Quality Assurance Project Plan
Health and Safety Plan
Performance Monitoring Plan
9.5 IMPLEMENTATION AND PERFORMANCE MONITORING
9.5.1 Introduction
9.5.2 Implementation Phase
9.5.2.1 Pre-construction Activities
9.5.2.2 ISCO Implementation Infrastructure
9.5.2.3 Baseline Monitoring
9.5.2.4 Initiating ISCO Operations
9.5.3 Delivery Performance Monitoring Phase
9.5.4 Treatment Performance Monitoring Phase
9.6 SUMMARY
References
CHAPTER 10: SITE CHARACTERIZATION AND ISCO TREATMENT GOALS
10.1 INTRODUCTION
10.2 CONCEPTUAL SITE MODELS
10.2.1 General Description
10.2.2 Developing a CSM for ISCO
10.3 CHARACTERIZATION STRATEGIES AND APPROACHES
10.3.1 Introduction
10.3.2 Overview of the Triad Approach
10.3.2.1 Systematic Planning
10.3.2.2 Dynamic Work Strategies
10.3.2.3 Real-Time Measurements
10.4 CHARACTERIZATION METHODS AND TECHNIQUES
10.4.1 Site Features and Land Use Attributes
10.4.2 Nature and Extent of Contamination
10.4.2.1 Characterizing the Contaminants of Concern
10.4.2.2 Contaminant Mass Flux
10.4.3 Hydrogeologic Conditions
10.4.4 Geochemical Conditions
10.4.5 Fate and Transport Processes
10.4.6 Analysis and Visualization of Characterization Data
10.5 SITE CHARACTERIZATION DATA NEEDED FOR ISCO
10.6 ISCO TREATMENT OBJECTIVES AND GOALS
10.7 PERSPECTIVES ON CHARACTERIZATION AND ISCO
10.8 SUMMARY
References
CHAPTER 11: OXIDANT DELIVERY APPROACHES AND CONTINGENCY PLANNING
11.1 INTRODUCTION
11.2 PRIMARY TRANSPORT MECHANISMS AFFECTING DISTRIBUTION OF LIQUID OXIDANTS
11.2.1 Advection During Injection of Liquid Oxidants
11.2.2 Advection After Injection
11.2.3 Diffusion After Advective Delivery into the Subsurface
11.3 OXIDANT DELIVERY METHODS
11.3.1 Direct-Push Probes for Liquid Injection
11.3.2 Installed Wells for Liquid Injection
11.3.3 Installed Wells for Gaseous Sparging
11.3.4 Recirculation of Liquids
11.3.5 Trench or Curtain Emplacement of Oxidants
11.3.6 Mechanical Mixing of Oxidants and Soil
11.3.7 Fracturing for Oxidant Emplacement
11.3.8 Surface Application or Infiltration Gallery Methods
11.4 GENERAL CONSIDERATIONS FOR OXIDANT DELIVERY
11.4.1 Aquifer Heterogeneity
11.4.2 Contaminant Distribution
11.4.3 Underground Utilities and Other Preferential Pathways
11.4.4 Contaminant Displacement
11.4.5 Need for Oxidant Activation
11.5 ABOVEGROUND OXIDANT HANDLING AND MIXING
11.6 OBSERVATIONAL METHOD AND CONTINGENCY PLANNING
11.6.1 Observational Method
11.6.2 Contingency Planning
11.7 SUMMARY
References
CHAPTER 12: ISCO PERFORMANCE MONITORING
12.1 INTRODUCTION
12.2 GENERAL CONSIDERATIONS
12.2.1 Establishment of Operational Objectives
12.2.2 Accounting for ISCO Interactions in the Subsurface
12.2.3 Performance Monitoring for Site-Specific Conditions
12.3 MONITORING OF BASELINE CONDITIONS
12.3.1 Purpose and Scope
12.3.2 Approach and Methodologies
12.3.2.1 Baseline Monitoring Approach
12.3.2.2 Media and Locations to Be Monitored
12.3.2.3 Parameters and Analysis Methods
12.3.2.4 Sampling Methods
12.3.2.5 Frequency and Duration of Monitoring
12.4 MONITORING DURING OXIDANT DELIVERY
12.4.1 Purpose and Scope
12.4.2 Approach and Methodologies
12.4.2.1 Delivery Performance Monitoring Approach
12.4.2.2 Media and Locations to Be Sampled
12.4.2.3 Parameters and Analysis Methods
12.4.2.4 Sampling Methods
12.4.2.5 Frequency and Duration of Monitoring
12.5 MONITORING OF TREATMENT PERFORMANCE
12.5.1 Purpose and Scope
12.5.2 Approach and Methodologies
12.5.2.1 Treatment Performance Monitoring Approach
12.5.2.2 Media and Locations to Be Sampled
12.5.2.3 Parameters and Analysis Methods
12.5.2.4 Sampling Methods
12.5.2.5 Frequency and Duration of Monitoring
12.5.3 Data Evaluation
12.5.3.1 Aquifer Re-equilibration Evaluation
12.5.3.2 Rebound and Recontamination
12.5.3.3 Consideration of Changes to Site Conditions
12.5.3.4 Statistical Methods
12.6 SUMMARY
References
CHAPTER 13: PROJECT COST AND SUSTAINABILITY CONSIDERATIONS
13.1 INTRODUCTION
13.2 COST ESTIMATING APPROACHES
13.2.1 Classes of Estimates and Level of Details
13.2.2 Cost Estimating Methods
13.2.2.1 Historical and Parametric Cost Estimates
13.2.2.2 Spreadsheet-Based Cost Estimates
13.2.2.3 Remediation Cost-Estimating Software
13.3 PRIMARY COST COMPONENTS
13.4 HISTORICAL AND ILLUSTRATIVE COST ESTIMATES
13.4.1 ISCO Project Costs Based on Case Study Data
13.4.2 ISCO Project Costs Based on an Illustrative Example
13.4.3 Comparing ISCO Project Costs
13.5 SUSTAINABILITY CONSIDERATIONS
13.5.1 Sustainability Concepts and Definitions
13.5.2 Making Technologies More Sustainable
13.5.2.1 Net Impacts of ISCO
13.5.2.2 Making ISCO More Sustainable
13.6 SUMMARY
References
CHAPTER 14: ISCO STATUS AND FUTURE DIRECTIONS
14.1 INTRODUCTION
14.2 STRIVING FOR OPTIMAL APPLICATIONS OF ISCO
14.3 EMERGING APPROACHES AND TECHNOLOGIES
14.3.1 Combining ISCO with Other Technologies and Approaches
14.3.2 Enhanced Delivery Methods for ISCO
14.3.3 Improved ISCO Monitoring and Assessment
14.4 RESEARCH NEEDS AND BREAKTHROUGH AREAS
14.4.1 ISCO Process Chemistry
14.4.2 ISCO Delivery
14.4.3 ISCO System Design
14.4.4 ISCO Process Control and Assessment
14.5 SUMMARY
References
APPENDIX A LIST OF ACRONYMS, ABBREVIATIONS, AND SYMBOLS
CHEMICAL FORMULAS
MATHEMATICAL SYMBOLS (FROM CHAPterS2-6)
APPENDIX B UNIT CONVERSIO N TABLE
APPENDIX C GLOSSARY
APPENDIX D SUPPORTING INFORMATION FOR SITE-SPECIFIC ENGINEERING OF ISCO
D.1 TEST PROCEDURES FOR MEASUREMENT OF NATURAL OXIDANT DEMAND AND OXIDANT PERSISTENCE
D.1.1 Introduction
D.1.2 Sample Collection, Preservation, and Storage
D.1.3 Test Procedure for Measuring Oxidant Persistence
Test Procedure Steps
D.1.4 Example of Test Procedure and Data Analysis
Example D.1
D.1.5 References
D.2 TEST PROCEDURES FOR EVALUATING CONTAMINANT TREATABILITY AND REACTION PRODUCTS
D.2.1 Introduction
D.2.2 Test Procedures to Optimize Oxidation Chemistry
D.2.3 Test Procedures to Explore Additional System Chemistry Considerations
D.2.4 General Guidance
D.2.5 Precautions with Interpretation and Application of Results
D.3 ANALYTICAL METHODS FOR OXIDANT CONCENTRATIONS
D.3.1 Readily Available Methods
D.3.2 References
D.4 CONSIDERATIONS FOR ISCO PILOT-SCALE TESTING UNDER FIELD CONDITIONS
D.4.1 Pilot Test Objective
D.4.2 Injection Probe or Well Spacing and Volume/Mass of Oxidant
D.4.3 Equipment
D.4.4 Monitoring
D.4.5 Examples
D.5 EXAMPLE PRELIMINARY BASIS OF DESIGN REPORT OUTLINE FOR IN SITU CHEMICAL OXIDATION BY PERMANGANATE DIRECT INJECTION
D.6 TYPICAL COMPONENTS OF AN OPERATION PLAN FOR ISCO IMPLEMENTATION
D.6.1 Operational Metrics
D.6.2 ISCO Treatment Milestones
D.7 DEVELOPMENT OF ISCO PERFORMANCE SPECIFICATIONS AND/OR DETAILED DESIGN SPECIFICATIONS AND DRAWINGS
D.7.1 Performance Specifications
D.7.2 Detailed Design Specifications and Drawings
D.8 QUALITY ASSURANCE PROJECT PLAN (QAPP) CONTENT
D.9 DESCRIPTION OF POTENTIAL PRE-CONSTRUCTION ACTIVITIES FOR AN ISCO PROJECT
D.9.1 Injection Permitting
D.9.2 Utility Clearance
D.9.3 Potential Receptor Survey
D.9.4 Engineering Controls for ISCO Implementation
D.9.5 Administrative Activities
D.9.6 Health and Safety Preparations
D.9.7 References
D.10 CONSTRUCTION AND DELIVERY EFFECTIVENESS QUALITY ASSURANCE AND QUALITY CONTROL (QA/QC) GUIDELINES
APPENDIX E CASE STUDIES AND ILLUSTRATIVE APPLICATIONS
E.1 CASE STUDY: OZONE PILOT TEST
E.1.1 Abstract
E.1.2 Summary of Site Characteristics
E.1.3 Summary of Pilot Test Features and Results
E.1.4 References
E.2 CASE STUDY: PERSULFATE PILOT TEST
E.2.1 Abstract
E.2.2 Summary of Site Characteristics
E.2.3 Summary of Pilot Test Features and Results
E.2.4 References
E.3 CASE STUDY: HYDROGEN PEROXIDE PILOT TEST
E.3.1 Abstract
E.3.2 Summary of Site Characteristics
E.3.3 Summary of Pilot Test Features and Results
E.3.4 References
E.4 ILLUSTRATIVE APPLICATIONS: COMBINED APPROACHES
E.4.1 Impacts of Potassium Permanganate on Anaerobic Microbial Communities for Remediation of Chlorinated Solvents
E.4.2 Catalyzed Hydrogen Peroxide and Associated Exothermicity for PAH Recovery and Remediation at a Former Manufactured Gas Plant Site
E.4.3 Excavation Combined with Catalyzed Hydrogen Peroxide and Sodium Permanganate ISCO to Achieve Maximum Contaminant Levels at a PCE Site
E.4.4 References
INDEX
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This volume provides comprehensive up-to-date descriptions of the principles and practices of in situ chemical oxidation (ISCO) for groundwater remediation based on a decade of intensive research, development, and demonstrations, and lessons learned from commercial field applications.
Contents
List of Figures
List of Tables
CHAPTER 1: IN SITU CHEMICAL OXIDATION: TECHNOLOGY DESCRIPTION AND STATUS
1.1 CONTAMINATED SITES AND IN SITU REMEDIATION
1.1.1 Introduction
1.1.2 Characteristics of Contaminated Sites
1.1.3 Site Remediation Approaches
1.1.4 Organization of This Volume on ISCO
1.2 ISCO AS A REMEDIATION TECHNOLOGY
1.3 EVOLUTION OF ISCO
1.3.1 Research and Development Activities
1.3.2 Field Applications
1.4 SYSTEM SELECTION, DESIGN, AND IMPLEMENTATION
1.5 PROJECT PERFORMANCE AND COSTS
1.6 SUMMARY
REFERENCES
CHAPTER 2: FUNDAMENTALS OF ISCO USING HYDROGEN PEROXIDE
2.1 INTRODUCTION
2.2 CHEMISTRY PRINCIPLES
2.2.1 Physical and Chemical Properties
2.2.2 Oxidation Reactions
2.2.2.1 Direct Oxidation
2.2.2.2 Free Radicals and Other Reactive Intermediates
Hydroxyl Radical (OH)
Superoxide Anion (O2-)
Perhydroxyl Radical (HO2)
Hydroperoxide Anion (HO2-)
Ferryl Ion [Fe(IV) FeO2+]
Solvated Electrons [e-(aq)]
Singlet Oxygen (1O2)
Atmospheric Oxygen (O2)
2.2.2.3 Impact of pH on Radical Intermediates
2.2.3 Catalysis of Hydrogen Peroxide
2.2.3.1 Catalysis with Dissolved Iron
2.2.3.2 Catalysis with Natural Minerals
2.2.3.3 Catalysis with Chelated Metals and Impacts of Other Organo-Metallic Complexes
2.2.4 CHP Reaction Kinetics
2.2.4.1 Fundamental Reaction Kinetics and Modeling Approaches
Fundamental Chemistry Models
Competition Kinetics Analysis
Other Approaches
2.2.4.2 Hydrogen Peroxide Decomposition Kinetics in Porous Media (Oxidant Persistence)
Hydrogen Peroxide Stabilization
Oxidant Persistence
2.2.5 Factors Affecting Efficiency and Effectiveness of Oxidation
2.2.5.1 Competing Nonproductive Reactions
Carbonate and Bicarbonate
Chloride
Sulfate
Hydrogen Peroxide
Other Anions
Biologic Enzymes
2.2.5.2 Contaminant Mineralization and Byproduct Formation
2.2.5.3 Natural Organic Matter
2.2.5.4 Temperature
2.2.5.5 Oxygen Gas
2.3 OXIDANT INTERACTIONS IN THE SUBSURFACE
2.3.1 Impact of Oxidant Persistence on Oxidant Transport
2.3.2 Impacts on Metal Mobility
2.3.2.1 Studies of Increased Metal Mobility during CHP treatment
2.3.2.2 Oxidative Alteration or Destruction of NOM
2.3.2.3 Alteration of pH
2.4 CONTAMINANT TREATABILITY
2.4.1 Halogenated Aliphatic Compounds
2.4.1.1 Chloroethenes
2.4.1.2 Chloroethanes
2.4.1.3 Halomethanes
2.4.1.4 Other Halogenated Aliphatic Compounds
2.4.2 Chlorinated Aromatic Compounds
2.4.2.1 Chlorobenzenes and Chlorophenols
2.4.2.2 Polychlorinated Biphenyls, Dioxins, and Furans
2.4.3 Fuel Hydrocarbons
2.4.3.1 Methyl Tert-Butyl Ether
2.4.3.2 Benzene, Toluene, Ethylbenzene, and Total Xylenes
2.4.3.3 Total Petroleum Hydrocarbons and Fuel Mixtures
2.4.4 Polycyclic Aromatic Hydrocarbons
2.4.5 High Explosives, Nitro- and Amino-Organic Compounds
2.4.6 Pesticides
2.4.7 Sorbed or NAPL Contaminants
2.5 SUMMARY
References
CHAPTER 3: FUNDAMENTALS OF ISCO USING PERMANGANATE
3.1 INTRODUCTION
3.2 CHEMISTRY PRINCIPLES
3.2.1 Physical and Chemical Properties
3.2.2 Oxidation Reactions
3.2.3 Reaction Mechanisms and Pathways
3.2.4 Permanganate Reaction Kinetics
3.2.5 Manganese Dioxide Production
3.2.6 Carbon Dioxide Gas Evolution
3.2.7 Oxidation of Natural Organic Matter
3.3 OXIDANT INTERACTIONS IN THE SUBSURFACE
3.3.1 Natural Oxidant Demand
3.3.1.1 Process Description
3.3.1.2 NOD Magnitude
3.3.1.3 NOD Kinetics
Overview of Considerations
Instantaneous NOD Approach
Rate-Limited NOD Approaches
3.3.1.4 Impact of NOD on Permanganate Transport
3.3.2 Permanganate Impacts on Subsurface Transport Processes
3.3.2.1 Impact of MnO2 on Flow and Transport
3.3.2.2 Impact of Gas Evolution on Flow and Transport
3.3.2.3 Impacts on DNAPL Mass Transfer Processes
Dissolution Enhancement by COC Oxidation
Dissolution Inhibition Due to MnO2 Deposition
Encapsulation of DNAPLs by MnO2
Mitigating Efficiency Problems Caused by MnO2 Deposition
3.3.2.4 Oxidation Impacts on Contaminant Sorption
3.3.2.5 Impacts of Permanganate ISCO on Metal Mobility
Alteration of pH and Eh
Formation of MnO2
Alteration of Ionic Content
Destruction or Alteration of NOM
Introduction of Metals as Impurities in Permanganate
Metals Mobilization Observed During Permanganate ISCO
3.3.2.6 Density-Driven Advection
3.4 CONTAMINANT TREATABILITY
3.4.1 Chloroethenes
3.4.2 Chloroethanes and Chloromethanes
3.4.3 BTEX, MTBE, and Saturated Aliphatic Compounds
3.4.4 Phenols
3.4.5 Polycyclic Aromatic Hydrocarbons
3.4.6 High Explosives and Related Compounds
3.4.7 Pesticides
3.5 SUMMARY
References
CHAPTER 4: FUNDAMENTALS OF ISCO USING PERSULFATE
4.1 INTRODUCTION
4.2 CHEMISTRY PRINCIPLES
4.2.1 Physical and Chemical Properties
4.2.2 Oxidation Reactions
4.2.2.1 Direct Oxidation
4.2.2.2 Free Radical Oxidation
4.2.2.3 Impact of pH on Radical Intermediates
4.2.3 Persulfate Activation and Propagation Reactions
4.2.3.1 Activation Methods
Heat Activation
Activation with Dissolved Iron and Other Transition Metals
Activation with Chelated Metals
Activation with Hydrogen Peroxide
Activation with Alkaline pH
4.2.3.2 Propagation Reactions
4.2.4 Persulfate Reaction Kinetics
4.2.4.1 Persulfate Decomposition Kinetics in Porous Media (Oxidant Persistence)
4.2.4.2 Fundamental Reaction Kinetics and Modeling Approaches
4.2.5 Factors Affecting Efficiency and Effectiveness of Oxidation
4.2.5.1 Carbonate and Bicarbonate
4.2.5.2 Chloride
4.2.5.3 Porous Media
4.3 PERSULFATE INTERACTIONS IN THE SUBSURFACE
4.3.1 Impacts on Subsurface Transport Processes
4.3.1.1 Impacts on NAPL
Conceptual Model of NAPLs in the Subsurface During ISCO
Reactions at the NAPL-Water Interface
Potential for Impacts to Persulfate Reaction Chemistry
Potential for Gas Evolution
4.3.1.2 Impacts on Contaminant Sorption
4.3.2 Impacts on Metal Mobility
4.4 CONTAMINANT TREATABILITY
4.4.1 Halogenated Aliphatics
4.4.1.1 Chloroethenes
4.4.1.2 Chloroethanes
4.4.1.3 Halogenated Methanes
4.4.2 Chlorinated Aromatics
4.4.2.1 Chlorobenzenes and Chlorophenols
4.4.2.2 Polychlorinated Biphenyls
4.4.3 Fuel Hydrocarbons
4.4.3.1 Methyl Tert-Butyl Ether
4.4.3.2 BTEX and Other Aromatic Hydrocarbons
4.4.3.3 Aliphatic Hydrocarbons
4.4.4 Polycyclic Aromatic Hydrocarbons
4.4.5 Nitro-Aromatic Compounds
4.4.6 Pesticides
4.5 SUMMARY
References
CHAPTER 5: FUNDAMENTALS OF ISCO USING OZONE
5.1 INTRODUCTION
5.2 CHEMISTRY PRINCIPLES
5.2.1 Physical and Chemical Properties
5.2.2 Oxidation Reactions
5.2.2.1 Gas Phase Reactions
5.2.2.2 Aqueous Phase Reactions
Direct Oxidation Reactions
Free Radical Reactions
Impact of pH on Reaction Pathways
5.2.2.3 Peroxone Reactions
5.2.3 Ozone Reaction Kinetics
5.3 OXIDANT INTERACTIONS IN THE SUBSURFACE
5.3.1 Interactions Affecting Reaction Chemistry
5.3.1.1 Impact of Metal Oxides
5.3.1.2 Impact of Natural Organic Matter
5.3.1.3 Impact of Dissolved Solutes
5.3.2 Interactions Affecting Ozone Transport
5.3.2.1 Ozone Reaction Characteristics
5.3.2.2 Subsurface Conditions Impacting Ozone Transport
Porous Media Water Content
Natural Organic Matter Content
Contaminant Concentrations
Metal Oxides and Other Minerals
5.3.3 Ozone Transport Processes
5.3.3.1 Vadose Zone Processes
5.3.3.2 Saturated Zone Processes
Ozone Sparging and Gas Flow
Ozone Mass Transfer and Reaction
Impact of Ozone on Contaminant Transport
5.3.4 Modeling of ISCO Using Ozone
5.3.5 Ozone Impacts on Metal Mobility
5.3.5.1 Changes in Subsurface Conditions
Alteration of pH and Eh
Alteration or Destruction of NOM
Changes in Water Content
5.3.5.2 Assessing Metal Mobility Under Field Conditions
5.4 CONTAMINANT TREATABILITY
5.4.1 Chlorinated Aliphatics
5.4.2 Chlorinated Aromatics
5.4.3 Fuel Components and Total Petroleum Hydrocarbons
5.4.3.1 Aliphatic Hydrocarbons
5.4.3.2 Aromatic Hydrocarbons
5.4.3.3 Methyl Tert-Butyl Ether
5.4.4 Coal Tars, Creosote, and Hydrocarbon Wastes
5.4.4.1 Polycyclic Aromatic Hydrocarbons
5.4.4.2 Phenolic Compounds
5.4.5 Nitroaromatics and Nitroamine Explosives
5.4.6 Pesticides
5.5 SUMMARY
References
CHAPTER 6: PRINCIPLES OF ISCO RELATED SUBSURFACE TRANSPORT AND MODELING
6.1 INTRODUCTION
6.2 SOURCE ZONE ARCHITECTURE
6.3 CONTAMINANT MASS TRANSFER
6.3.1 NAPL Dissolution
6.3.2 Contaminant Sorption/Desorption
6.4 PRIMARY REAGENT TRANSPORT PROCESSES
6.4.1 Advection
6.4.2 Dispersion
6.4.3 Diffusion
6.4.4 Density-Induced Flow
6.4.5 Sorption
6.4.6 Gas Injection
6.5 PROCESSES IMPACTING HYDRAULIC CONDITIONS
6.5.1 Permeability Reductions Caused by Immobile Components
6.5.1.1 NAPL Content
6.5.1.2 Solids Formation
6.5.2 Gas Formation
6.6 OXIDANT/CONTAMINANT KINETIC REACTION EXPRESSIONS
6.6.1 Permanganate Reaction
6.6.2 Ozone Reaction
6.6.3 Hydrogen Peroxide Reaction
6.6.4 Persulfate Reaction
6.7 OXIDANT CONSUMPTION BY NONPRODUCTIVE REACTIONS
6.7.1 Permanganate Nonproductive Oxidant Demand
6.7.2 Ozone Nonproductive Oxidant Demand
6.7.3 Hydrogen Peroxide Nonproductive Oxidant Demand
6.7.4 Persulfate Nonproductive Oxidant Demand
6.8 PUBLISHED ISCO MODELING STUDIES
6.8.1 Ozone Modeling
6.8.2 Permanganate Modeling
6.9 AVAILABILITY OF ISCO MODELING TOOLS
6.9.1 Model Dimensions (1-D/2-D/3-D)
6.9.2 Analytical Solutions
6.9.3 Conceptual Design for ISCO
6.9.3.1 CDISCO Permanganate Transport Model
6.9.3.2 CDISCO Cost Estimating Procedure
6.9.3.3 Application of CDISCO to Persulfate and CHP
6.9.4 Chemical Oxidation Reactive Transport in Three-Dimensions
6.9.4.1 CORT3D Model Formulation
6.9.4.2 CORT3D Model Code Verification
6.9.4.3 CORT3D Simulation of Navy Training Center Site, Florida
6.10 SUMMARY
REFERENCES
CHAPTER 7: PRINCIPLES OF COMBINING ISCO WITH OTHER IN SITU REMEDIAL APPROACHES
7.1 INTRODUCTION
7.2 IN SITU BIOLOGICAL METHODS
7.2.1 Impacts of Oxidants on Geochemistry and Bioprocesses
7.2.2 Enhanced Biodegradability of Contaminants by Pre-oxidation
7.2.3 Monitored Natural Attenuation
7.2.4 Enhanced In Situ Bioremediation
7.2.4.1 Anaerobic Processes
7.2.4.2 Aerobic Processes
7.3 SURFACTANT/COSOLVENT FLUSHING METHODS
7.3.1 Oxidation in the Presence of Surfactants or Cosolvents
7.3.2 Oxidation Mechanism Shifts in the Presence of Cosolvents
7.3.3 Oxidant Compatibility with Surfactants and Cosolvents
7.3.4 Surfactant Production by Oxidation Reactions
7.4 ABIOTIC REDUCTION METHODS
7.4.1 Zero-Valent Iron
7.4.2 Other In Situ Chemical Reduction Technologies
7.5 AIR SPARGING METHODS
7.6 THERMAL METHODS
7.7 FIELD APPLICATIONS OF COMBINED APPROACHES
7.8 SUMMARY
References
CHAPTER 8: EVALUATION OF ISCO FIELD APPLICATIONS AND PERFORMANCE
8.1 INTRODUCTION
8.2 PREVIOUS CASE STUDY REVIEWS
8.3 DEVELOPMENT OF AN ISCO CASE STUDY DATABASE
8.3.1 Key Database Parameter Definitions
8.3.1.1 Site Geology
8.3.1.2 Oxidants
8.3.1.3 COC Groups
8.3.1.4 Treatability Studies
8.3.1.5 Project Goals
8.3.1.6 Design Parameters
Number of Pore Volumes Delivered
Oxidant Loading Rate
8.3.1.7 Percent Reduction in Maximum Groundwater Concentration
8.3.1.8 Cost
8.3.1.9 Coupling
8.3.1.10 Rebound
8.3.2 Case Study Database Development Construction
8.3.3 Potential Limitations
8.3.3.1 Data Collection Limitations
8.3.3.2 Data Reduction and Analysis Limitations
8.4 OVERVIEW OF ISCO CASE STUDY DATABASE CONTENTS
8.5 ANALYSIS OF CONDITIONS IMPACTING ISCO DESIGNS
8.5.1 COCs Treated
8.5.2 Hydrogeologic Conditions
8.5.3 Oxidant
8.6 ANALYSIS OF CONDITIONS IMPACTING ISCO TREATMENT PERFORMANCE
8.6.1 Use of Performance Metrics
8.6.2 Performance Experiences and Effects of Design and Environmental Conditions
8.7 SECONDARY ISCO IMPACTS
8.8 SUMMARY OF KEY FINDINGS
8.9 SUMMARY
References
CHAPTER 9: SYSTEMATIC APPROACH FOR SITE-SPECIFIC ENGINEERING OF ISCO
9.1 INTRODUCTION
9.2 SCREENING OF ISCO APPLICABILITY
9.2.1 Introduction
9.2.2 Site Characterization Data Needed for CSM Development and Screening of ISCO
9.2.3 Screening ISCO for Site-Specific Contaminants, Site Conditions, and Treatment Goals
9.2.3.1 Determine ISCO Applicability for COCs
9.2.4 The Conceptual Site Model for ISCO Screening
9.2.5 Consideration of Pre-ISCO Remediation
9.2.6 Detailed Screening of ISCO
9.2.7 Consideration of ISCO Coupling
9.2.8 Outcomes of the ISCO Screening Process
9.3 CONCEPTUAL DESIGN OF AN ISCO SYSTEM
9.3.1 Introduction
9.3.2 The Target Treatment Zone
9.3.3 Tier 1 Conceptual Design
9.3.3.1 Design Considerations
9.3.3.2 Tier 1 Design Approaches
Tier 1 Mass Balance Design Approach
Tier 1 Analytical Model Design Approach
9.3.4 Feasibility of Conceptual Design Options
9.3.5 Ranking Oxidant and Delivery Approach Options
9.3.6 Tier 2 Conceptual Design
9.3.6.1 Cost and Performance Confidence
9.3.6.2 Consider Additional Data Needs
9.3.6.3 Consider Additional Modeling Needs
9.3.6.4 Refining the Tier 1 Conceptual Design
9.3.6.5 Cost Estimation
9.4 DETAILED DESIGN AND PLANNING OF AN ISCO SYSTEM
9.4.1 Introduction
9.4.2 Preliminary Design Phase
9.4.2.1 The Preliminary Basis of Design Report
9.4.2.2 Data Adequacy for Design
9.4.2.3 The Operation and Contingency Plan
9.4.3 Final Design Phase
9.4.3.1 Contracting Approaches
9.4.3.2 Constructability Review
9.4.3.3 Value Engineering/Design Optimization Assessment
9.4.3.4 Construction Cost/Engineer´s Estimate
9.4.3.5 Projected Cost Versus Budget
9.4.3.6 Cost Optimization
9.4.4 Planning Phase
9.4.4.1 Procurement Packages, Bidding, and Contractor Selection
9.4.4.2 Quality Assurance, Health and Safety, and Performance Monitoring Plans
Quality Assurance Project Plan
Health and Safety Plan
Performance Monitoring Plan
9.5 IMPLEMENTATION AND PERFORMANCE MONITORING
9.5.1 Introduction
9.5.2 Implementation Phase
9.5.2.1 Pre-construction Activities
9.5.2.2 ISCO Implementation Infrastructure
9.5.2.3 Baseline Monitoring
9.5.2.4 Initiating ISCO Operations
9.5.3 Delivery Performance Monitoring Phase
9.5.4 Treatment Performance Monitoring Phase
9.6 SUMMARY
References
CHAPTER 10: SITE CHARACTERIZATION AND ISCO TREATMENT GOALS
10.1 INTRODUCTION
10.2 CONCEPTUAL SITE MODELS
10.2.1 General Description
10.2.2 Developing a CSM for ISCO
10.3 CHARACTERIZATION STRATEGIES AND APPROACHES
10.3.1 Introduction
10.3.2 Overview of the Triad Approach
10.3.2.1 Systematic Planning
10.3.2.2 Dynamic Work Strategies
10.3.2.3 Real-Time Measurements
10.4 CHARACTERIZATION METHODS AND TECHNIQUES
10.4.1 Site Features and Land Use Attributes
10.4.2 Nature and Extent of Contamination
10.4.2.1 Characterizing the Contaminants of Concern
10.4.2.2 Contaminant Mass Flux
10.4.3 Hydrogeologic Conditions
10.4.4 Geochemical Conditions
10.4.5 Fate and Transport Processes
10.4.6 Analysis and Visualization of Characterization Data
10.5 SITE CHARACTERIZATION DATA NEEDED FOR ISCO
10.6 ISCO TREATMENT OBJECTIVES AND GOALS
10.7 PERSPECTIVES ON CHARACTERIZATION AND ISCO
10.8 SUMMARY
References
CHAPTER 11: OXIDANT DELIVERY APPROACHES AND CONTINGENCY PLANNING
11.1 INTRODUCTION
11.2 PRIMARY TRANSPORT MECHANISMS AFFECTING DISTRIBUTION OF LIQUID OXIDANTS
11.2.1 Advection During Injection of Liquid Oxidants
11.2.2 Advection After Injection
11.2.3 Diffusion After Advective Delivery into the Subsurface
11.3 OXIDANT DELIVERY METHODS
11.3.1 Direct-Push Probes for Liquid Injection
11.3.2 Installed Wells for Liquid Injection
11.3.3 Installed Wells for Gaseous Sparging
11.3.4 Recirculation of Liquids
11.3.5 Trench or Curtain Emplacement of Oxidants
11.3.6 Mechanical Mixing of Oxidants and Soil
11.3.7 Fracturing for Oxidant Emplacement
11.3.8 Surface Application or Infiltration Gallery Methods
11.4 GENERAL CONSIDERATIONS FOR OXIDANT DELIVERY
11.4.1 Aquifer Heterogeneity
11.4.2 Contaminant Distribution
11.4.3 Underground Utilities and Other Preferential Pathways
11.4.4 Contaminant Displacement
11.4.5 Need for Oxidant Activation
11.5 ABOVEGROUND OXIDANT HANDLING AND MIXING
11.6 OBSERVATIONAL METHOD AND CONTINGENCY PLANNING
11.6.1 Observational Method
11.6.2 Contingency Planning
11.7 SUMMARY
References
CHAPTER 12: ISCO PERFORMANCE MONITORING
12.1 INTRODUCTION
12.2 GENERAL CONSIDERATIONS
12.2.1 Establishment of Operational Objectives
12.2.2 Accounting for ISCO Interactions in the Subsurface
12.2.3 Performance Monitoring for Site-Specific Conditions
12.3 MONITORING OF BASELINE CONDITIONS
12.3.1 Purpose and Scope
12.3.2 Approach and Methodologies
12.3.2.1 Baseline Monitoring Approach
12.3.2.2 Media and Locations to Be Monitored
12.3.2.3 Parameters and Analysis Methods
12.3.2.4 Sampling Methods
12.3.2.5 Frequency and Duration of Monitoring
12.4 MONITORING DURING OXIDANT DELIVERY
12.4.1 Purpose and Scope
12.4.2 Approach and Methodologies
12.4.2.1 Delivery Performance Monitoring Approach
12.4.2.2 Media and Locations to Be Sampled
12.4.2.3 Parameters and Analysis Methods
12.4.2.4 Sampling Methods
12.4.2.5 Frequency and Duration of Monitoring
12.5 MONITORING OF TREATMENT PERFORMANCE
12.5.1 Purpose and Scope
12.5.2 Approach and Methodologies
12.5.2.1 Treatment Performance Monitoring Approach
12.5.2.2 Media and Locations to Be Sampled
12.5.2.3 Parameters and Analysis Methods
12.5.2.4 Sampling Methods
12.5.2.5 Frequency and Duration of Monitoring
12.5.3 Data Evaluation
12.5.3.1 Aquifer Re-equilibration Evaluation
12.5.3.2 Rebound and Recontamination
12.5.3.3 Consideration of Changes to Site Conditions
12.5.3.4 Statistical Methods
12.6 SUMMARY
References
CHAPTER 13: PROJECT COST AND SUSTAINABILITY CONSIDERATIONS
13.1 INTRODUCTION
13.2 COST ESTIMATING APPROACHES
13.2.1 Classes of Estimates and Level of Details
13.2.2 Cost Estimating Methods
13.2.2.1 Historical and Parametric Cost Estimates
13.2.2.2 Spreadsheet-Based Cost Estimates
13.2.2.3 Remediation Cost-Estimating Software
13.3 PRIMARY COST COMPONENTS
13.4 HISTORICAL AND ILLUSTRATIVE COST ESTIMATES
13.4.1 ISCO Project Costs Based on Case Study Data
13.4.2 ISCO Project Costs Based on an Illustrative Example
13.4.3 Comparing ISCO Project Costs
13.5 SUSTAINABILITY CONSIDERATIONS
13.5.1 Sustainability Concepts and Definitions
13.5.2 Making Technologies More Sustainable
13.5.2.1 Net Impacts of ISCO
13.5.2.2 Making ISCO More Sustainable
13.6 SUMMARY
References
CHAPTER 14: ISCO STATUS AND FUTURE DIRECTIONS
14.1 INTRODUCTION
14.2 STRIVING FOR OPTIMAL APPLICATIONS OF ISCO
14.3 EMERGING APPROACHES AND TECHNOLOGIES
14.3.1 Combining ISCO with Other Technologies and Approaches
14.3.2 Enhanced Delivery Methods for ISCO
14.3.3 Improved ISCO Monitoring and Assessment
14.4 RESEARCH NEEDS AND BREAKTHROUGH AREAS
14.4.1 ISCO Process Chemistry
14.4.2 ISCO Delivery
14.4.3 ISCO System Design
14.4.4 ISCO Process Control and Assessment
14.5 SUMMARY
References
APPENDIX A LIST OF ACRONYMS, ABBREVIATIONS, AND SYMBOLS
CHEMICAL FORMULAS
MATHEMATICAL SYMBOLS (FROM CHAPterS2-6)
APPENDIX B UNIT CONVERSIO N TABLE
APPENDIX C GLOSSARY
APPENDIX D SUPPORTING INFORMATION FOR SITE-SPECIFIC ENGINEERING OF ISCO
D.1 TEST PROCEDURES FOR MEASUREMENT OF NATURAL OXIDANT DEMAND AND OXIDANT PERSISTENCE
D.1.1 Introduction
D.1.2 Sample Collection, Preservation, and Storage
D.1.3 Test Procedure for Measuring Oxidant Persistence
Test Procedure Steps
D.1.4 Example of Test Procedure and Data Analysis
Example D.1
D.1.5 References
D.2 TEST PROCEDURES FOR EVALUATING CONTAMINANT TREATABILITY AND REACTION PRODUCTS
D.2.1 Introduction
D.2.2 Test Procedures to Optimize Oxidation Chemistry
D.2.3 Test Procedures to Explore Additional System Chemistry Considerations
D.2.4 General Guidance
D.2.5 Precautions with Interpretation and Application of Results
D.3 ANALYTICAL METHODS FOR OXIDANT CONCENTRATIONS
D.3.1 Readily Available Methods
D.3.2 References
D.4 CONSIDERATIONS FOR ISCO PILOT-SCALE TESTING UNDER FIELD CONDITIONS
D.4.1 Pilot Test Objective
D.4.2 Injection Probe or Well Spacing and Volume/Mass of Oxidant
D.4.3 Equipment
D.4.4 Monitoring
D.4.5 Examples
D.5 EXAMPLE PRELIMINARY BASIS OF DESIGN REPORT OUTLINE FOR IN SITU CHEMICAL OXIDATION BY PERMANGANATE DIRECT INJECTION
D.6 TYPICAL COMPONENTS OF AN OPERATION PLAN FOR ISCO IMPLEMENTATION
D.6.1 Operational Metrics
D.6.2 ISCO Treatment Milestones
D.7 DEVELOPMENT OF ISCO PERFORMANCE SPECIFICATIONS AND/OR DETAILED DESIGN SPECIFICATIONS AND DRAWINGS
D.7.1 Performance Specifications
D.7.2 Detailed Design Specifications and Drawings
D.8 QUALITY ASSURANCE PROJECT PLAN (QAPP) CONTENT
D.9 DESCRIPTION OF POTENTIAL PRE-CONSTRUCTION ACTIVITIES FOR AN ISCO PROJECT
D.9.1 Injection Permitting
D.9.2 Utility Clearance
D.9.3 Potential Receptor Survey
D.9.4 Engineering Controls for ISCO Implementation
D.9.5 Administrative Activities
D.9.6 Health and Safety Preparations
D.9.7 References
D.10 CONSTRUCTION AND DELIVERY EFFECTIVENESS QUALITY ASSURANCE AND QUALITY CONTROL (QA/QC) GUIDELINES
APPENDIX E CASE STUDIES AND ILLUSTRATIVE APPLICATIONS
E.1 CASE STUDY: OZONE PILOT TEST
E.1.1 Abstract
E.1.2 Summary of Site Characteristics
E.1.3 Summary of Pilot Test Features and Results
E.1.4 References
E.2 CASE STUDY: PERSULFATE PILOT TEST
E.2.1 Abstract
E.2.2 Summary of Site Characteristics
E.2.3 Summary of Pilot Test Features and Results
E.2.4 References
E.3 CASE STUDY: HYDROGEN PEROXIDE PILOT TEST
E.3.1 Abstract
E.3.2 Summary of Site Characteristics
E.3.3 Summary of Pilot Test Features and Results
E.3.4 References
E.4 ILLUSTRATIVE APPLICATIONS: COMBINED APPROACHES
E.4.1 Impacts of Potassium Permanganate on Anaerobic Microbial Communities for Remediation of Chlorinated Solvents
E.4.2 Catalyzed Hydrogen Peroxide and Associated Exothermicity for PAH Recovery and Remediation at a Former Manufactured Gas Plant Site
E.4.3 Excavation Combined with Catalyzed Hydrogen Peroxide and Sodium Permanganate ISCO to Achieve Maximum Contaminant Levels at a PCE Site
E.4.4 References
INDEX
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