Suthersan, Suthan S. “Frontmatter” Natural and Enhanced Remediation Systems Edited by Suthan S. Suthersan Boca Raton: CRC Press LLC, 2001 ©2001 CRC Press LLC Natural and Enhanced Remediation Systems by Suthan S. Suthersan ©2001 CRC Press LLC This book contains information obtained from authentic and highly regarded sources. Reprinted material is quoted with permission, and sources are indicated. A wide variety of references are listed. Reasonable efforts have been made to publish reliable data and information, but the author and the publisher cannot assume responsibility for the validity of all materials or for the consequences of their use. Neither this book nor any part may be reproduced or transmitted in any form or by any means, electronic or mechanical, including photocopying, microfilming, and recording, or by any information storage or retrieval system, without prior permission in writing from the publisher. 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Suthersan. p. cm. — (Arcadis Geraghty & Miller science and engineering) Includes bibliographical references and index. ISBN 1-56670-282-8 1. Soil remediation. 2. Groundwater–Purification. 3. Hazardous wastes–Natural attenuation. 4. Bioremediation. I. Title. II. Geraghty & Miller environmental science and engineering series. TD878.S873 2001 628.5—dc21 2001029566 CIP ©2001 CRC Press LLC Sincere Thanks To: Sumathy, Shauna, and Nealon for their enthusiastic support and unending patience. STP, MTP, MLM, and SBB for their insight, support, inspiration, and trust. Dedicated with utmost humility to the heroes and heroines of Eelam who have put their lives in the line of fire to express their intellectual freedom. ©2001 CRC Press LLC Foreword I have worked with Dr. Suthersan for the past 13 years and have seen firsthand the impact he has had on the evolution of our business. Over this period, environ- mental remediation has moved from a world of standard operation and application of proven technology to one where more innovative concepts can be applied, tested, and developed for the benefit of the environment, the regulatory community, and industry. Dr. Suthersan has worked assiduously to develop new remediation tech- nologies, move them to pilot testing in cooperation with industry, and make them demonstrated techniques. As our industry has matured, the pressures on all parties have increased: pressure to assure protection of human health and the environment, to remediate faster, to rapidly return sites to beneficial use, to reduce costs, etc. Finding a solution to these competing objectives has become more and more intricate and must include the impacts of social, economic, business, and environmental factors. Dr. Suthersan is one of the most talented purveyors of remediation technology as a tool to solve these complex problems in a world where competing priorities are the rule not the excep- tion. The author has focused on finding these total business solutions for our industry, using the innovative technical solutions he or others have created. Finding total business solutions to multifaceted environmental problems is one of the hallmarks of Dr. Suthersan’s career. In this book, Dr. Suthersan explains some of the pioneering remediation tech- nologies developed over the past few years. The focus is on those techniques that modify or enhance the natural environment to aid in the remediation of contaminants. When applied correctly, these engineered, natural systems have proven to be more efficient and cost effective than their more intrusive predecessors. Assuring that these techniques are applied correctly and tailored to each particular setting is a key component of any system’s success. The impact of biological, chemical, and hydro- geologic settings on these technologies is thoroughly discussed. Dr. Suthersan describes each technique in detail: its processes, the science behind it, its application, and the constraints. This book will be an invaluable resource to the practicing remediation engineer, the regulatory community charged with evaluating these tech- niques, and the industry applying them. It has been a privilege to have worked with Dr. Suthersan for these past years and to have seen the influence of his knowledge and skill in our industry. I believe that those who read this book will gain from his wisdom. Steve Blake Executive Board, ARCADIS, N.V. Denver, Colorado ©2001 CRC Press LLC Preface Remediation of hazardous wastes present in the subsurface has evolved with time and has been influenced by various factors over the years. During the early years, direction and efforts were mostly influenced by the regulations in place and the need for compliance and protection of human health and environment. The contaminants primarily focused upon during this time were the petroleum-related contaminants stemming from leaking underground storage tanks (USTs). In later years, remediation efforts were driven by a combination of economic and regulatory factors. During this time contaminants that caught most of the atten- tion were the chlorinated solvents, heavy metals, and chlorinated and nonchlorinated polynuclear aromatic hydrocarbons (PAHs). The current focus seems to be taking a different direction: instead of focusing on the type of contaminants, emphasis is on evaluating the damage to the environment (and thus the risk) and repairing that damage in a cost-effective manner. 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 engineered anaerobic bioremediation systems of the 1990s. Significant reliance and dependence on natural remediation systems have increased as a result of recent acceptance that landfills behave as bioreactors and the very recent focus on dealing with ecological risks and natural resources damage (NRD) assessments. Ever increasing understanding of the behav- ior of most contaminants in the natural environment has also led to the effort of maximizing the remediation potential of natural systems. The thematic focus of this book is to highlight the current phase in the evolution of remediation technologies. All the technologies discussed in the book utilize or enhance the natural biogeochemical environment for remediation of hazardous con- taminants. The discussion throughout the book is focused towards helping practitioners of remediation to engineer remediation systems utilizing the natural environment. These natural systems or reactors still have to be properly designed and engineered to optimize the performance and maximize contaminant removal efficiencies. The basic understanding of environmental and contaminant characteristics required to design these systems is provided in Chapter 2. I had just coined the phrase “ in situ reactive zones (IRZ)” when I wrote my previous book in 1996 and was able to provide only an introduction of the technology. I have made a signif- icant effort in Chapter 4 to describe the IRZ technology and its various modified applications. The manner in which the application of this technology is exploding may justify a book of its own. I am proud to see the advances and expansion of this technology pioneered by my colleagues and me at ARCADIS G & M, Inc. Due to the shortage of space I could not present data from all the successful sites using this technology. Technical advances and theoretical insights on the applica- tion of in situ chemical oxidation are also presented in Chapter 4 (special thanks to Dr. Fred Payne). ©2001 CRC Press LLC I also had the privilege of being involved in some of the earliest phytoremediation and phyto-cover applications. Some contributions to the science of designing phyto- covers are presented in Chapter 7 (special thanks to Dr. Scott Potter). I have provided only a summary on the current state of the science of phytoremediation in Chapter 5. Basic concepts of treatment wetlands are provided in Chapter 6. I truly believe that this technology will have more applications in the field of hazardous waste remediation. I wrote this book to reach a wide audience: remediation design engineers, scientists, regulatory specialists, graduate students in environmental engineering, and people from the industry who have general responsibility for site cleanups. I have tried to provide a general, basic description of the technologies in all chapters in addition to detailed information on basic principles and fundamentals in most chapters. Readers who are not interested in basic principles can skip these passages and still receive the general knowledge they need. Suthan S. Suthersan Yardley, Pennsylvania ©2001 CRC Press LLC Acknowledgments First and foremost, I would like to thank members and colleagues from the Innovative Strategies Group (ISG) of ARCADIS — Frank Lenzo, Mike Hansen, and Jeff Burdick — for their enthusiasm and hard work in trying to experiment with innovative and cutting edge technologies in the field. Insights and advice provided by Drs. Scott Potter and Fred Payne in formulating the theoretical and mathematical foundations behind the technical concepts are immense. In addition, the patience and excitement exhibited by Chris Lutes and David Liles during the laboratory “proof of concept” experiments always boosted my confidence to proceed to the next level in implementing many of the technologies. Taking these technologies from the conceptual level to field scale applications would not have been possible without these individuals. I have to thank Eileen Schumacher and Ben Tufford for patiently drafting all the figures and Amy Weinert and Gail Champlin for typing the manuscript. The management of my employer ARCADIS G & M, Inc. deserves special mention for all the support given to me over the years. The opportunities and encouragement provided to me in order to “think out of the box” are a reflection of the company’s culture. I owe a special debt to all the engineers and project managers who helped me to implement many innovative and challenging remediation projects. This list is a long one, but special mention is due to the following: Mike Maierle, Don Kidd, Gary Keyes, Steve Brussee, Jack Kratzmeyer, Mark Wagner, Jim Drought, Tina Stack, Eric Carman, Al Hannum, John Horst, Kurt Beil, Dave Vance, Nanjun Shetty, and Pat Hicks. The encouragement, support, and feedback on the state of the science approaches in phytoremediation by Drs. Steve Rock and Steve McCutcheon, of the USEPA, are very much appreciated. ©2001 CRC Press LLC The Author Suthan S. Suthersan , Ph.D., P.E., is senior vice president and director of Innovative Remediation Strategies at ARCADIS G & M, Inc., an international environmental and infrastructure services company. In his 12 years with the company, Dr. Suthersan has helped make AG&M one of the most respected environmental engineering compa- nies in the U.S., specifically in the field of in situ remedi- ation of hazardous wastes. Many of the technologies he pioneered have since become industry standards. His big- gest contribution to the industry, beyond the technology development itself, has been to convince the regulatory community that these innovative technologies are better than traditional ones, not only from a cost viewpoint, but also for technical effec- tiveness. His experience is derived from working on at least 500 remediation projects in design, implementation, and technical oversight capacities during the past 15 years. Dr. Suthersan’s technology development efforts have been rewarded with seven patents awarded and more pending. His most important recent contributions are reflected by the following patents: Engineered In Situ Anaerobic Reactive Zones, US Patent 6,143,177; In Well Air Stripping, Oxidation, and Adsorption, US Patent 6,102,623; In Situ Anaerobic Reactive Zone for In Situ Metals Precipitation and to Achieve Microbial De-Nitrification, US Patent 5,554,290; In Situ Reactive Gate for Groundwater Remediation, US Patent 6,116,816. Dr. Suthersan has a Ph.D. in environmental engineering from the University of Toronto, a M.S. degree in environmental engineering from the Asian Institute of Technology, and a B.S. degree in civil engineering from the University of Sri Lanka. In addition to his consulting experience Dr. Suthersan has taught courses at several universities. He is the founding editor in chief of the Journal of Strategic Environ- mental Management and is a member of the editorial board of the International Journal of Phytoremediation . ©2001 CRC Press LLC Contents Chapter 1 Hazardous Wastes Pollution and Evolution of Remediation 1.1 Introduction 1.2 The Concept of Risk 1.2.1 The Decision Making Framework 1.3 Evolution of Understanding of Fate and Transport in Natural Systems 1.4 Evolution of Remediation Technologies References Chapter 2 Contaminant and Environmental Characteristics 2.1 Introduction 2.2 Contaminant Characteristics 2.2.1 Physical/Chemical Properties 2.2.1.1 Boiling Point 2.2.1.2 Vapor Pressure 2.2.1.3 Henry’s Law Constant 2.2.1.4 Octanol/Water Partition Coefficients 2.2.1.5 Solubility in Water 2.2.1.6 Hydrolysis 2.2.1.7 Photolytic Reactions in Surface Water 2.2.2 Biological Characteristics 2.2.2.1 Cometabolism 2.2.2.2 Kinetics of Biodegradation 2.3 Environmental Characteristics 2.3.1 Sorption Coefficient 2.3.1.1 Soil Sorption Coefficients 2.3.1.2 Factors Affecting Sorption Coefficients 2.3.2 Oxidation-Reduction Capacities of Aquifer Solids 2.3.2.1 pe and pH 2.3.2.2 REDOX Poise 2.3.2.3 REDOX Reactions References Chapter 3 Monitored Natural Attenuation 3.1 Introduction 3.1.1 Definitions of Natural Attenuation 3.2 Approaches for Evaluating Natural Attenuation 3.3 Patterns vs. Protocols [...]... 7 .11 General Phyto-Cover Maintenance Activities 7 .11 .1 Site Inspections 7 .11 .2 Soil Moisture Monitoring 7 .11 .2 .1 Drainage Measurement 7 .11 .3 General Irrigation Guidelines 7 .11 .4 Tree Evaluation 7 .11 .4 .1 Stem 7 .11 .4.2 Leaves 7 .11 .5 Agronomic Chemistry Sampling ©20 01 CRC Press LLC 7 .11 .6 Safety and Preventative Maintenance 7 .11 .7 Repairs and Maintenance 7 .12 Operation and Maintenance (O&M) Schedule 7 .12 .1. .. Barriers 6.2 Types of Constructed Wetlands 6.2 .1 Horizontal Flow Systems 6.2.2 Vertical Flow Systems 6.3 Microbial and Plant Communities of a Wetland 6.3 .1 Bacteria and Fungi 6.3.2 Algae 6.3.3 Species of Vegetation for Treatment Wetland Systems 6.3.3 .1 Free-Floating Macrophyte-Based Systems 6.3.3.2 Emergent Aquatic Macrophyte-Based Systems 6.3.3.3 Emergent Macrophyte-Based Systems with Horizontal Subsurface... Zones 4 .1 Introduction 4.2 Engineered Anaerobic Systems 4.2 .1 Enhanced Reductive Dechlorination (ERD) Systems 4.2 .1. 1 Early Evidence 4.2 .1. 1 .1 Biostimulation vs Bioaugmentation 4.2 .1. 2 Mechanisms of Reductive Dechlorination 4.2 .1. 3 Microbiology of Reductive Dechlorination 4.2 .1. 3 .1 Cometabolic Dechlorination 4.2 .1. 3.2 Dechlorination by Halorespiring Microorganisms 4.2 .1. 4 Electron Donors 4.2 .1. 4 .1 Production... Plants ©20 01 CRC Press LLC CHAPTER 1 Hazardous Wastes Pollution and Evolution of Remediation CONTENTS 1. 1 1. 2 Introduction The Concept of Risk 1. 2 .1 The Decision Making Framework 1. 3 Evolution of Understanding of Fate and Transport in Natural Systems 1. 4 Evolution of Remediation Technologies References The earth was made so various that the mind of desultory man, studious of change and pleased with novelty,... 4.2 .1. 4.2 Competition for H2 4.2 .1. 5 Mixture of Compounds on Kinetics 4.2 .1. 6 Temperature Effects 4.2 .1. 7 Anaerobic Oxidation ©20 01 CRC Press LLC 4.2 .1. 8 4.2 .1. 9 Electron Acceptors and Nutrients Field Implementation of IRZ for Enhanced Reductive Dechlorination 4.2 .1. 10 Lessons Learned 4.2 .1. 11 Derivation of a Completely Mixed System for Groundwater Solute Transport of Chlorinated Ethenes 4.2 .1. 12 IRZ... Late 19 70s - Early 19 80s Figure 1. 4 In Situ Extractive Techniques Early 19 80s - Late 19 80s In Situ Extractive Techniques Early 19 90s - Present In Situ Mass Destruction Techniques Mid 19 90s - Present MNA Current Evolution reduction in remediation costs IRZ In Situ Reactive Zones MNA Monitored Natural Attenuation Cost ($) Creation of IRZ Natural Rate of Decline Enhanced Rate of Decline Time Figure 1. 5... Partitioning and Storage 6.5.3 Hydraulic Retention Time ©20 01 CRC Press LLC 6.6 Treatment Wetlands for Groundwater Remediation 6.6 .1 Metals-Laden Water Treatment 6.6 .1. 1 A Case Study for Metals Removal 6.6.2 Removal of Toxic Organics 6.6.2 .1 Biodegradation 6.6.3 Removal of Inorganics 6.6.4 Wetland Morphology, Hydrology, and Landscape Position References Chapter 7 Engineered Vegetative Landfill Covers 7 .1 Historical... reasonable risk reduction 10 -5 Associated Risk Cost of Remediation ($) 10 -3 10 -6 10 -7 Figure 1. 2 A hypothetical analysis of cost to risk reduction beneÞt ratios during remediation activities 1. 3 EVOLUTION OF UNDERSTANDING OF FATE AND TRANSPORT IN NATURAL SYSTEMS Predicting the hazard of an organic contaminant to humans, animals, and plants requires information not only on its toxicity to living organisms... Phytoremediation Design 5.4 .1 Contaminant Levels 5.4.2 Plant Selection 5.4.3 Treatability 5.4.4 Irrigation, Agronomic Inputs, and Maintenance 5.4.5 Groundwater Capture Zone and Transpiration Rate References Chapter 6 Constructed Treatment Wetlands 6 .1 Introduction 6 .1. 1 Beyond Municipal Wastewater 6 .1. 2 Looking Inside the “Black Box” 6 .1. 3 Potential “Attractive Nuisances” 6 .1. 4 Regulatory Uncertainty and. .. technologies and improvements in efÞciencies monitored natural attenuation (MNA) — this remediation approach has taken root as a viable remediation approach at the appropriate site and under the right biogeochemical conditions Used in conjunction with already ongoing remediation systems or as a stand-alone remedy, MNA can increase significantly the probability of a successful, cost-effective, and well-documented . 7 .11 .4 Tree Evaluation 7 .11 .4 .1 Stem 7 .11 .4.2 Leaves 7 .11 .5 Agronomic Chemistry Sampling ©20 01 CRC Press LLC 7 .11 .6 Safety and Preventative Maintenance 7 .11 .7 Repairs and Maintenance 7 .12 . Application 7 .10 Summary of Phyto-Cover Water Balance 7 .11 General Phyto-Cover Maintenance Activities 7 .11 .1 Site Inspections 7 .11 .2 Soil Moisture Monitoring 7 .11 .2 .1 Drainage Measurement 7 .11 .3 General. Pollution and Evolution of Remediation 1. 1 Introduction 1. 2 The Concept of Risk 1. 2 .1 The Decision Making Framework 1. 3 Evolution of Understanding of Fate and Transport in Natural Systems 1. 4 Evolution