In Situ Remediation Engineering

by Suthersan; Suthan S.

• ISBN13: 9781566706537
• ISBN10: 156670653X
• Format: Hardcover
• Copyright: 2004-12-28
• Publisher: CRC Press

Summary

In Situ Remediation Engineering provides a comprehensive guide to the design and implementation of reactive zone methods for treatment of all major classes of groundwater contamination. It teaches the fundamentals that underlie development of cost-effective reactive zone strategies, guides the selection of cost-effective remedial strategies and provides environmental engineers and scientists with tools to achieve optimal deployment of source area, reactive barrier, and site-wide treatments. It offers extensive coverage of remedial system operation, discussing reagent injection strategies, interpretation of process monitoring results for biological and chemical reactive zone systems, and impacts of treatment processes on aquifer hydraulic characteristics.

Table of Contents

Introduction	1	(64)
Legacy of Pollution	1	(1)
Development of in Situ Approaches	2	(3)
Types of in Situ Reactions	5	(23)
Microbial Reactions	8	(2)
Biochemical Energetics	10	(4)
Microbial Oxidation Reactions	14	(1)
Microbial Reduction Reactions	15	(1)
Microbial Metals Precipitation	16	(1)
Chemical Reactions	17	(1)
Chemically Oxidizing Reactions	18	(1)
Chemically Reducing Reactions	19	(1)
Hydrolytic Reactions	19	(3)
Acid-Base Reactions	22	(6)
Reactants and Solvents	28	(22)
Water-Solvent Reaction Medium	28	(2)
Solubility in Water	30	(1)
Reactants	31	(1)
Molecular Structures of Compounds	32	(13)
Functionalities and Environmental Behavior	45	(5)
Reversible vs. Irreversible Processes	50	(2)
Hydrogeology and Hydraulic Impacts	52	(2)
System Poise and Flux of Competing Compounds	54	(1)
Current Status	55	(10)
Regulatory Acceptance and Permitting	55	(3)
Biostimulation vs. Bioaugmentation	58	(1)
Biostimulation	58	(1)
Bioaugmentation	59	(1)
Contaminant Types	60	(1)
Emerging Contaminants	60	(2)
References	62	(3)
Microbial Reactive Zones	65	(162)
Types of Microbial Reactions	66	(2)
Microbial Oxidizing Zones	68	(10)
Engineered Aerobic Systems	68	(1)
Direct Aerobic Oxidation	69	(4)
Microbial Oxidation by Fe(III), Nitrate, and Sulfate	73	(2)
Aerobic Cometabolic Oxidation	75	(2)
Microbial Oxidation of MTBE	77	(1)
Microbial Reducing Zones	78	(109)
Enhanced Reductive Dechlorination	78	(7)
Microbial Ecology of Reductive Dechlorination	85	(3)
The Aquifer as an Ecosystem	88	(14)
Biochemistry of Reductive Dechlorination	102	(10)
Dechlorinating Bacterial Species and Consortia	112	(6)
Review of Field-Scale Bioaugmentation Studies	118	(5)
Summary of Bioaugmentation	123	(1)
Review of Field-Scale Biostimulation Studies	123	(26)
Evaluating Degradation Signatures	149	(6)
Summary and Conclusions	155	(3)
Abiotic Reductive Dechlorination	158	(3)
In Situ Precipitation of Heavy Metals	161	(4)
Principles of Heavy-Metal Precipitation	165	(5)
Chromium Precipitation	170	(4)
Nickel Precipitation	174	(1)
Arsenic Precipitation	175	(7)
Cadmium	182	(1)
Aquifer Parameters and Transport Mechanisms	182	(2)
Contaminant Removal Mechanisms	184	(1)
In Situ Denitrification	185	(2)
Emerging Contaminants	187	(40)
Perchlorate Reduction	188	(7)
1,4-Dioxane	195	(1)
Prospects for Mass Transfer	196	(1)
Biological Remedies	197	(3)
Explosives	200	(6)
Radionuclides	206	(1)
Uranium	207	(5)
Technetium-99 (99Tc)	212	(2)
Plutonium	214	(1)
N-Nitrosodimethylamine (NDMA)	215	(1)
References	216	(11)
Chemical Reactive Zones	227	(88)
Introduction to Chemical Reactive Zones	227	(1)
Chemical Reactivity	228	(17)
Oxidation States	229	(2)
Thermodynamic Feasibility of Reactions	231	(1)
Bond Energies	231	(1)
Gibbs Free Energy	232	(1)
Nonstandard Conditions --- The Nernst Equation	233	(1)
Kinetic Control of Reaction Rates	234	(1)
Reaction Order and Rate Equations	234	(5)
Kinetic Feasibility	239	(2)
Effect of Temperature on Reaction Rates	241	(1)
Estimating Temperature Effect on Thiosulfate-Mediated Destruction of Methyl Bromide	242	(1)
Effect of pH on Reactions	243	(1)
Effect of Ionic Strength on Reactions	243	(2)
Reaction Mechanisms	245	(21)
Electron Transfer Reactions	245	(1)
Electron Transfer (Oxidation--Reduction) Reactions	245	(3)
Radical Reactions	248	(2)
Carbonate Interference	250	(5)
Nucleophilic Substitution and Elimination Reactions	255	(3)
Nucleophilicity	258	(3)
Precipitation Reactions	261	(1)
Solubility in Aqueous Phase	262	(1)
The Solubility Product	262	(1)
Calculation of Nickel Concentrations from Ksp	263	(2)
Aging of Precipitated Solids	265	(1)
Heterogeneous Reactions	266	(1)
Chemical Oxidation Zones	266	(31)
Fenton's Reagent	266	(2)
Hydroxyl Radical Production Strategies	268	(1)
Conventional Fenton's Process	269	(1)
Iron Chelation Strategies	270	(1)
Mineral Iron Strategies	271	(1)
Radical Consumption by Carbonates and Other Competitive Inhibitors	271	(1)
Common Reaction By-Products	272	(1)
Monitoring Fenton's Reagent Applications	273	(1)
Permanganate Oxidation	274	(2)
Permanganate Demand Estimation and Injection Loading Requirements	276	(1)
Permanganate Reaction Mechanisms	277	(1)
By-Product Formation	278	(2)
Permanganate Reaction Kinetics	280	(1)
Sorption Effects on Permanganate Oxidation	280	(4)
Phase-Transfer Catalysts	284	(2)
Ozone	286	(1)
Ozone as the Sole Oxidant Source	286	(5)
Ozone-Peroxide Systems	291	(1)
Bench-Scale Ozonation of 1,4-Dioxane	292	(3)
By-Products	295	(1)
Persulfate	295	(2)
Chemical Reducing Zones	297	(12)
Hydrogen	297	(1)
Dithionite	297	(1)
Dithionite Chemistry	297	(3)
Dithionite-Driven Reduction of Chromium	300	(3)
Zero-Valent Iron	303	(1)
Zero-Valent Iron Reaction Mechanisms	304	(1)
Zero-Valent Iron Applicability	305	(2)
Reduced Vitamin B12	307	(2)
Chemical Precipitation Strategies	309	(6)
References	310	(5)
Components of an in Situ Reactive Zone	315	(80)
Site Screening	320	(10)
Site Access	320	(6)
Safety Considerations	326	(1)
Vapor Migration	327	(2)
Trends in Contaminant Concentration and Electron Acceptor Processes	329	(1)
Oxidation State of Contaminants	330	(3)
Site Conceptual Model	333	(8)
Hydrogeologic Model	333	(4)
Contaminant Distribution	337	(2)
Biogeochemical Characterization	339	(2)
Performance Measures	341	(16)
Process Monitoring	342	(1)
Performance Monitoring	343	(1)
Groundwater Sampling and Analysis	344	(3)
Dissolved Gases	347	(1)
Dissolved Oxygen Field Measurement	348	(1)
Analysis of Biogeochemical Parameters	348	(3)
Oxidation--Reduction Potential and EH	351	(2)
Microbial Assessments	353	(4)
System Design	357	(15)
Design Considerations	357	(1)
Geology	358	(1)
Hydraulic Conductivity	359	(1)
Groundwater Flow Characteristics	360	(1)
Saturated Thickness and Depth to Water	360	(1)
Geochemistry	361	(2)
Groundwater Chemistry	363	(1)
pH	364	(1)
Role of Sulfur in Enhanced Reductive Dechlorination Systems	365	(1)
IRZ Layout Options	366	(1)
Injection Well/Point Placement	367	(5)
Monitoring Well Placement	372	(1)
Reagents	372	(4)
Microbial IRZ Systems	372	(2)
Suitability of Different Electron Donors	374	(2)
Chemical IRZ Systems	376	(1)
Delivery System Design	376	(7)
Reagent Injection Strategy	381	(2)
Pilot Testing	383	(12)
Pilot Test Wells --- Number and Location	384	(2)
Duration of Pilot Study	386	(1)
Scaleup Issues	387	(1)
Sustainability and Reliability	388	(2)
Biofilm Developments	390	(1)
Site Closure	391	(1)
References	392	(3)
Building Reactive Zone Strategies	395	(74)
Introduction to Reactive Zone Strategies	395	(1)
A Conceptual Model for Contaminant Distribution	396	(31)
Reactive Zone Hydrogeology	396	(1)
Darcy's Law, Permeability, and Groundwater Velocity	397	(3)
A Dual-Porosity Pore-Scale Model	400	(2)
Contaminant Classes and Their Behaviors	402	(1)
High-Solubility Inorganics (Salts)	402	(1)
Transition Compounds	403	(1)
Miscible Organics	403	(1)
Hydrophobic Organics	403	(1)
Sorption and Desorption Processes	404	(1)
Adsorption	404	(1)
Absorption	405	(1)
Conventional Calculation of Sorbed-Phase and Total Contaminant Mass	406	(2)
Multi-Compartment Sorption Models	408	(3)
Cation Exchange Capacity	411	(1)
Contaminant Distribution in Aquifer Matrices	412	(1)
A Multi-Phase Conceptual Model for Contaminant Distribution	412	(3)
Distribution of Hydrophobic Organics	415	(3)
Distribution of Miscible Organics and Soluble Salts	418	(1)
Distribution of Metals	419	(1)
Steady-State and Non-Steady-State Distributions	420	(5)
Propagation of a Clean Water Front	425	(2)
Reactive Zone Structure	427	(13)
Injection Zone Management	429	(1)
Injection Radius	430	(1)
Injection Zone Tracer Test Example	431	(2)
Injection Volume Limitations	433	(1)
Balancing Injection Volumes and Frequencies	434	(1)
The Reactive Zone	435	(1)
The in Situ Bioreactor Concept	435	(2)
Bioreactor Acclimation --- Microbial Population Buildup Phase	437	(1)
Chemical Reactive Zones	438	(1)
The Desorption Zone	439	(1)
The Recovery Zone	439	(1)
Reactive Zone Strategies	440	(12)
Reactive Barriers	440	(1)
Source Treatments	441	(3)
Biological Reducing Zone Strategy for Nickel Precipitation	444	(5)
In Situ Oxidation of N-Nitrosodimethylamine	449	(2)
Reactive Zone Sequencing and Whole-Plume Treatments	451	(1)
Limitations of Aqueous-Phase Reactions in Contaminated Porous Media	452	(3)
Achieving Contact between Reactants and Targets	452	(2)
Contaminant Shielding by Organic Matter	454	(1)
Phase Transfer Catalysts and Surfactants in Chemical Reactive Zones	454	(1)
Partitioning Electron Donors, Surfactants, and Cosolvents in Biological Reactive Zones	455	(1)
Reaction Products and Consequences	455	(14)
Type Curves for Enhanced Reductive Dechlorination	456	(1)
The Taxonomy of Type Curves	456	(4)
Results of Partial Oxidation	460	(2)
Release of Sorbed 1,1,1-Trichloroethane Associated with Partial Oxidation by Fenton's Reagent	462	(1)
Reactions with Nontarget Organics	463	(1)
Redox Effects on Nontarget Inorganic Species	463	(1)
Redox Reduction Effects	464	(1)
Oxidation Effects	464	(1)
Reaction Product Effects on Hydraulic Conductivity	464	(1)
Chemical Oxidation Effects on Aquifer Conductivity	465	(1)
Chemical Reduction Effects on Aquifer Conductivity	465	(1)
Biological Reactive Zone Effects on Aquifer Conductivity	466	(1)
References	466	(3)
Appendix	469	(18)
Index	487