Natural and Enhanced PDF

NATURAL and
ENHANCED
REMEDIATION
SYSTEMS
L1282_fm_frame Page 2 Monday, June 18, 2001 10:20 AM
NATURAL and
ENHANCED
REMEDIATION
SYSTEMS
Suthan S. Suthersan
LEWIS PUBLISHERS
Boca Raton London New York Washington, D.C.
Library of Congress Cataloging-in-Publication Data

Suthersan, Suthan S.
Natural and enhanced remediation systems / by Suthan S. Suthersan.
p. cm. (Arcadis Geraghty & Miller science and engineering)
Includes bibliographical references and index.
ISBN 1-56670-282-8
1. Soil remediation. 2. GroundwaterPurification. 3. Hazardous wastesNatural
attenuation. 4. Bioremediation. I. Title. II. Geraghty & Miller environmental science and
engineering series.
TD878.S873 2001
628.5dc21
2001029566
CIP
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International Standard Book Number 1-56670-282-8
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Printed in the United States of America 1 2 3 4 5 6 7 8 9 0
Printed on acid-free paper
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.
L1282_fm_frame Page 7 Tuesday, June 19, 2001 12:56 PM
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, environmental 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 technologies, 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 exception. 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. Suthersans career.
In this book, Dr. Suthersan explains some of the pioneering remediation technologies 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 systems success. The impact of biological, chemical, and hydrogeologic 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 techniques, 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
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 attention 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 behavior 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 contaminants. 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 significant 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 application of in situ chemical oxidation are also presented in Chapter 4 (special thanks
to Dr. Fred Payne).
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 phytocovers 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
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 companys
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.
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 companies in the U.S., specifically in the field of in situ remediation of hazardous wastes. Many of the technologies he
pioneered have since become industry standards. His biggest 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 effectiveness. 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. Suthersans 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 Environmental Management and is a member of the editorial board of the International
Journal of Phytoremediation.
Contents
Chapter 1
Hazardous Wastes Pollution and Evolution of Remediation....................................1
1.1 Introduction ......................................................................................................1
1.2 The Concept of Risk ........................................................................................2
1.2.1 The Decision Making Framework .......................................................3
1.3 Evolution of Understanding of Fate and Transport in
Natural Systems ...............................................................................................4
1.4 Evolution of Remediation Technologies .........................................................7
References................................................................................................................11
Chapter 2
Contaminant and Environmental Characteristics ....................................................13
2.1 Introduction ....................................................................................................14
2.2 Contaminant Characteristics ..........................................................................18
2.2.1 Physical/Chemical Properties ............................................................18
2.2.1.1 Boiling Point.......................................................................18
2.2.1.2 Vapor Pressure ....................................................................18
2.2.1.3 Henrys Law Constant ........................................................19
2.2.1.4 Octanol/Water Partition Coefficients..................................20
2.2.1.5 Solubility in Water..............................................................20
2.2.1.6 Hydrolysis ...........................................................................22
2.2.1.7 Photolytic Reactions in Surface Water...............................24
2.2.2 Biological Characteristics ..................................................................26
2.2.2.1 Cometabolism .....................................................................27
2.2.2.2 Kinetics of Biodegradation.................................................32
2.3 Environmental Characteristics .......................................................................38
2.3.1 Sorption Coefficient ...........................................................................38
2.3.1.1 Soil Sorption Coefficients...................................................43
2.3.1.2 Factors Affecting Sorption Coefficients .............................48
2.3.2 Oxidation-Reduction Capacities of Aquifer Solids ...........................51
2.3.2.1 pe and pH............................................................................51
2.3.2.2 REDOX Poise .....................................................................52
2.3.2.3 REDOX Reactions ..............................................................53
References................................................................................................................58
Chapter 3
Monitored Natural Attenuation ...............................................................................63
3.1 Introduction ....................................................................................................64
3.1.1 Definitions of Natural Attenuation ....................................................64
3.2 Approaches for Evaluating Natural Attenuation ...........................................65
3.3 Patterns vs. Protocols .....................................................................................70
3.3.1
3.3.2
Protocols for Natural Attenuation......................................................70

Patterns of Natural Attenuation .........................................................71
3.3.2.1 Various Patterns of Natural Attenuation.............................72
3.4 Processes Affecting Natural Attenuation of Compounds..............................79
3.4.1 Movement of Contaminants in the Subsurface .................................79
3.4.1.1 Dilution (Recharge) ............................................................79
3.4.1.2 Advection ............................................................................81
3.4.1.3 Dispersion ...........................................................................83
3.4.2 Phase Transfers ..................................................................................85
3.4.2.1 Sorption...............................................................................85
3.4.2.2 Stabilization ........................................................................88
3.4.2.3 Volatilization .......................................................................89
3.4.3 Transformation Mechanisms..............................................................89
3.4.3.1 Biodegradation ....................................................................90
3.5 Monitoring and Sampling for Natural Attenuation .....................................109
3.5.1 Dissolved Oxygen (DO) ..................................................................113
3.5.2 OxidationReduction (REDOX) Potential (ORP)...........................117
3.5.3 pH .....................................................................................................119
3.5.4 Filtered vs. Unfiltered Samples for Metals .....................................120
3.5.4.1 Field Filtration and the Nature of
Groundwater Particulates..................................................121
3.5.4.2 Reasons for Field Filtration..............................................122
3.5.5 Low-Flow Sampling as a Paradigm for Filtration ..........................124
3.5.6 A Comparison Study........................................................................125
References..............................................................................................................126
Chapter 4
In Situ Reactive Zones...........................................................................................131
4.1 Introduction ..................................................................................................132
4.2 Engineered Anaerobic Systems ...................................................................135
4.2.1 Enhanced Reductive Dechlorination (ERD) Systems .....................135
4.2.1.1 Early Evidence..................................................................135
4.2.1.1.1 Biostimulation vs. Bioaugmentation ................136
4.2.1.2 Mechanisms of Reductive Dechlorination .......................138
4.2.1.3 Microbiology of Reductive Dechlorination .....................142
4.2.1.3.1 Cometabolic Dechlorination .............................142
4.2.1.3.2 Dechlorination by Halorespiring
Microorganisms.................................................144
4.2.1.4 Electron Donors ................................................................147
4.2.1.4.1 Production of H2 by Fermentation ...................149
4.2.1.4.2 Competition for H2 ...........................................152
4.2.1.5 Mixture of Compounds on Kinetics.................................155
4.2.1.6 Temperature Effects ..........................................................158
4.2.1.7 Anaerobic Oxidation.........................................................158
4.2.1.8
4.2.1.9
Electron Acceptors and Nutrients.....................................158

Field Implementation of IRZ for Enhanced Reductive
Dechlorination...................................................................160
4.2.1.10 Lessons Learned ...............................................................163
4.2.1.11 Derivation of a Completely Mixed System for
Groundwater Solute Transport of Chlorinated Ethenes...170
4.2.1.12 IRZ Performance Data......................................................177
4.2.2 In Situ Metals Precipitation .............................................................183
4.2.2.1 Principles of Heavy Metals Precipitation.........................187
4.2.2.2 Aquifer Parameters and Transport Mechanisms ..............195
4.2.2.3 Contaminant Removal Mechanisms.................................196
4.2.3 In Situ Denitrification.......................................................................197
4.2.4 Perchlorate Reduction ......................................................................199
4.3 Engineered Aerobic Systems .......................................................................200
4.3.1 Direct Aerobic Oxidation.................................................................200
4.3.1.1 Aerobic Cometabolic Oxidation.......................................202
4.3.1.2 MTBE Degradation ..........................................................204
4.4 In Situ Chemical Oxidation Systems...........................................................205
4.4.1 Advantages .......................................................................................206
4.4.2 Concerns...........................................................................................207
4.4.3 Oxidation Chemistry ........................................................................208
4.4.3.1 Hydrogen Peroxide ...........................................................211
4.4.3.2 Potassium Permanganate ..................................................213
4.4.3.3 Ozone ................................................................................216
4.4.4 Application .......................................................................................218
4.4.4.1 Oxidation of 1,4-Dioxane by Ozone................................222
4.4.4.2 Biodegradation Enhanced by Chemical
Oxidation Pretreatment.....................................................223
4.5 Nano-Scale Fe (0) Colloid Injection within an IRZ ...................................223
4.5.1 Production of Nano-Scale Iron Particles .........................................228
4.5.2 Injection of Nano-Scale Particles in Permeable Sediments............231
4.5.3 Organic Contaminants Treatable by Fe (0) .....................................231
References..............................................................................................................233
Chapter 5
Phytoremediation ...................................................................................................239
5.1 Introduction ..................................................................................................240
5.2 Chemicals in the SoilPlant System............................................................241
5.2.1 Metals ...............................................................................................241
5.2.2 Organics............................................................................................242
5.3 Types of Phytoremediation ..........................................................................244
5.3.1 Phytoaccumulation ...........................................................................245
5.3.2 Phytodegradation..............................................................................248
5.3.3 Phytostabilization .............................................................................250
5.3.4 Phytovolatilization............................................................................251
5.3.5 Rhizodegradation..............................................................................252
5.3.6 Rhizofiltration...................................................................................256
5.3.7 Phytoremediation for Groundwater Containment ...........................259
5.3.8 Phytoremediation of Dredged Sediments ........................................260
5.4 Phytoremediation Design .............................................................................261
5.4.1 Contaminant Levels .........................................................................265
5.4.2 Plant Selection..................................................................................265
5.4.3 Treatability .......................................................................................266
5.4.4 Irrigation, Agronomic Inputs, and Maintenance .............................266
5.4.5 Groundwater Capture Zone and Transpiration Rate .......................267
References..............................................................................................................267
Chapter 6
Constructed Treatment Wetlands...........................................................................269
6.1 Introduction ..................................................................................................270
6.1.1 Beyond Municipal Wastewater ........................................................272
6.1.2 Looking Inside the Black Box .....................................................273
6.1.3 Potential Attractive Nuisances......................................................274
6.1.4 Regulatory Uncertainty and Barriers ...............................................275
6.2 Types of Constructed Wetlands ...................................................................276
6.2.1 Horizontal Flow Systems.................................................................276
6.2.2 Vertical Flow Systems......................................................................277
6.3 Microbial and Plant Communities of a Wetland.........................................278
6.3.1 Bacteria and Fungi ...........................................................................278
6.3.2 Algae ................................................................................................279
6.3.3 Species of Vegetation for Treatment Wetland Systems...................279
6.3.3.1 Free-Floating Macrophyte-Based Systems.......................282
6.3.3.2 Emergent Aquatic Macrophyte-Based Systems ...............284
6.3.3.3 Emergent Macrophyte-Based Systems with Horizontal
Subsurface Flow ...............................................................285
6.3.3.4 Emergent Macrophyte-Based Systems with Vertical
Subsurface Flow ...............................................................285
6.3.3.5 Submerged Macrophyte-Based Systems ..........................285
6.3.3.6 Multistage Macrophyte-Based Treatment Systems..........287
6.4 Treatment-Wetland Soils..............................................................................287
6.4.1 Cation Exchange Capacity...............................................................289
6.4.2 Oxidation and Reduction Reactions ................................................290
6.4.3 pH .....................................................................................................292
6.4.4 Biological Influences on Hydric Soils.............................................292
6.4.5 Microbial Soil Processes..................................................................292
6.4.6 Treatment Wetland Soils ..................................................................293
6.5 Contaminant Removal Mechanisms ............................................................294
6.5.1 Volatilization ....................................................................................294
6.5.2 Partitioning and Storage...................................................................295
6.5.3 Hydraulic Retention Time................................................................297
6.6
Treatment Wetlands for Groundwater Remediation....................................299

6.6.1 Metals-Laden Water Treatment........................................................300
6.6.1.1 A Case Study for Metals Removal ..................................302
6.6.2 Removal of Toxic Organics .............................................................306
6.6.2.1 Biodegradation ..................................................................306
6.6.3 Removal of Inorganics .....................................................................309
6.6.4 Wetland Morphology, Hydrology, and Landscape Position............309
References..............................................................................................................310
Chapter 7
Engineered Vegetative Landfill Covers .................................................................313
7.1 Historical Perspective on Landfill Practices................................................314
7.2 The Role of Caps in the Containment of Wastes........................................315
7.3 Conventional Landfill Covers ......................................................................316
7.4 Landfill Dynamics........................................................................................317
7.5 Alternative Landfill Cover Technology .......................................................321
7.6 Phyto-Cover Technology..............................................................................321
7.6.1 Benefits of Phyto-Covers over Traditional RCRA Caps.................326
7.6.2 Enhancing In Situ Biodegradation...................................................326
7.6.3 Gas Permeability ..............................................................................327
7.6.4 Ecological and Aesthetic Advantages..............................................327
7.6.5 Maintenance, Economic, and Public Safety Advantages ................329
7.7 Phyto-Cover Design .....................................................................................329
7.7.1 Vegetative Cover Soils .....................................................................330
7.7.2 Nonsoil Amendment ........................................................................331
7.7.3 Plants and Trees ...............................................................................331
7.8 Cover System Performance..........................................................................332
7.8.1 Hydrologic Water Balance ...............................................................332
7.8.2 Precipitation .....................................................................................335
7.8.3 Runoff...............................................................................................335
7.8.4 Potential Evapotranspiration Measured Data .............................337
7.8.5 Potential Evapotranspiration Empirical Data .............................339
7.8.6 Effective Evapotranspiration ............................................................340
7.8.7 Water Balance Model.......................................................................343
7.9 Example Application....................................................................................344
7.10 Summary of Phyto-Cover Water Balance....................................................347
7.11 General Phyto-Cover Maintenance Activities .............................................348
7.11.1 Site Inspections ................................................................................348
7.11.2 Soil Moisture Monitoring ................................................................349
7.11.2.1 Drainage Measurement.....................................................350
7.11.3 General Irrigation Guidelines ..........................................................352
7.11.4 Tree Evaluation ................................................................................356
7.11.4.1 Stem ..................................................................................356
7.11.4.2 Leaves ...............................................................................356
7.11.5 Agronomic Chemistry Sampling .....................................................357
7.11.6 Safety and Preventative Maintenance..............................................359

7.11.7 Repairs and Maintenance.................................................................359
7.12 Operation and Maintenance (O&M) Schedule............................................359
7.12.1 Year 1 Establishment ..................................................................360
7.12.2 Years 2 and 3 Active Maintenance.............................................360
7.12.3 Year 4 Passive Maintenance .......................................................361
7.13 Specific Operational Issues..........................................................................362
7.13.1 Irrigation System Requirements ......................................................362
7.13.2 Tree Replacement.............................................................................362
References..............................................................................................................362
Appendix A
Physical Properties of Some Common Environmental Contaminants .................365
Appendix B
Useful Information for Biogeochemical Sampling...............................................383
Appendix C
Common and Scientific Names of Various Plants ................................................405
Index......................................................................................................................409
L1282_C01_frame Page 1 Monday, June 18, 2001 10:18 AM
CHAPTER
Hazardous Wastes Pollution and

Evolution of Remediation
CONTENTS
1.1
1.2
Introduction ......................................................................................................1
The Concept of Risk ........................................................................................2
1.2.1 The Decision Making Framework .......................................................3
1.3 Evolution of Understanding of Fate and Transport in Natural Systems ........4
1.4 Evolution of Remediation Technologies .........................................................7
References................................................................................................................11
The earth was made so various that the mind of desultory man, studious of
change and pleased with novelty, might be indulged.
1.1
INTRODUCTION
Among the many environmental problems that have received attention in recent
decades is subsurface contamination caused by hazardous wastes. This has been due
to the growing concern over short and long term health and environmental effects
of toxic substances released into the environment.
The public policy maker is faced with particular difficulties in regulating hazardous pollutants, most notably because of the high levels of uncertainty surrounding
the issue. Such uncertainty exists in determining the precise impacts in relation to
both human health effects and long term effects on the environment, especially with
recalcitrant pollutants, or pollutants with extremely slow degradation rates. Nevertheless, policy makers have been required to formulate environmental regulations
using some dependable basis. While theoretical methods of decision making such
as dose-response and risk-benefit analysis may be employed to assist regulators,
NATURAL AND ENHANCED REMEDIATION SYSTEMS
they are still faced with conflicting pressures for example, between political and
economic priorities or between public demands and technical expertise.
Estimating the damage function of a pollutant is an exercise that underpins
regulatory formulation for hazardous waste management. Figure 1.1 outlines the
basic steps involved in this estimation. Determining the transfer function of a hazardous pollutant raises several problems. Persistent, nondegradable substances will
tend to accumulate in the environment often becoming concentrated in the food
chain. In the past, the potential life span of persistent substances in the subsurface
was considered to be decades or even centuries. Research performed and scientific
advancements, specifically in the last decade, indicate that compounds deemed to
be persistent or nondegradable in the past are considered to be less persistent or at
least partially degradable under natural conditions.
Release of
Pollutants
Transfer
Function
Rate and Mass

at a Particular
Place and Time
Figure 1.1
Ambient
Conditions
Exposure
Pathways
Damage
Effects
Concentrations
of Pollutants in
Different Media
Dose-Response
Function
Physical, Ecological,
Health, Property,
Natural Resources
Monetary
Evaluation of pollution damage.
1.2
THE CONCEPT OF RISK
Many of the problems associated with hazardous waste management, such as uncertainty, irreversibility, and persistence make the concept of risk relevant to this discussion.
From an engineering or scientific standpoint, risk may be defined in quantitative terms
by applying probabilistic measures. If hazard is defined as the potential for adverse
consequences of some event, then risk may be defined as the chance of a particular
hazard occurring. It combines two aspects the probabilistic measure of the occurrence
of the event with a measure of the consequences of the event (in this case the level of
toxicity of the pollutant). Further aspects of risk are highlighted by social scientists who
examine risk perception in recognition that a particular risk or hazard may mean
different things to different people in different contexts.
The concept of risk is not without problems, particularly in relation to the issue
of hazardous pollutants. For example, an initial problem is determining the probability of such risks; there have been only a few decades of experience in dealing
with many pollutants. Their effects on human beings had been largely unknown,
and thus the probabilistic calculations of risk on exposure and associated health and
ecological impacts were mostly conservative.
In relation to the assumed, perceived, or calculated risks associated with hazardous pollutants until recently, it is important to highlight two significant features:
1) the subjective probability of the hazard (caused by toxicity of the released
pollutant) occurring may be very low, but, 2) the consequence of the hazard was
assumed or perceived to be very high, often as irreversible because of assumptions
HAZARDOUS WASTES POLLUTION AND EVOLUTION OF REMEDIATION
of persistence and negligible degradation of many pollutants in the natural environment. Thus the low probability tends to cancel out the assumed or perceived impacts
associated with the risk.
Recent research shows that pollutants and other organic chemicals present in the
subsurface become less available or create lesser levels of hazard (in other words
become less toxic) due to interactions between the compound and the subsurface
environment. This drop in availability and toxicity lowers the risk of these chemicals
to human and ecological receptors. Furthermore, the availability of an organic
chemical in the subsurface is not a function of its measured concentration; rather,
it depends upon the geologic and biogeochemical characteristics of the subsurface,
the physicochemical properties of the chemical itself, and the time of contact between
the chemical and the subsurface media, i.e., aging, as well as the type and extent of
treatment, natural or anthropogenic, to which it has been subjected.
1.2.1
The Decision Making Framework
In the face of the many uncertainties surrounding hazardous waste management

with respect to the assumed, perceived, or calculated risks, the regulatory authorities
are faced with an initial decision about the appropriate framework for decisionmaking: should it be a balancing approach such as cost-benefit or risk-benefit
analysis, or should it be an approach which emphasizes the protection of human
health and natural resources regardless of costs?
Three types of approaches have been utilized to implement hazardous waste
management policies in the U.S. during the past three decades:
1. Health-based approaches zero risk, significant risk, or acceptable risk
2. Balancing approaches cost-benefit, risk-benefit, or decision analysis
3. Technology-based approaches best available technology, risks as low as reasonably practicable
Environmental threats, rather than the scientific evidence and theory from which
they may be deduced, have been ill-defined during the past three decades. The
evidence from which a threat is deduced has been challenged by conflicting evidence
or placed into a context of associations which heightens its significance. A scenario
for an exposure pathway typically used in the past, where a kid climbing an eightfoot fence and eating a few grams of soil every day for a decade is an example of
such an association. For many years, there was a widespread but unfounded assumption that some toxic pollutants stemming from industrial releases and/or accidents
and landfills would not be degraded in the natural environment. The measurement
of damage, and thus the risk, requires an understanding of the physical processes
of transportation and of the distribution and deposition of pollutants, including their
chemical and biological transformations on the way.
The creation of new knowledge usually involves institutions very different from
those concerned with its acceptance, application, and dissemination. A genuine
science-based environmental policy should be a dynamic one and evolve via continuous monitoring of pollutants in many media, as well as of their impacts on the
ecosystem and human health (or any other selected target organisms). The technical
means for such monitoring must, of course, be available, as must the baselines for
the establishment of a time series so that change can be observed over time in the
natural environment. There must be agreement on which pollutants to monitor and
how to synthesize and use the masses of data that will accumulate.
Even complete understanding of how the subsurface works as a bio-geo-physico-chemical system cannot give ready answers as to the proper regulatory response,
i.e., how to use the earth in the common interest of humanity and without degrading
it for future generations. This is probably why the government, more out of frustration than intent, has come to rely less on science, engineering, and economics and
more on caution and law.
Figure 1.2 describes the shortcomings of the health-based, conservative approach
of the past and the more credible, balanced approach still evolving. Understanding
the contribution by Mother Nature towards a natural remediation process has had a
significant influence on this evolution.
10 -4
Remediation expenditure
which justifies 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 benefit 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 but also on the
degree of exposure of the organisms to the compound. The mere release or discharge
of a pollutant does not, in itself, constitute a hazard; the individual human, animal,
or plant must also be exposed to it. In evaluating exposure, the transport of the
chemical and its fate must be considered. A molecule that is not subject to environmental transport is not a health or environmental problem except to species at the
specific point of release.
Information on dissemination of the chemical from the point of its release to the
point where it could have an effect is of great relevancy for risk calculations.
However, the chemical may be modified structurally or totally destroyed during its
transport, and the fate of the compound during transport, that is, its modification or
destruction, is crucial to defining the exposure. A compound modified to yield
products that are less or more toxic, or totally degraded to harmless end products,
or bio-magnified factors associated with the fate of the molecule represents
greater or lesser hazard to the species potentially exposed to injury.
At the specific site of discharge or during its transport, the pollutant molecule
or ion may be acted on by abiotic mechanisms. Photochemical transformations occur
in the atmosphere and at or very near the surfaces of water, soil, and vegetation,
and these processes may totally destroy or appreciably modify a number of different
types of organic chemicals. Nonenzymatic, nonphotochemical reactions are also
prominent in soil, sediment, and surface and groundwater, and these may bring about
significant changes; however, such processes rarely, if ever, totally convert organic
compounds to harmless end products or mineralized compounds in nature. Many of
these nonenzymatic reactions only bring about a slight modification of the molecule
so that the product is frequently similar in structure, and often in toxicity, to the
precursor compound.
However, biological processes may modify organic molecules at the site of their
release or during their transport. Such biological transformations, which involve
enzymes as catalysts, frequently bring about extensive modification in the structure
and toxicological properties of pollutants or potential pollutants. These biotic processes may result in the complete conversion of the organic molecule to inorganic
products, cause major changes resulting in new organic products, or occasionally
lead to only minor modifications. The available body of information suggests that
the major agents causing the biological transformations in soil, sediment, surface
and groundwater, and many other sites are the microorganisms that inhabit these
environments.
The earth is thought to be about 4.6 109 years (4.6 eons) old.2 The original
atmosphere surrounding the earth was reducing and probably included the gases
CH4, CO2, CO, NH3 and H2O. Although abiotic organic synthesis probably occurred
since the earths beginnings, life probably did not appear until about 0.51 billion
years later, according to present thinking.
The first form of life that was established on the infant earth was anaerobic.1
As anaerobic life became more firmly established, the organic nutrients must have
begun to be depleted at a faster rate than they could be replenished by abiotic
synthesis. Hence, an alternative mechanism for producing organic matter was
required to sustain life. The subsequent evolutionary developments led to the emergence of photosynthesis and eventually resulted in the emergence of aerobic heterotrophic organisms. These aerobic organisms ended up much more efficient than
their anaerobic counterparts in sustaining life.
Billions of years of evolution by Mother Nature have shown that the natural
communities of microorganisms in the various habitats have an amazing physiological versatility. These communities are adaptable, flexible, versatile, and robust. They
are able to metabolize and often mineralize an enormous number of organic molecules. Probably every natural product, regardless of its complexity, is degraded by
one or another species in some particular environment; if not, this long after the
appearance of life on earth, such compounds would have accumulated in enormous
amounts.
The compounds that caught the most attention in the remediation industry,
initially during the 1970s and 1980s, were the BTEX compounds released via
petroleum spills natural products formed as the result of decomposition of plants
and other organic materials over millions of years. It has been proven during the
last decade that the BTEX compounds will naturally attenuate in the groundwater
through microbial degradation. Although certain bacteria and fungi act on a broad
range of organic compounds, no organism known to date is sufficiently omnivorous
to destroy a very large percentage of the natural chemicals.2
Bioremediation is now a widely accepted technique for contaminant cleanup.
But a few short decades ago, its use for anything as effective as the in situ cleanup
of groundwater contamination was considered laughable. At that time, there was a
myth, widely held by the geological and hydrological community, that the subsurface
was sterile, that there were no bacteria, and therefore no biological processes of
consequence.3 This thinking was mainly due to the information available from the
textbooks at that time.
Microbial ecology is the study of interrelationships between different microorganisms; among microorganisms, plants, and animals; and between microorganisms
and their environment. Microbial biogeochemistry is the study of microbially catalyzed reactions and their kinetics with emphasis on environmental mass transfer and
energy flow.
In subsequent chapters, this book summarizes and systematizes current understanding of abiotic and biotic transformations of organic and inorganic pollutants in
the natural environment. Knowledge of abiotic transformations can provide a conceptual framework for understanding biologically mediated transformations. Most
abiotic transformations are slow, but they can still be significant within the time
scales commonly associated with groundwater movement. In contrast, biotic transformations typically proceed much faster, provided the biogeochemical environment
is conducive to mediate such transformations.
The ability to predict the behavior of a chemical substance in a biological or
environmental system largely depends on knowledge of the physical-chemical properties and reactivity of that compound or closely related compounds. Chemical
properties frequently used in environmental fate assessment include melting/boiling
temperature, vapor pressure, various partition coefficients, water solubility, Henrys
Law Constant, sorption coefficient, and diffusion properties. Reactivities by processes such as biodegradation, hydrolysis, photoysis, and oxidation/reduction are
also critical determinants of environmental fate. Unfortunately, measured values
often are not available and, even if they are, the reported values may be inconsistent
or of doubtful validity. In this situation it may be appropriate or even essential to
use estimation methods. The evolution of understanding of half-lives of chlorinated

aliphatic compounds and the refinement of those values by precisely measured values
have been remarkable during the last decade. Half-lives which were estimated to be
in the two to three year range have been measured in the field to be in the range of
three to six months. Later chapters describe the marked difference in the accepted
half-lives during the last decade.
1.4
EVOLUTION OF REMEDIATION TECHNOLOGIES
Remediation technologies have undergone many changes over the last two decades
during which they have been applied to clean up subsurface and hazardous waste
contamination problems. These changes have occurred at a relatively rapid pace; during
this period some of the most profound changes have occurred in how we apply remedial
technologies as a result of pressure from the industry to continuously improve technical
efficiency and cost effectiveness of the preferred technologies.
Initially contaminated groundwater was a driving concern because it was mobile
and, as a result, transported the liability off site. Also, the need to contain the
contamination on site led to universal application of pump and treat systems for
source control and mass removal. A decade of experience has taught that pump and
treat is not the solution and, in fact, is an inefficient technology for fast and cheap
site cleanup.
The realization that mass removal efficiencies can be significantly enhanced
using air as an extractive media instead of water led to the development and application of in situ extractive technologies such as soil vapor extraction and in situ air
sparging. While it can be argued that the initial motive for applying these technologies has been one of saving money, the end result is much quicker cleanup times
to more acceptable cleanup levels (Figure 1.3). This win-win situation for the entire
remediation industry fostered continuous innovation, which led to 1) faster, cheaper
solutions, 2) less invasive in situ technologies, and 3) technologies complementary
to the natural environment which took advantage of natures capacity to degrade the
pollutants. Thus holistically, environmentally, and economically sound and sustainable solutions were provided.
Figure 1.4 illustrates the evolutionary reduction in remediation costs from the
late 1970s to the present time. Ex situ extractive techniques such as pump and treat
systems were replaced by in situ extractive techniques, namely, soil vapor extraction
(SVE) and in situ air sparging. Subsequently these in situ extractive techniques gave
way to in situ nonextractive techniques such as funnel and gate systems and, eventually, to in situ mass destruction techniques such as in situ reactive zones (IRZ) as
the preferred remediation technologies. This evolutionary pattern has focused
towards more natural solutions and/or enhancing existing subsurface biogeochemical
conditions that contribute to remediation.
The most recent shift occurred approximately 5 years ago, with the recognition
and demonstrated value of natural mechanisms that contributed towards the containment, control, and mass reduction of contaminants in soil and groundwater. Under a
host of names including natural attenuation, bioattenuation, natural remediation,
MNA with Source Reduction
MNA - Monitored Natural Attenuation
Conventional Pump and Treat
Concentration
In Situ Reactive Zones (IRZ)

In Situ Air Sparging
Only When
Contaminants
Are Aerobically
Biodegradable
Clean-Up Standards
Time
Figure 1.3
Evolution of in situ remediation technologies and improvements in efficiencies.
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 restoration of a contaminated site.
The development of in situ reactive zones (IRZ), which are engineered in situ
anaerobic or aerobic systems, is essentially an outgrowth of the efforts to enhance the
natural processes which contribute towards degradation of many contaminants. For
example, the use of an engineered IRZ to reductively dechlorinate chlorinated aliphatic
hydrocarbons, such as PCE and TCE, in essence, enhances the rate of natural degradation by providing the optimum biogeochemical conditions (Figure 1.5).
At many contaminated sites, the bulk of the contaminant mass may still be
present in what remediation professionals call source areas. Even though the plume
length has reached a stable equilibrium and the contaminant concentrations have
reached steady or declining concentrations at the compliance points, it may be
desirable to enhance the rates of natural degradation if the plume has crossed the
property boundary (Figure 1.6a). Surgical reduction of the mass at the source areas
and enhancement of natural degradation along the property boundary will enable
such properties to be restored within a reasonable time frame (Figure 1.6b). The
duration of the containment IRZ at the property boundary will be significantly longer
if mass removal is not accomplished at the source area.
Capital Costs
O&M Costs
Cost ($)
MNA Monitored Natural Attenuation
Ex Situ Extractive
Techniques
Late 1970s - Early 1980s
Figure 1.4
In Situ Extractive
Techniques
Early 1980s - Late 1980s
In Situ Extractive
Techniques
Early 1990s - Present
In Situ Mass Destruction

Techniques
Mid 1990s - 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
Implementation of an IRZ for enhanced biodegradation has an impact on the time

towards closure in comparison to reliance on MNA.
10
Engineered IRZ
Source Area
Stable Plume
Compliance
Points
Property Boundary
Figure 1.6a
Implementation of a containment IRZ and a source reduction IRZ to reduce the

cleanup time.
Concentraation at Compliance Point(s)
Creation of IRZ
Time
Figure 1.6b
Reduction in cleanup time as a result of enhanced rate of mass removal.
11
The evolutionary trend towards more natural remediation solutions should not be
surprising due to the recognition for decades, even centuries, of the value of natural
wetlands to buffer the effects of human activity in waterways. Today engineered
wetlands, phyto-covers and phytoremediation are our attempts to mimic natural systems by engineering remediation solutions using nature as the material of construction trees and microorganisms instead of pumps and air compressors.
REFERENCES
1. Ehrlich, H.L., Geomicrobiology, Marcel Dekker Inc., New York, 1981.
2. Alexander, M., Biodegradation and Bioremediation, 2nd ed., Academic Press, New
York, 1999.
3. Harvey, M.A., Quotation by John Wilson in Germ Warfare, Environ. Prot., 23-26,
October 1999.
CHAPTER
Contaminant and Environmental

Characteristics
CONTENTS
2.1
2.2
Introduction ....................................................................................................14
Contaminant Characteristics ..........................................................................18
2.2.1 Physical/Chemical Properties ............................................................18
2.2.1.1 Boiling Point.......................................................................18
2.2.1.2 Vapor Pressure ....................................................................18
2.2.1.3 Henrys Law Constant ........................................................19
2.2.1.4 Octanol/Water Partition Coefficients..................................20
2.2.1.5 Solubility in Water..............................................................20
2.2.1.6 Hydrolysis ...........................................................................22
2.2.1.7 Photolytic Reactions in Surface Water...............................24
2.2.2 Biological Characteristics ..................................................................26
2.2.2.1 Cometabolism .....................................................................27
2.2.2.2 Kinetics of Biodegradation.................................................32
2.3 Environmental Characteristics .......................................................................38
2.3.1 Sorption Coefficient ...........................................................................38
2.3.1.1 Soil Sorption Coefficients...................................................43
2.3.1.2 Factors Affecting Sorption Coefficients .............................48
2.3.2 Oxidation-Reduction Capacities of Aquifer Solids ...........................51
2.3.2.1 pe and pH............................................................................51
2.3.2.2 REDOX Poise .....................................................................52
2.3.2.3 REDOX Reaction ...............................................................53
References................................................................................................................58
13
14
Water is scientifically very different in comparison to other liquids. With its rare
and distinctive property of being denser as a liquid than as a solid, it is different.
Water is different in that it is the only chemical compound found naturally in solid,
liquid, or gaseous states at ambient conditions. Water is sometimes called the
universal solvent. This is a fitting name, especially when you consider that water is
a powerful reagent, which is capable in time of dissolving everything on earth.
2.1
INTRODUCTION
The primary management goal during remediation of a contaminated site is to

obtain closure, that is, to achieve a set of conditions that is considered environmentally acceptable and which will ensure that no future action will be required at the
site. A substantial ongoing national debate associated with site closure centers on
the definition of how clean is clean for contaminated subsurface media. The key
issue in this debate is, What concentration of residual contaminant in the subsurface,
particularly adsorbed to the soil, is environmentally acceptable?
In this context, the term contaminant availability becomes an important concept;
it refers to the rate and extent to which the chemical will be released from the
subsurface into the environment and/or is bioavailable to ecological and human
receptors. The dissemination of a contaminant after its release into the environment
is determined by its partition among the water, soil and sediment, and atmospheric
phases, and its degradability via biotic and/or abiotic means. These processes determine both the impact and the extent of its dissemination.
Within the context of overall site management, measurements of contaminant
availability are not intended to replace other approaches, required regulatorily, to
achieve site closure; rather, they are meant to broaden the range of options or tools
available to environmental professionals. This chapter will discuss the basis and
parameters for the development of procedures and determination of partitioning,
transport, and fate of various types of contaminants in the subsurface. These parameters will also provide the basis for the development of the tools to determine
contaminant availability and incorporate those estimations into a decision framework
to define environmentally acceptable endpoints for the different media. In addition,
how these parameters and characteristics influence contaminant fate and transport
and how they impact remediation system design are woven together in the discussions in subsequent chapters.
The reactions that contaminants undergo in the natural environment, such as sorption, desorption, precipitation, complexation, biodegradation, biotransformation,
hydrolysis, oxidation-reduction, and dissolution, are critical in determining their fate
and mobility in the subsurface environment. Reaction time scales can vary from microseconds for many ion association reactions microseconds and milliseconds for some
ion exchange and sorption reactions, to days, weeks, or months for some microbially
catalyzed reactions, or years for many mineral solution and crystallization reactions.
Both transport and chemical reaction processes can affect the reaction rates in
the subsurface environment. Transport processes include: (1) transport in the solution
phase, across a liquid film at the particle/liquid interface (film diffusion), and in
CONTAMINANT AND ENVIRONMENTAL CHARACTERISTICS
15
liquid-filled macropores, all of which are nonactivated diffusion processes and occur
in mobile regions; (2) particle diffusion processes, which include diffusion of sorbate
occluded in micropores (pore diffusion) and along pore-wall surfaces (surface diffusion) and diffusion processes in the bulk of the solid, all of which are activated
diffusion processes (Figure 2.1).1 Pore and surface diffusion within the immediate
region can be referred to as intra-aggregate (intraparticle) diffusion and diffusion in
the solid can be called interparticle diffusion. The actual chemical reaction at the
surface, e.g., adsorption, is usually instantaneous. The slowest of the chemical
reaction and transport process is the ratelimiting reaction.
2
3
4
6
Film
5
6
Solid (Soil Grain)
Liquid (Groundwater)
1
2
3
4
5
6
Figure 2.1
Transport in the Soil Solution (Macro Pores)

Transport Across a Liquid Film at the Solid-Liquid Interface
Transport in a Liquid-Filled Macropore
Diffusion of a Sorbate at the Surface of the Solid
Diffusion of a Sorbate Occluded in a Micropore
Diffusion in the Bulk of the Solid
Transport processes in solid-liquid soil reactions (adapted from Sparks, 1998).
As an introduction to the various organic compounds which end up as contaminants once discharged into the environment, Table 2.1 gives the basic structure of
the different compounds.
R
RNH
NH 2
R C
OH
O
OH
R C O
R C O
R 4N X
C O
NR 2 X
OH
CH 3CH2OH
CH 3CH 2OCH2CH 3
Bromide
Alcohol
Ether
Carboxylic acid
Ketone
CH3 C
CH3CH2C
OH
CH 3
CH3CH2CH
Aldehyde
H
CH3(CH2)9N(CH3)3Cl
Quaternary
ammonium
salt
CH3CH2CH2NH2
CH
CH3Br
Chloride
CH 2CH2Cl
Alkyne
Amine
HC
Alkene
CH 2
CH 3CH 3
H 2C
Alkane
Formula
Ethanoic acid
(Continued)
Acetic acid
Methyl ethyl
ketone
Propionaldehyde
Propanal
2-Butanone
DecyltrimethylAmmonium
chloride
DecyltrimethylAmmonium
chloride
Propylamine
Diethyl ether
Ethoxyethane
1-Aminopropane 3
Ethyl alcohol
Methyl bromide
Ethyl chloride
Ethanol
Bromomethane
Chloroethane
Acetylene
Ethyne
Ethane
Common Name
Ethylene
Ethene
Ethane
IUPAC Name
Example
16
OH
Br
Br
Cl
Cl
CnH 2n
C
CnH 2n-2
CnH 2n+2
None
General
Name
General
Formula
Functional
Group
Table 2.1 Some Common Functional Groups.
OH
Sulfone
Sulfoxide
CH3 S
CH3 S
CH 3 S
CH 3
CH 3
CH3
OH
CH3
The italicized portion indicates the group.

A primary (1) amine; there are also secondary (2), R NH,
and tertiary (3), R N,3 amines.
2
Another name is propanamine.
O
R
O
R
OH
O
S
Sulfonic acid
CH 3 S
Disulfide
CH 3
CH3 S
Thioether
(sulfide)
CH3 SH
Thiol
SH
CH3 NO2
Nitrile
Cl
NH 2
OC2H5
CH3 C O C
CH3 C
CH 3 C
Nitro
Acid anhydride
Acid chloride
Amide
CH
Formula
NO 2
SH
NO 2
O
R C O C
Cl
C O C
R C
Cl
NH 2
OR'
Ester
General
Name
1
Dimethyl disulfide
Methanesulfonic
acid
Dimethyl disulfide
Methanesulfonic acid
Dimethyl sulfone
Dimethyl sulfone
Dimethyl sulfoxide
Dimethyl sulfide
Dimethyl thioether
Dimethyl sulfoxide
Methyl mercaptan
Nitromethane
Acetonitrile
Acetic anhydride
Acetyl chloride
Acetamide
Acetic acid
Common Name
Methanethiol
Nitromethane
Ethanenitrile
Ethanoic anhydride
Ethanoyl chloride
Ethanamide
Ethyl ethanoate
IUPAC Name
Example
O
R C
NH 2
R C
OR'
General
Formula
Functional
Group
Table 2.1 (Cont.)

17
18
2.2
2.2.1
CONTAMINANT CHARACTERISTICS
Physical/Chemical Properties
2.2.1.1 Boiling Point

The boiling point is defined as the temperature at which a liquids vapor pressure
equals the pressure of the atmosphere on the liquid.2 If the pressure is exactly 1
atmosphere (101,325 Pa), the temperature is referred to as the normal boiling point.
Pure chemicals have a unique boiling point, and this fact can be used in some
laboratory investigations to check on the identity and/or purity of a material. Mixtures
of two or more compounds have a boiling point range.
For organic compounds, boiling points range from 162 to over 700C, but for
most chemicals of interest the boiling points are in the range of 300 to 600C.2
Having a value for a chemicals boiling point, whether measured or estimated, is
significant because it defines the uppermost temperatures at which the chemical can
exist as a liquid. Also, the boiling point itself serves as a rough indicator of volatility,
with higher boiling points indicating lower volatility at ambient temperatures. The
boiling point is associated with a number of molecular properties and features. Most
important is molecular weight; boiling points generally increase with this parameter.
Next is the strength of the intermolecular bonding because boiling points increase
with increasing bonding strength. This bonding, in turn, is associated with processes
and properties such as hydrogen bonding, dipole moments, and acid/base behavior.
2.2.1.2 Vapor Pressure
The vapor pressure of a chemical is the pressure its vapor exerts in equilibrium
with its liquid or solid phase.2 Vapor pressures importance in environmental work
results from its effects on the transport and partitioning of chemicals among the
environmental media (air, water, and soil). The vapor pressure expresses and controls
the chemicals volatility. The volatilization of a chemical from the water surface is
determined by its Henrys Law Constant, which can be estimated from the ratio of
a chemicals vapor pressure to its water solubility. The volatilization of a chemical
from the soil surface is determined largely by its vapor pressure, although this is
tempered by its sorption to the soil matrix and its Henrys Law Constant between
the soil water content and air.
A substances vapor pressure determines whether it will occur as a free molecule
in the vapor phase or will be associated with the solid phase. For volatile substances
that boil at or below 100C, the vapor pressure is likely to be known, but, for many
high-boiling substances with low vapor pressure, the value may be unknown or
poorly known. An estimation procedure may be needed to help convert the known
vapor pressure at the normal boiling point (i.e., 1 atmosphere) to the vapor pressure
at the lower temperatures of environmental importance. For some of these high
boiling compounds, the actual boiling point may also be unknown, since the substance may decompose before it boils.
19
2.2.1.3 Henrys Law Constant

Along with the octanol-water and octanol-air partition coefficients, the Henrys
Law Constant determines how a chemical substance will partition among the three
primary media of accumulation in the environment, namely air, water, and organic
matter present in soils, solids, and biota. Volatile organic compounds (VOCs) with
large values of Henrys Law Constant evaporate appreciably from soils and water,
and their fate and effects are controlled primarily by the rate of evaporation and the
rate of subsequent atmospheric processes. For such chemicals, an accurate value of
this parameter KAW is essential. Even a very low value of KAW for example, 0.001,
can be significant and must be known accurately, because the volume of the accessible atmosphere is much larger than that of water and soils by at least a factor of
1000; thus even a low atmospheric concentration can represent a significant quantity
of chemical. Further, the rate of evaporation from soils and water is profoundly
influenced by KAW because that process involves diffusion in water and air phases
in series, or in parallel, and the relative concentrations which can be established in
these phases control these diffusion rates.2,3
Accurate values of KAW are thus essential for any assessment of the behavior of
existing chemicals or prediction of the likely behavior of new chemicals. Air-water
partitioning can be viewed as the determination of the solubility of a gas in water
as a function of pressure, as first studied by William Henry in 1803. A plot of
concentration or solubility of a chemical in water expressed as mole fraction x, vs.
partial pressure of the chemical in the gaseous phase P, is usually linear at low partial
pressures, at least for chemicals which are not subject to significant dissociation or
association in either phase. This linearity is expressed as Henrys Law. The Henrys
Law Constant (H) which in modern SI units has dimensions of Pa/(mol fraction).
For environmental purposes, it is more convenient to use concentration units in water
CW of mol /m3 yielding H with dimensions of Pa m3/mol.
P (Pa) = H (Pa m3/mol) CW (mol/m3)
(2.1)
The partial pressure can be converted into a concentration in the air phase CA by
invoking the ideal gas law:
CA = n/V = P/RT
(2.2)
Where n is mols, V is volume (m3), R is the gas constant (8.314 Pa m3/mol K) and
T is absolute temperature (K).
CA = P/RT = (H/RT) CW = KAWCW
(2.3)
The dimensionless air-water partition coefficient KAW (which can be the ratio in units
of mol/m3 or g/m3 or indeed any quantity/volume combination) is thus (H/RT).
A plot of CA vs. CW is thus usually linear with a slope of KAW as Figure 2.2
illustrates. For organic chemicals which are sparingly soluble in water, these concentrations are limited on one axis by the water solubility and on the other by the
20
Concentration in Air CA
(Vapor Pressure/RT)
Slope = Kaw
= H/RT
[Solubility of
Compound]
Concentration in Water Cw
Figure 2.2
Description of Henrys Law Constant.
maximum achievable concentration in the air phase which corresponds to the vapor
pressure, as Figure 2.2 shows. To the right of or above the saturation limit, a separate
organic phase is present. Strictly speaking, this saturation vapor pressure is that of
the organic phase saturated with water, not the pure organic phase.2,3
2.2.1.4 Octanol/Water Partition Coefficients
The usefulness of the ratio of the concentration of a solute between water and
octanol as a model for its transport between phases in a physical or biological system
has long been recognized.2,4,5 It is expressed as POCT = CO /CW = KOW . This ratio is
essentially independent of concentration, and is usually given in logarithmic terms
(log POCT or log KOW). The importance of bioconcentration in environmental hazard
assessment and the utility of this hydrophobic parameter in its prediction led to an
intense interest in the measurement of POCT and also its prediction from molecular
structure. (So many calculation methods have been published in the last five years
that it is not possible to examine them all in detail.)
2.2.1.5 Solubility in Water
Solubility in water is one of the most important physical chemical properties of
a substance, having numerous applications to the prediction of its fate and its effects
in the environment. It is a direct measurement of hydrophobicity, i.e., the tendency
of water to exclude the substance from solution. It can be viewed as the maximum
concentration which an aqueous solution will tolerate before the onset of phase
separation.
21
Substances which are readily soluble in water, such as lower molecular weight
alcohols, will dissolve freely in water if accidentally spilled and will tend to remain
in aqueous solution until degraded. On the contrary, sparingly soluble substances
dissolve more slowly and, when in solution, have a stronger tendency to partition
out of aqueous solution into other phases. They tend to have larger airwater partition
coefficients or Henrys Law Constants, and they tend to partition more into solid
and biotic phases such as soils, sediments, and fish. As a result, it is common to
correlate partition coefficients from water to those media with solubility in water.
Solubility normally is measured by bringing an excess amount of a pure chemical
phase into contact with water at a specified temperature, so that equilibrium is
achieved and the aqueous phase concentration reaches a maximum value. It is rare
to encounter a single compound as the contaminant present in the groundwater at a
contaminant site.
C *i = C 0i x i i
(2.4)
where,
Ci*
Ci0
xi
i
=
=
=
=
equilibrium solute concentration for component i in the mixture

equilibrium solute concentration for component i as a pure compound
mole fraction of compound i in the mixture
activity coefficient of compound i in the mixture.
Possible equilibrium situations may exist, depending on the nature of the chemical phase, each of which requires separate theoretical treatment and leads to different
equations for expressing solubility. These equations form the basis of the correlations
discussed later.
Single compound is an immiscible liquid (e.g., Benzene)
C* = Co x
(2.5)
In this case, C* is also C. Thus the product x is 1.0 and x is 1/. Sparingly
soluble substances act in such a way because the value of is large.2
For example, at 25C benzene has a solubility in water of 1780 g/m3 or 22.8
mol/m.3 Since 1 m3 of solution contains approximately 106/18 mol water (1m3 is
106 g and 18 g /mol is the molecular mass of water), the mole fraction x is
22.8/(106/18) or 0.00041. The activity coefficient is thus 2440; i.e., a benzene
molecule in aqueous solution behaves as if its concentration were 2440 times
higher.
Substances such as polychlorinated biphenyls (PCBs) can have activity coefficients exceeding 1 million. Hydrophobicity thus is essentially an indication of the
magnitude of . Some predictive methods focus on estimating , from which solubility can be deduced.
22
Single compound is a miscible substance (e.g., Ethanol)

If the activity coefficient is relatively small, i.e., < 20, it is likely that the liquid
is miscible with water and no solubility can be measured. The relevant descriptor
of hydrophobicity in such cases is the activity coefficient. Correlations of other
environmental partitioning properties with solubility are then impossible.2
Solubility is a function of temperature because both vapor pressure and are
temperature dependent. Usually falls with increasing temperature, thus solubility
increases. This implies that the process of dissolution is endothermic. Exceptions
are frequent and in some cases, such as benzene, there may be a solubility minimum
as a function of the temperature at which the enthalpy of dissolution is zero.2
Under natural conditions, dissolved organic matter such as humic and fulvic
acids frequently increases the apparent solubility. This is the result of sorption of
the chemical to organic matter which is sufficiently low in molecular mass to be
retained permanently in solution. The true solubility or concentration in the pure
aqueous phase probably is not increased. The apparent solubility is the sum of the
true or dissolved concentration and the quantity which is sorbed.
The solubility of substances such as carboxylic acids, which dissociate or form
ions in solution, is also a function of pH, a common example being pentachlorophenol. Data must thus be at a specific pH. Alternatively, the solubility of the parent
(nonionic) form may be given, and pKa or pKb given, to permit the ratio of ionic to
nonionic forms to be calculated as
Ionic/non-ionic = 10(pHpKa)
(2.6)
The total solubility is then that of the parent and ionic forms.
2.2.1.6 Hydrolysis
Hydrolysis is a bond-making, bond-breaking process in which a molecule, RA,
reacts with water, forming a new RO bond with the oxygen atom from water and
breaking the RA bond in the original molecule. One possible pathway is the direct
displacement of A with OH, as Equation 2.7 shows.
RA + H2O ROH + HA
(2.7)
Hydrolytic processes provide the baseline loss rate for any chemical in an
aqueous environment. Although various hydrolytic pathways account for significant
degradation of certain classes of organic chemicals, other organic structures are
completely inert. Strictly speaking, hydrolysis should involve only the reactant
species water provides that is, H+, OH and H2O but the complete picture
includes analogous reactions and thus the equivalent effects of other chemical species
present in the local environment, such as HS in anaerobic bogs, Cl in seawater,
and various ions in laboratory buffer solutions.
Hydrolysis results in reaction products that may be more susceptible to biodegradation, as well as more soluble. The likelihood that a halogenated solvent will
23
undergo hydrolysis depends in part on the number of halogen substituents. More

halogen substituents on a compound will decrease the chance for hydrolysis reactions
to occur and will therefore decrease the rate of the reaction. Hydrolysis rates can
generally be described using first-order kinetics, particularly in groundwater where
water is the dominant nucleophile. Bromine substituents are more susceptible to
hydrolysis than chlorine substituents. As the number of chlorine atoms in the molecule increases, dehydrohalogenation may become more important.12,47
Dehydrohalogenation is an elimination reaction involving halogenated alkanes
in which a halogen is removed from one carbon atom, followed by subsequent
removal of a hydrogen atom from an adjacent carbon atom. In this two-step reaction
an alkene is produced. Although the oxidation state of the compound decreases due
to the removal of a halogen, the loss of a hydrogen atom increases it. This results
in no external electron transfer, and there is no net change in the oxidation state of
the reacting molecule.47 Contrary to the patterns observed for hydrolysis, the likelihood of dehydrohalogenation increases with the number of halogen constituents.
Under normal environmental conditions, monohalogenated aliphatics apparently do
not undergo dehydrohalogenation. The compounds 1,1,1-TCA and 1,1,2-TCA are
known to undergo dehydrohalogenation and are transformed to 1,1-DCE, which is
then reductively dechlorinated to VC and ethene. Tetrachloroethanes and pentachloroethanes are transformed to TCE and PCE via dehydrohalogenation pathways.47
Methods to predict the hydrolysis rates of organic compounds for use in the
environmental assessment of pollutants have not advanced significantly since the
first edition of the Lyman Handbook.8 Two approaches have been used extensively
to obtain estimates of hydrolytic rate constants for use in environmental systems.2
The first and potentially more precise method is to apply quantitative structure/activity relationships (QSARs).2,9 To develop such predictive methods, one needs a set
of rate constants for a series of compounds that have systematic variations in structure
and a database of molecular descriptors related to the substituents on the reactant
molecule. The second and more widely used method is to compare the target
compound with an analogous compound or compounds containing similar functional
groups and structure, to obtain a less quantitative estimate of the rate constant.
Predictive methods can be applied for assessing hydrolysis for simple one-step
reactions where the product distribution is known. Generally, however, pathways are
known only for simple molecules. Often, for environmental studies, the investigator
is interested in not only the parent compound but also the intermediates and products.
Therefore, estimation methods may be required for several reaction pathways.
Some preliminary examples of hydrolysis reactions illustrate the very wide range
of reactivity of organic compounds. For example, triesters of phosphoric acid hydrolyze in near-neutral solution at ambient temperatures with half-lives ranging from
several days to several years,10 whereas the halogenated alkanes such as tetrachloroethane, carbon tetrachloride, and hexachloroethane have half-lives of about 2
hours, 50 years, and 1000 millennia (at pH = 7, and 25C), respectively.11,12 On the
other hand, pure hydrocarbons from methane through the PAHs are not hydrolyzed
under any circumstances that are environmentally relevant.
Hydrolysis can explain the attenuation of contaminant plumes in aquifers where
the ratio of rate constant to flow rate is sufficiently high. Thus 1,1,1-trichloroethane
24
(TCA) has been observed to disappear from a mixed chlorinated hydrocarbon plume
over time, while trichloroethene and its biodegradation product cis-1,2-dichloroethene persist. The hydrolytic loss of organophosphate pesticides in sea water, as
determined from both laboratory and field studies, suggests that these compounds
will not be long-term contaminants despite runoff into streams and, eventually,
the sea.
2.2.1.7 Photolytic Reactions in Surface Water
Photolysis (or photolytic reaction) can be defined as any chemical reaction that
occurs only in the presence of light. Environmental photoreactions necessarily take
place in the presence of sunlight, which has significant photon fluxes only above
295 nm in the near ultraviolet (UV) range, extending into the infrared region of the
electromagnetic spectrum.2,13 Environmental photoreactions occur in surface waters,
on solid ground, and in the atmosphere, sometimes rapidly enough to make them
the dominant environmental transformation processes for many organic compounds.
In the atmosphere, for example, photooxidation, mediated by hydroxyl radical (OH),
is the dominant removal process for more than 90% of the organic compounds
found there.
Photolytic reactions are often complex reactions that not only control the fate
of many chemicals in air and surface water, but also often produce products with
chemical, physical, and biological properties quite different from those of their parent
compounds: more water soluble, less volatile, and less likely to be taken up by biota.
Photooxidation removes many potentially harmful chemicals from the environment,
although occasionally more toxic products form in oil slicks and from pesticides.14
Biogeochemical cycling of organic sulfur compounds in marine systems involves
photooxidation on a grand scale in surface waters, as well as in the troposphere.2
Environmental photoreactions can be divided into two broad categories of reactions: direct and indirect. A direct photoreaction occurs when a photon is absorbed
by a compound leading to formation of excited or radical species, which can react
in a variety of different ways to form stable products. In dilute solution, rate constants
for these reactions are the products of the rate constants for light absorption and the
reaction efficiencies. An indirect photoreaction occurs when a sunlight photon is
absorbed by one compound or group of compounds to form oxidants of excited
states, which then react with or transfer energy to other compounds present in the
same environmental compartment to form new products. For example, NO2 and O3
in air form hydroxyl radicals (OH), and humic acids in water form singlet oxygen
and oxyradicals, when they absorb sunlight photons. These oxidants react with other
chemicals in thermal (dark) reactions, and the rates for these processes follow simple
bimolecular kinetics.
Direct Photoreactions: Only a small proportion of synthetic organic compounds
absorb UV light in the sunlight region of the spectrum (above 295 nm) and then
photolyze at significant rates.13 Most aliphatic and oxygenated compounds, such as
alcohols, acids, esters, and ethers, absorb only in the far UV region (below 220 nm),
25
and simple benzene derivatives with alkyl groups or one heteroatom substituent
absorb strongly only in the far and middle UV region. Nitro or polyhalogenated
benzenes, naphthalene derivatives, polycyclic aromatics and aromatic amines,
nitroalkanes, azaolkanes, ketones, and aldehydes absorb sunlight between 300 and
450 nm; polycyclic and azoaromatics (dyes), as well as quinones, also absorb visible
light, in some cases to beyond 700 nm.2,13
The rate of a direct photoprocess depends only on the product of the rate of light
(photon) absorption by compound C,(IA) and the efficiency with which the absorbed
light is used to effect reaction (quantum yield, ):13
Rate =
dc
= Efficiency Photons Absorbed / time = I A
dt
(2.8)
Under most environmental conditions, chemicals are present in surface water or

air at low concentrations, so their light absorbing properties lead to simple kinetic
expressions for direct photolysis in water.13
Indirect Photoreactions: Indirect photolysis is most important for compounds
that absorb little or no sunlight. Light absorption by chromophores (sensitizers) other
than the compound of interest begin the process, forming intermediate (and transient)
oxidants or excited states that affect chemical changes in the compound of interest.2,15,16 Examples of sensitizers that serve this purpose are dissolved organic matter
(DOM or humic acid) and nitrate ion in water, and ozone and NO2 in the atmosphere.
Transient species formed by indirect photoreactions in water include singlet oxygen
and peroxy radicals, both of which are relatively selective and electrophilic. As a
result, only electron-rich compounds, such as phenols, furans, aromatic amines,
polycyclic aromatic hydrocarbons (PAHs), and alkyl sulfides can undergo relatively
rapid indirect photoprocesses with these oxidants. Nitroaromatics, though not oxidized, appear to be sensitized by triplet DOM or scavenged by solvated electrons.
Many of these compounds (e.g., PAHs, nitroaromatics, and aromatic amines) also
undergo rapid direct photoreactions.2,16
By contrast, OH radical, which dominates tropospheric photochemistry, oxidizes
all classes of organic compounds (except perhalogenated compounds such as PCE),
including alkanes, olefins, alcohols, and simple aromatics.160,166 Aqueous OH. radical, derived mainly from the photolysis of nitrate ion, plays an important role in
converting marine DOM to simpler carbonyl compounds, even though the average
concentration is extremely low (<2 108).17 OH also appears important in degrading
synthetic chemicals in a variety of nitrate-bearing freshwaters, where the OH concentrations appear to be one to two orders of magnitude higher.2,13
In many cases, detailed pathways for forming these oxidants and reductants
remain unclear, but identities of several of the transients are fairly well established.2,13
Transient species are transient because they react rapidly with themselves or with a
variety of natural organic and metal species in natural waters,2 balancing formation
rates to give low average concentrations.
26
2.2.2
Biological Characteristics
It is generally conceded that biological reactions are of the greatest significance

in determining the fate and persistence of organic compounds in most natural aquatic
ecosystems. It is essential at the start to make a clear distinction between biodegradation and biotransformation. Biodegradation is a process in which the destruction
of a chemical is accomplished by the action of a living microorganism. During
biotransformation, on the other hand, only a restricted number of metabolic reactions
is accomplished, and the basic framework of the molecule remains essentially
intact.18 Even though biodegradation and biotransformation, considered as alternatives, are not mutually exclusive.
Biodegradation can be categorized into three types that have importance in an
ecosystem setting:
Primary Biodegradation: biodegradation to the minimum extent necessary to change
the identity of the compound.
Ultimate Biodegradation: biodegradation to water, carbon dioxide, and inorganic compounds (if elements other than C, H, and O are present). This is also called mineralization. Under anaerobic conditions, methane may be formed in addition to carbon
dioxide during fermentation reactions.
Acceptable Biodegradation: biodegradation to the minimum extent necessary to remove
some undesirable property of the compound, such as toxicity. Conversion of vinyl
chloride to ethene is an example and in many instances this can also be considered
biotransformation.
Although biological degradation conceivably might be accomplished by any

living organism, available information indicates that, by far, the most significant
biological systems involved in ultimate biodegradation of contaminants are bacteria
and fungi. Critical and necessary conditions necessary for biodegradation of contaminants to take place are summarized below:
A microbial population must exist that has the necessary enzymes to bring about
the biodegradation.
This population must be present in the environment where the contaminant is
present.
The contaminant must be accessible to the microorganisms having the requisite
enzymes, and most of the time this requires the contaminant to be available in
the dissolved phase.
If the initial enzyme bringing about the degradation is extracellular, the bonds
acted upon by that enzyme must be exposed for the catalytic enzyme to function.
Should the enzyme catalyzing the initial degradation be intracellular, the molecule
must penetrate the surface of the cell to the internal sites where the enzyme acts.
Alternatively, for the transformation to proceed further, the products of an extracellular reaction must penetrate the cell.
Because the population or biomass of bacteria or fungi acting on many synthetic
compounds is initially small, conditions in the environment must be optimum to
allow for proliferation of the potentially active microorganisms.
27
The initial concentration of the microbial population and the contaminant somewhat affects the growth and proliferation; a lag period often occurs between the
addition of a chemical and the onset of biodegradation. This lag period, usually
attributed to the need for acclimation,19,20 could result from enzyme induction, gene
transfer or mutation, predation by protozoa, or growth in the population of responsible organisms.
The initial species present, their relative concentrations, the induction of their
enzymes, and their ability to acclimate once exposed to a chemical are likely to vary
considerably, depending upon environmental parameters such as temperature, salinity, pH, oxygen concentration (aerobic or anaerobic), redox potential, concentration
and nature of various substrates and nutrients, concentration of heavy metals (toxicity), and effects (synergistic and antagonistic) of associated microflora.21 Many of
these parameters affect the biodegradation of contaminants in the environment.
One important parameter is the chemical substrate concentration. A number of
chemicals have biodegradation rates proportional to substrate concentration, but
there are also examples of thresholds and inhibitions.22 Recently, the bioavailability
of the chemical to the catalytic enzyme has been identified as a major factor in
determining biodegradability in nature. Several studies have demonstrated that,
although a chemical freshly added to soil is biodegraded at a moderate rate, the
biodegradation rate for some chemicals present in the soil sample for a long time
is very low.19 Thus, depending on the chemical, the longer a chemical remains in
the soil, the greater the potential for it to become sequestered and less bioavailable.
Some microorganisms are capable of biodegrading contaminants without population growth. In this process, known as cometabolism,19 the microorganism
degrades the contaminant from which it derives no carbon or energy; instead, it is
sustained on other organic substrates and nutrients.
2.2.2.1 Cometabolism
The transformation of an organic compound by a microorganism that is unable
to use the substrate as a source of energy or as one of its growth substrate is termed
cometabolism. The active populations thus derive no nutritional benefit from the
substrates they cometabolize. Energy sufficient to fully sustain growth is not acquired
even if the conversion is an oxidation and releases energy. In addition, the C, N, S,
or P that may be in the molecule is not used as a source of these elements for growth
and energy deriving purposes. Because of the prefix co, which often is appended to
a word to indicate that something is done jointly or together (as in copilot or
cooperate), there has been some debate regarding the use of the term cometabolism.
Specifically, some classical microbiologists argue that the term should be applied
only to circumstances in which a substrate that is not used for growth is metabolized
in the presence of a second substrate that is used to support multiplication.19 According to this view, the transformation of a substance that is not used as a nutrient or
energy source but which occurs in the absence of a chemical supporting growth
should be designated by another term, for example, fortuitous metabolism. However,
the prefix co also has another meaning, namely, the same or similar. The latter
usage implies that the cometabolic transformation is similar to some other metabolic
28
reaction, which is consistent with one explanation for the phenomenon. Fortuitous
metabolism is, indeed, a more attractive term because it suggests an explanation for
cometabolism, but the term will be used here as in the original definition, if for no
other reason than it has gained wide acceptance.
The term cooxidation is sometimes used in studies of pure cultures of bacteria,
referring specifically to oxidations of substrates that do not support growth in the
presence of a second compound that does support multiplication. Cooxidation has
historical precedence in the debate but since it is restricted to oxidation, the word
does not have sufficient breadth to include many reactions that are not oxidations.19
In summary, two types of reactions called cometabolism take place in the environment. In one, the cometabolized compound is transformed only in the presence
of a second substrate, which indeed may be the compound that supports growth.
For heterotrophs, the energy-providing substrate is organic; for autotrophs, it is
inorganic. In the other type, the compound is metabolized even in the absence of a
second substrate.
Important reasons for using the more general definition, and even for maintaining
cometabolism as a term apart from bioconversion or biotransformation, are the
environmental consequences of cometabolism. Cometabolic reactions have impacts
in nature that are different from growth-linked biodegradations, and when the transformations take place, it is usually totally unclear whether the microorganisms do
or do not have a second substrate available on which they are growing.
A large number of chemicals are subject to cometabolism in nature. Among
cometabolic conversions that appear to involve a single enzyme, the reactions may
be hydroxylations, oxidations, denitrations, deaminations, hydrolyses, acylations, or
cleavages of ether linkages; however, many of the conversions are complex and
involve several enzymes. Some of the unique cometabolic reactions brought about
by bacteria and fungi in nature come as no surprise in view of the vast array of
growth linked biological transformations that heterotrophic bacteria and fungi are
capable of in nature. An example which has no significant importance in contaminant
removal is the methane monooxygenase of methanotrophic bacteria which is able
to oxidize alkanes, alkenes, secondary alcohols, methylene chloride, chloroform,
dialkyl ethers, cycloalkanes, and various aromatic compounds.19
Caution needs to be exercised in concluding that cometabolism is occurring
merely because an organism cannot be isolated from an environment in which a
chemical is undergoing a biological reaction.19 The isolation of bacteria acting on
specific substrates is usually performed by enriching the organism in a medium when
the only C source is the test chemical, and the agar medium used to plate the
enrichments contains that single organic supplement. Yet, many bacteria that are
able to grow at the expense of that substrate will not develop in such simple media
because they require amino acids, B vitamins, or other growth factors. These essential
growth factors are not routinely included in such liquid media, and hence bacteria
and fungi needing them fail to proliferate. If the only organisms in the environment
able to metabolize a contaminant need these growth factors, no isolate will be
obtained, and an erroneous conclusion will be reached that the compound is cometabolized. If a chemical supports the growth of many species, some will undoubtedly
require no growth factors (these organisms are called prototrophs), and they will be
29
enriched and ultimately can be isolated. If the compound is acted on by only one
species, in contrast, it is likely that the responsible organism will need amino acids,
B vitamins, or other growth factors; these species are termed auxotrophs. Hence,
the failure to isolate a bacterium or fungus capable of using the contaminant as the
sole C source for growth is not sufficient evidence for cometabolism.
Mechanisms of Cometabolic Reactions: Several reasons have been advanced to
explain cometabolism, that is, why an organic chemical that is a substrate does not
support growth but is converted to products that accumulate. Some of these reasons
have experimental support: (1) the initial enzyme converts the substrate to a product
that is not further transformed by other enzymes in the microorganism to yield the
metabolic intermediates ultimately used for biosynthesis and energy production; (2)
the initial substrate is transformed to products that inhibit the activity of later enzymes
in mineralization or that suppress growth of the organisms; and (3) the organism needs
a second substrate to bring about some particular reaction.
It could be speculated that the first explanation is the most common. The basis
for this explanation is the fact that many enzymes act on several structurally related
substrates; thus, an enzyme naturally present in the cell will catalyze reactions and
alter synthetic chemicals that are not typical cellular intermediates. These enzymes
are not absolutely specific for their substrates. Consider a normal metabolic sequence
involving the conversion of A to B by enzyme a, B to C by enzyme b, and C to D
by enzyme c in a sequence that ultimately yields CO2 energy for biosynthesis
reactions and intermediates that are converted to cell constituents.19
a
A B C D CO 2 + energy + cell C
(2.9)
The first enzyme a may have a low substrate specificity and act on a molecule
structurally similar to A, namely, A.1 The product (B1) would differ from B in the
same way that A differs from A1. However, if enzyme b is unable to act on B1
(because the structural features controlling which substrate it modifies differ from
those controlling the substrate specificity of enzyme a), B1 will accumulate:19
a
1
A B1
(2.10)
In addition, CO2 and energy will not be generated and, because cellular carbon
is not formed, the organisms do not multiply. The formation of B1 is thus entirely
fortuitous.19
In instances where the contaminant concentration is high, cometabolism may
result from the conversion of the parent compound to toxic products. In the sequence
just depicted, if the rate of reaction catalyzed by enzyme a is faster than the process
catalyzed by enzyme b, B will accumulate because it is not destroyed as readily as
it is generated. For example, a strain of pseudomonas that grows on benzoate but
not 2-fluorobenzoate converts the latter to fluorinated products that are toxic.23 The
inhibitor that accumulates may affect a single enzyme important for the further
metabolism of the toxin.
30
In some instances, an organism may not be able to metabolize an organic

compound because it needs a second substrate to bring about a particular reaction.
The second substrate may provide something that is present in insufficient supply
in the cells for the reaction to proceed for example, an electron donor for the
transformation.19
The above explanation is linked to the existence of enzymes acting on more than
a single substrate. Many enzymes are not absolutely specific for a single substrate.
As a rule, they act on a series of closely related molecules, but some carry out a
single type of reaction on a variety of somewhat dissimilar molecules. The following
are examples of single enzymes acting on a range of substrates:
Methane monoxygenase of methanotrophic bacteria: When grown on methane,
methanol, or formate, these aerobic bacteria are able to cometabolize a large array
of organic molecules, including several major pollutants. In each instance, methane
monooxygenase is the responsible catalyst. Other chlorinated aliphatic hydrocarbons transformed by one such methanotroph, Methylosinus trichosporium, are cisand trans-1,2-dichloroethylene, 1,1-dichloroethylene, 1,2-dichloropropane, and
1,3-dichloropropylene.24 Apparently the same enzyme in other bacteria, after
growth on methane, will catalyze the oxidation of n-alkanes with two to eight C
atoms, n-alkenes with two to six C atoms, and mono- and dichloroalkanes with
five or six C atoms, as well as dialkyl ethers and cycloakanes.19
Toluene dioxygenase of a number of aerobic bacteria: This enzyme incorporates
both atoms of oxygen from O2 (hence, it is a dioxygenase) into toluene as it
catalyzes the first step in the degradation of toluene by bacteria grown on that
aromatic hydrocarbon (Figure 2.3a). However, that same enzyme has very low
specificity and also is able to bring about the degradation of TCE,19,25,26 to convert
2- and 3-nitrotoluene to the corresponding alcohols, and to hydroxylate the ring
of 4-nitrotoluene.19,27
Toluene monooxygenase of several aerobic bacteria: Differing from the dioxygenase, this enzyme incorporates only one atom of oxygen from O2 into toluene to
give o-cresol (Figure 2.3b). However, because of this enzyme, bacteria can cometabolize TCE, convert 3- and 4-nitrotoluenes to the corresponding benzyl alcohols
and benzaldehydes, and add hydroxyl groups to other aromatic compounds.19,28,29
Oxygenase of propane-utilizing bacteria: Aerobes using propane as C and energy
source for growth also have an oxygenase of broad specificity. This enzyme
cometabolizes TCE, vinyl chloride, and 1,1-di- and trans- and cis-1,2-dichloroethylene and has been recently known to degrade MtBE.19,30
Ammonia monooxygenase of Nitrosomonas europaea: This bacterium, which is a
chemoautotroph whose energy source in nature is NH4+ and whose C source is
CO2, cometabolizes TCE, 1,1-dichloroethylene, various mono- and polyhalogenated ethanes, and a variety of monocyclic aromaticcompounds and thioethers, as
well as methyl fluoride and dimethyl ether.19,31
An alkane hydroxylase hydroxylates a number of alkylbenzenes and linear,
branched, and cyclic alkanes.19,23
An alkane monooxygenase degrades TCE, vinyl chloride, and dichloroethylenes
and propylenes.19
Naphthalene dioxygenase acts on xylene, isomers of nitrotoluene, and ethylbenzene.19,33
Biphenyl dioxygenase transforms several PCB congeners.19,34
31
CH3
OH
2H
H
OH
O2
H
TOLUENE
CH2OH
CH3
NO2
NO2
2-NITROTOLUENE
CH2OH
CH3
NO2
NO2
3-NITROTOLUENE
CH3
CH3
CH3
OH
OH
+
OH
NO2
NO2
NO2
4-NITROTOLUENE
O
CCI2 CICH
TCE
Figure 2.3a
HC
COOH + HCOOH + CI-
Reactions catalyzed by toluene dioxygenase (adapted from Alexander, 1999).
32
CH3
CH3
OH
TOLUENE
Figure 2.3b
o-CRESOL
Reactions catalyzed by toluene monooxygenase (adapted from Alexander,

1999).
The organism containing these enzymes may be able to use one of several of
the enzymes substrates for growth. However, many of the substrates are transformed
but do not support growth. The product of the reactions then accumulates.
Because cometabolism generally leads to a slow degradation of the substrate,
attention has been given to enhancing its rate.19 The addition of a number of organic
compounds to the contaminated zone promotes the rate of cometabolism of a number
of chlorinated aliphatic and aromatic compounds and chlorinated phenols, but the
responses to such additions are not predictable. No relation is known to exist between
the metabolic pathways involved in the degradation of the added mineralized substrate and the compound that is cometabolized in these circumstances. The added
substrates were randomly chosen in these trials, and sometimes they do and sometimes they do not stimulate cometabolism. In instances in which stimulation occurs,
the benefit probably results from an unpredicted increase in the biomass of organisms, some of which fortuitously cometabolize the compound of interest.
An alternative approach is to add mineralizable compounds that are structurally
analogous to the compound whose cometabolism one wishes to promote. Presumably, the microorganism that grows on the mineralizable compound contains
enzymes transforming the analogous molecule that is cometabolized. This larger
biomass thus has more of the degradative enzyme than is present in the unsupplemented water or soil. This method of analogue enrichment has been used to enhance
the cometabolism of PCBs by additions of biphenyl. The unchlorinated biphenyl
was selected for addition to soil since it is mineralizable, nontoxic, and serves as a
C source for microorganisms that are able to cometabolize PCBs.19
Analogue enrichment is a procedure that is similar to the usual means of isolating
bacteria that can cometabolize a compound. The enrichment culture contains a C
source that supports growth, and the pure cultures thus obtained also cometabolize
structurally related compounds that would not support growth. For example, bacteria
isolated on diphenylmethane and containing enzymes to degrade it also cometabolize
chlorinated diphenylmethanes. Many of the latter do not sustain growth.19
2.2.2.2 Kinetics of Biodegradation
Impacts of the Environment: Soil, water, sediment, and wastewater environments have different microbial populations and different available nutrients which
may affect considerably the rate of biodegradation. For example, wastewater
33
treatment plants may have high levels of nutrients and high microbial populations
that may have been pre-exposed to a contaminant (acclimated microbial population),
but the contact (retention) time is relatively short.
In contrast, marine waters are usually fairly low in nitrogen and phosphorous
which may limit the biodegradation of chemicals (e.g., oil spills). Sediment often
has high levels of organic nutrients, but often is anaerobic, while surface waters
tend, by comparison, to have low levels of organic nutrients.18 Digestor sludge from
wastewater treatment plants has high organic nutrients and is anaerobic. Surface
soils have high concentrations of organic nutrients (depending on the type of soil),
but this usually decreases with depth.
In the past, it was believed that groundwater aquifers were devoid of microbial
life. However, a number of studies have demonstrated that microorganisms are quite
plentiful in certain aquifers, and, in some instances, the bacterial concentration and
activity in aquifers may be higher than those in surface waters.19,35 In addition,
availability of the chemical to the microbial population can be affected considerably
by the conditions of the microenvironment (e.g., organic concentration or clay
content may bind the chemical tightly).
A contaminant may become less available or essentially unavailable for biodegradation if it enters or is deposited in a micropore that is inaccessible even to the
microorganisms. These micropores may be filled entirely with water, as in sediments
or groundwater aquifers, and the contaminant would have to move out of a micropore
by diffusion to be accessible to bacteria for its destruction. The tortuous path the
contaminant molecule must traverse before it gets destroyed dramatically affects
bioavailability if the contaminant not only is physically remote from potentially
active microorganisms, but also is strongly sorbed to solid surfaces associated with
that remote micropore.19
Some organic compounds that persist in the subsurface often undergo a time
dependent decline in bioavailability. Since this process is slow and time dependent
it is appropriately called aging. This modification in bioavailability to microorganisms as a result of aging is also called sequestration.19 In the initial period, the
compound gradually disappears as a result of biodegradation, and possibly by other
mass removal mechanisms, but little or none of the compound is destroyed after it
has resided in the soil or sediment for some time. Witness the finding that although
80% of hexachlorobenzene deposited in the early 1970s in a lake bottom sediment
was dechlorinated in the succeeding 20 years, all sediment cores still contained at
least 40 ppb of hexachlorebenzene. This time-dependent change in the rate of
degradation, which has been observed with a number of insecticides, was the first
line of evidence for sequestration.19 Because these aged molecules are solvent
extractable, albeit by vigorous treatment, they are presumed to be present in an
uncomplexed form and thus considered to be contaminants and subject to the regulations and cleanup standards. In addition to the above mentioned contaminants,
PAHs with three or more rings, such as phenanthrene, anthracene, fluorene, pyrene,
chrysene, and others will also undergo sequestration.
It has been known for some time that it is increasingly difficult to remove strongly
hydrophobic compounds from soil with mild extractants as the residence time of
34
those compounds in the soil increases. This phenomenon is not restricted to soils;
a similar decline in extractability is witnessed also from sediment samples.36
The amount of a contaminant that is sequestered increases with time. Expressed
in another way, the percentage of the chemical that is bioavailable diminishes with
increasing persistence. This presumably occurs because more of the contaminant is
diffusing into inaccessible sites. However, after a period of time that varies with the
soil and the compound, sequestration of additional quantities slows and possibly
stops. The reason for this rate of decline is not presently known.36
Based on the preceding discussion, it can be seen that the rates of biodegradation
are likely to vary considerably, depending on the environment to which a contaminant
is released, the type of contaminant(s), and the age of contamination. Also, the rates
under different conditions may vary depending upon the type of chemical structure.
For example, nitro aromatic compounds are usually fairly resistant to biodegradation
under aerobic conditions but are reduced rapidly to amines under anaerobic conditions. In contrast, degradation of benzene takes place significantly faster under
aerobic conditions than under anaerobic conditions.
Structural Effects on Biodegradation: In addition to contaminant concentration, chemical structure and physical/chemical properties have considerable impact
on the rate and pathways of biodegradation. The chemical structure determines the
possible pathways that a substrate may undergo, generally classified as oxidative,
reductive, hydrolytic, or conjugative. Figure 2.4 provides some examples of common
microbial degradation pathways.37 Recently, a computer program was developed that
will predict the most probable metabolites, and another computer program was also
developed that simulates the biodegradation of synthetic chemicals through the
sequential application of plausible biochemical reactions.38,39
Over the years, structure/biodegradability rules of thumb have been developed.40,41 Figures 2.4a and b summarize these. Some of these structure/biodegradibility relationships have some biochemical mechanistic underpinings. For
example, highly branched compounds frequently are resistant to biodegradation
because increased substitution hinders -oxidation, the process by which alkyl
chains and fatty acids usually are biodegraded. This structural relationship was
discovered in the 1950s when detergent scientists found that alkylbenzene sulfonate (ABS) detergents passed through wastewater treatment plants causing foaming problems in rivers and streams. This problem was solved by switching from
the highly branched ABS detergents to linear alkylbenzene sulfonate (LAS) detergents, thus illustrating the importance of understanding the relationship between
structure and biodegradability.
Few other rules of thumb have such mechanistic bases, but there are some general
trends. Functional groups commonly seen by microorganisms in natural products
usually are degraded easily, probably because the microbes have had eons to develop
the required enzyme systems in order to gain carbon and energy from the metabolism.
Conversely, functional groups less common in nature or newly synthesized by man
usually make a chemical more resistant to biodegradation. Aromatic substituents
that are electron withdrawing (e.g., nitro groups and halogens) increase the persistence of a chemical, possibly by making it more difficult for enzymes to attack the
aromatic ring, whereas electron donating functionalities (e.g., carboxylic acids,
phenols, amines) generally increase biodegradation rates.
L1282_C02_frame Page 35 Tuesday, June 19, 2001 12:57 PM
Type of Reactions (not all steps are given)
Example of Chemicals
Subject to Reaction
-oxidation
Fatty acids and straight chain

hydrocarbons (after oxidation
of chain to carboxylic acid see methyl oxidation)
CH3[CH2]x
CO2H
CH3[CH2]x
CO2H
Methyl oxidation
R
CH3
CH2OH
CHO
CH2H
Epoxide formation
35
Aromatic and aliphatic

methyl groups
Olefins
O
R
Hydroxylation and ketone formation
Aromatic to form phenols

and hydrocarbons to alcohols
and then ketones
OH
OH
R
O
R
Nitrogen oxidation
R
NH2
Aromatic amines to
nitroaromatic
NHOH
N=O
NO2
NHOH
NH2
Nitro reduction
R
NO2
N=O
Nitrile/amide metabolism
Nitroaromatics aromatic
amines (e.g., parathion)
especially fast under
anaerobic conditions
Bromoxynil, Dichlobenil
O
R
CN
CO2H
Sulfides such as aldicarb
S
R
NH2
Sulfur oxidation
S
R
Thiophosphate ester oxidation
Thiophosphate pesticides
O
S
S,OP
S,OP
S,O
S
S,O
S,OP
S,O
Dehalogenation
CI
Aromatic and aliphatic

halogens
OH
CH2CI
CH2OH
CCI3
CO2H
Hydrolysis
S,O
S,OP
S,O
O
R
S,O
Figures 2.4a
S,OP
S,O
O
R
R
Phosphate and carboxylic

esters
S,O
R
H2O
OH
R
H 2O
H
R
Common microbial degradation pathways (after Boethling and MacKay, 2000).
Physical/chemical properties affect the rate of biodegradation mostly by affecting

bioavailability. Compounds which are sparingly soluble in water tend to be more
resistant to biodegradation, possibly due to an inability to reach the microbial enzyme
site, a reduced rate of availability due to solubilization, or sequestration due to
adsorption or trapping in inert material.19,40
Biodegradation Rates: The study of the kinetics of biodegradation in natural
environments is often empirical, reflecting the rudimentary level of knowledge about
microbial populations and activity in these environments. An example of an empirical
approach is the power rate model.19
dC/dt = kCn
(2.11)
36
More Biodegradable
(Less Perisistent)
Less Biodegradable
(More Persistent)
Branching
Aliphatic functional groups

R
CH2OH
CO2H
NH2
SO3R
N
R
R
R
N
R
CI
R
N
R
Aromatic functional groups (benzene, naphthalene, pyridine rings)

OH
CI
CH3
OMe
SO3H
NO2
CO2H
NH2
CF3
Br
Aliphatic amines
R
Halophenols
CI
OH
OH
CI
CI
OH
CI
OH
OH
OH
CI
CI
CI
OH
CI
Br
CI
CI
OH
CI
OH
CI
CI
CI
CI
Br
CI
CI
OH
CI
CI
Polycyclic aromatics
3 rings
3 rings
Triazines
R
CI
CH2H3
N
CH3
N
CH3
Figure 2.4b
CH2H3
N
CH3
N
CH3
Relationship between chemical structure and biodegradability (after Boethling

and MacKay, 2000).
where C is substrate concentration, t is time, k is the rate constant for chemical

disappearance, and n is a fitting parameter. This model can be fit to substratedisappearance curves by varying n and k until a good fit is achieved. It is evident
from this equation that the rate is proportional to a power of the substrate concentration. The power-rate law provides a basis for comparison of different curves, but
it gives no insight into the reasons for the shapes. Therefore, often it may have no
predictive ability. Moreover, investigators interested in kinetics do not always state
whether the model they are using has a theoretical basis or is simply empirical, and
whether constants in an equation have physical meaning or are only fitting parameters.19 An appropriate introduction to the kinetics of biodegradation is to consider
37
a pure culture of a single bacterial population growing on and degrading a single,

soluble organic chemical, and to assume that no barriers exist between the substrate
and the cells.
Biodegradation kinetics, under the conditions described previously, have been
reviewed in detail and a number of kinetic models proposed, including the use of
screening tests for generating biodegradation kinetics. 19,42,43 Biodegradation rates
typically are interpreted through the Monod equation (Equation 2.12), which is
analogous to the Michaelis-Menten equation used in enzyme kinetics:
= m
[S]
K s + [S]
(2.12)
The parameters and m refer to the growth rate and maximum growth rate,
respectively, in the presence of substrate concentration S. Ks is the half-velocity
coefficient, i.e., the value of S at which = 0.5m (Figure 2.5). Equation 2.13 can
express the degradation rate of a substrate:
Growth Rate ()
max
0.5 max
Ks
Figure 2.5
Substrate Concentration (s)
Relationship between the growth rate of bacteria vs. the substrate concentration
as described by the Monod kinetics model.
m [S][B]
d[S]
=
dt
Y(K s + [S])
(2.13)
38
where B represents biomass and Y is the growth yield factor. The Monod equation
assumes that the compound of interest sustains growth and is the only source of
carbon and, thus, its applicability to a naturally contaminated environment may be
limited. For example, for cometabolic processes with m and Y defined as zero, the
equation would not apply. The equation also ignores toxicity and makes no provision
for acclimation. Experimentally, rates are measured either at low substrate concentrations where Ks > [S] and Equation 2.13 simplifies to Equation 2.14, or at
high substrate concentrations where [S] > Ks and Equation 2.15 follows from
Equation 2.13:
d[S] m
=
[S][B]
dt
YK s
(2.14)
d[S] m
=
[B]
dt
Y
(2.15)
For the former case (Equation 2.14), which is environmentally more relevant for
low contaminant concentrations typical of many sites, the rate obeys first-order
kinetics with respect to substrate and biomass (second-order overall), whereas in the
latter case (Equation 2.15), the kinetics have a first-order relationship to biomass
but are independent of substrate concentration (Figure 2.6). Methods for measuring
biomass, B, have varied widely, and, for studies involving mixed populations, in
which only a fraction of the organisms can degrade the substrate, a means for
quantifying the responsible fraction is not available.
The kinetics of cometabolism have received scant attention. If the microbial
populations are neither growing nor declining and the concentration of substrate for
cometabolism is below the Km of the active organisms, it is likely that the conversion
would be first-order. In a biofilm bioreactor inoculated with methane-oxidizing
bacteria, the cometabolism of TCE, 1,1,1-trichloroethane, and cis- and trans-1,2dichloroethylene is first-order at concentrations up to 1 mg/liter.19 However, in
environments in which the transformations are slow, the C source for growth probably is being depleted, so the kinetic patterns may change with time. Other models
have been developed for cometabolism by nongrowing or growing populations.19
2.3
2.3.1
ENVIRONMENTAL CHARACTERISTICS
Sorption Coefficient
Sorption processes play a major role in determining the environmental fate and
impact of contaminants, affecting a variety of specific fate processes, including
solubilization, volatilization, bioavailability, biodegradability, and hydrolysis. Sorption coefficients quantitatively describe the extent to which an organic contaminant
is distributed at equilibrium between an environmental solid (i.e., soil, sediment,
Log [Cs]
39
Second Order
Zero Order
First Order
Time
Figure 2.6
Concentration of substrate vs. time for zero-, first-, and second order biodegradation reactions.
suspended sediment, wastewater solids) and the aqueous phase with which it is in
contact. Sorption coefficients depend on (1) the variety of interactions occurring
between the solute and the solid and aqueous phases and (2) the effects of environmental variables such as organic matter quantity and type, clay mineral content and
type, clay to organic matter ratio, particle size distribution and surface area of the
sorbent, pH, ionic strength, suspended particles or colloidal material, temperature,
dissolved organic matter (DOM) concentration, solute and solid concentrations, and
phase separation process.
Adsorption, absorption, and sorption are terms used to describe the uptake of a
solute by another phase. Adsorption describes the concentration of a solute at the
interface of two phases, while absorption describes the process when a solute is
transferred from the bulk state of one phase into the bulk state of the other phase.
The term sorption is used frequently in environmental situations to denote the uptake
of a solute by a solid (soil or sediment or component of soil) without reference to
a specific mechanism, or when the mechanism is uncertain.44
Sorption occurs when the free energy of the interaction between an environmental solid sorbent and contaminant sorbate is negative. The sorption process can be
either enthalpy or entropy driven, depending on the properties of the solid sorbent
and chemical solute. Enthalpy-related forces include van der Waals interactions,
electrostatic interactions, hydrogen bonding, charge transfer, ligand exchange, direct
and induced dipole-dipole interactions, and chemisorption, while hydrophobic bonding or partitioning is considered the primary entropy driven force.2,44 Figure 2.7
shows the polarity of the H2O molecule.
40
Hydrogen
"+"
"-"
Oxygen
Positive
side of
105
H 2O
molecule
Negative
side of
H2O
molecule
"+"
Hydrogen
Figure 2.7
The polarity of the H2O molecule. Because of the non-linear position of H+s,
water is polar. The H2O molecule has one portion that is more negative than
positive and an opposite side that has two hydrogens which are more positive
than negative.
The complex and heterogeneous nature of environmental solids makes it difficult,

if not impossible, to identify specific sorption mechanisms for most solid-chemical
combinations; in most situations, several mechanisms operate simultaneously. In
most soils, and under most conditions, organic chemicals are sorbed on both organic
and inorganic constituents. The relative importance of organic vs. inorganic constituent depends on the amount, distribution, and properties of those constituents and
the properties of the organic chemical. As the polarity, number of functional groups,
and ionic nature of the organic chemical increases, so too does the number of
potential sorption mechanisms (Figure 2.8). Fortunately, for many solid-organic
chemical interactions, one or two mechanisms dominate the sorption process and
generalizations regarding sorption behavior can be made.44
For instance, the sorption of most neutral, hydrophobic organic chemicals by
environmental solids correlates highly with the organic matter content of the solid.
The extent to which clay minerals contribute to sorption depends on both the ratio
of clay mineral to organic carbon fractions of the soil or sediment and on the nature
of the organic sorbate. A ratio of 40 has been suggested as the cutoff for organic
carbon dominated sorption.45 Among the various inorganic soil constituents, smectites have the greatest potential for sorption of organic chemicals, due to their large
surface area and abundance in agricultural soils.44,46
Soil is a dynamic and life-sustaining system composed of solids, liquid, and gas,
with solids typically accounting for about one-half to two-thirds by volume. Living
41
NONPOLAR
Cl
POLAR
Cl
Cl
C
Cl
Chloride ion
Cl
Tetrachloroethylene (PCE)
d+
Water
H
H
H
H+
Hydrogen ion
Benzene
Propane
H
OH
Propanol
H
H
H
Naphthalene
Figure 2.8
Acetate Ion
Some examples of polar and nonpolar chemical species. Note that unbalanced
electrical charge, asymmetry, and the presence of oxygen all tend to make
chemicals more polar.
organisms are also very important parts of soil and contribute greatly to its general
properties and behavior. The solid phase of soil comprises fragmented mineral
matter, derived from the weathering of hard rock at the earths surface, and from
soil organic matter (SOM) consisting of a mixture of plant and animal residues in
various stages of decomposition and substances synthesized microbiologically.1
In its broadest sense, the term SOM encompasses all organic materials contained
in soil and is made up of live organisms, their decomposed and partly decomposed
remains, and microbially and/or chemically resynthesized products resistant to further biological attack. More specifically, the term SOM refers to the nonliving
organic components, which are largely composed of products resulting from microbial and chemical transformations of organic debris. Some scientists have defined
SOM as the total of organic components in soil, excluding undecayed plant and
42
animal tissues, their partial decomposition products (the organic residues), the soil
biomass (living microbial tissues), and macrofauna and macroflora. The terms SOM
and humus are thus generally interchangeable.1
To simplify this very complex system, SOM is generally divided into two groups
designated as nonhumic and humic substances.1 The nonhumic substance group
comprises organic compounds that belong to chemically recognizable classes and
are not unique to the soil. These include polysaccharides and simple carbohydrates,
amino sugars, proteins and amino acids, fats and waxes, lignin, resins, pigments,
nucleic acids, hormones, a variety of organic acids, and so on. Most of these
substances are relatively easily degradable and can be utilized as substrates by soil
microorganisms, and as such have a transient existence in the soil. In contrast, humic
substances comprise a heterogeneous mixture of chemically unidentifiable
macromolecules that are distinctive to and synthesized in the soil, and are relatively
resistant to chemical degradation and microbial attack.
Recent estimates of the average composition of SOM are the following: carbohydrates, 10%; N components, 10%; lipids (including alcanes, fatty acids, waxes,
and resins), 15%; humic substances, 65%. However, different soils may contain
widely different amounts of nonhumic and humic substances. The amount of carbohydrates can range from 5 to 25%; proteins may vary from 15 to 45%; lipids from
2% in forest SOM to 20% in acid peat soils, and humic substances from 33 to 75%
of the total SOM.1
Humic substances are the most widespread and ubiquitous natural nonliving
organic materials in all terrestrial and aquatic environments and represent a significant proportion of total organic C in the global C cycle. They constitute the major
fraction of SOM (up to 80%) and the largest fraction of natural organic matter
(NOM) in aquatic systems (up to 60% of dissolved organic C).1
Soil humic substances comprise a physically and chemically heterogeneous
mixture of naturally occurring, biogenic, relatively high-molecular weight, yellowto-black colored, amorphous, colloidal, polydispersed organic polyelectrolytes.
These polyelectrolytes are of mixed aliphatic and aromatic natures, formed by
secondary synthesis reactions (humification) during the decay process and transformation of organic matter originating from dead organisms and microbial activity.
These materials are distinctive of the soil system and exclusive of undecayed plant
and animal tissues, their partial decomposition products, and the soil biomass.
Soil water acts both as a solvent for the organic chemical and as a solute with
which the organic chemical has to compete for sorption sites on the solid surface.
Typically, soil water is a solution comprising mainly Ca+2, Mg+2, Na+, K+, SO42 ,
CO32 , and HCO3 . Ionic strengths are typically 0.5 mol/L or higher; pH values of
58.5 are common.44 The characteristics of the solution phase determine the reaction
chemistry and the dissolution/precipitation reactions, and they influence ion activity,
ion pairing, and speciation. All these potentially can influence a chemicals sorptive
behavior (Figures 2.9a, b, and 2.10).
In large lakes and estuaries, the natural organic material in sediments and suspended sediments is derived from a mixture of the remains of terrestrial and planktonic organisms. Generally, soils and sediments differ in the amount and type of
organic matter they contain. Soils typically contain higher percentages of cellulose
WATER
43
Air Where
Water has
Drained
WATER
SOIL
PARTICLE
SOIL
PARTICLE
Matric
Potential
Increases
toward
Particle
Surface
WATER
SOIL
PARTICLE
WATER
Air
Where
Water has
Drained
SOIL
PARTICLE
Water is Held
Strongly near
the Soil Particle
Surface
Figures 2.9a
A cross section of a soil pore and the solid particles that make up its walls.
Water is held strongly as the distance from the soil particle decreases; at some
distances from the surface, water is held so weakly that the pull of gravity causes
some of it to drain.
and hemicellulose, while sediments contain higher percentages of lipid-like material.

For neutral organic compounds, sorption is generally greater in sediments than in
soils, even when normalized to organic carbon content.
2.3.1.1 Soil Sorption Coefficients
Sorption coefficients quantitatively describe the extent to which an organic chemical distributes itself between an environmental solid (i.e., soil, sediment, suspended
sediment, wastewater solids, etc.) and the aqueous phase that it is in contact with at
equilibrium. Sorption coefficients generally are determined from an isotherm, a diagram that depicts the distribution of the test chemical between a solid sorbent and the
solution in equilibrium with it over a range of concentrations at constant temperature
(Figure 2.11). These isotherms can be linear or nonlinear, depending on the properties
of the chemical and solid and on the aqueous phase concentration, but tend to become
nonlinear (sorption tends to decrease) as the concentration of chemical in the aqueous
phase increases, especially for polar or ionizable chemicals or soils that are low in
organic carbon and high in clay. Linear sorption isotherms often are observed if the
equilibrium aqueous phase organic compound concentrations are below 105 M or
44
Solids
Cg = H'C w
Trapped gas
bubble
w
Advection - dispersion
Pore
Space
C w = Aqueous phase
concentration
C g = Gas phase
concentration
H = Dimensionless Henry's
Law Constant
Figure 2.9b
Trapped gas in saturated soil.
one-half the aqueous phase solubility (whichever is lower) and the organic content of
the solid is greater than 0.1%:
Kd = CS /CW
(2.16)
where, CS and CW are the concentrations of the organic chemical sorbed by the solid
phase (mg/Kg) and dissolved in aqueous phase (mg/L), respectively. Units of Kd
typically are given as L/kg, mL/g, or cm3/g.
For nonlinear isotherms, the Freundlich model most often is used to describe
the relationship between the sorbed (CS) and the solution phase concentrations (CW):
CS = Kf CWN
(2.17)
where, Kf is the Freundlich sorption coefficient and N (values of N are less than one
and typically range between 0.75 and 0.95) generally is a constant.47 However, in
some cases, N has been observed to exceed one. When N is equal to one, a linear
equation results, and Kf and Kd are equivalent.
The Langmuir and Brumnauer, Emmett, and Teller (BET) models also have been
used to describe nonlinear sorption behavior for environmental solids, particularly
45
Air
Meniscus
Air
C
BA B
Soil
Grain
B
C
0
Porewater Pressure
Meniscus
Height
A only
A and B
A, B, C
0
Water Pressure
Figure 2.10
Soil water under three different values of water content. At high water content
(condition C) porewater pressure is rendered negative by the force of surface
tension acting over a meniscus of relatively large area. The meniscus may be
thought of as a flexible diaphragm that is under tension, thus pulling on the water
on its convex side. As water content is decreased and the meniscus retreats
into smaller pore spaces (B, then A), surface tension forces act over a smaller
area of water, and the resulting water pressure is more negative. The same
effect occurs in capillary tubes, where the most suction (more negative pressure,
and thus more capillary rise) is developed in the tube of smallest diameter.
for mineral dominated sorption.44 The Langmuir model assumes that maximum
adsorption corresponds to a saturated monolayer of solute molecule on the adsorbent
surface, that there is no migration of the solute on the surface, and that the energy
of adsorption is constant. The BET model is an extension of the Langmuir model
that postulates multiplayer sorption. It assumes that the first layer is attracted most
strongly to the surface, while the second and subsequent layers are more weakly
held.47
The most commonly used method for expressing the distribution of an organic
compound between the aquifer matrix and the aqueous phase is the distribution
coefficient, Kd, which is described by Equation 2.16.
The transport and partitioning of a contaminant are strongly dependent on the
chemicals soil-water distribution coefficient and water solubility. The distribution
coefficient is a measure of the sorption/desorption potential and characterizes the
tendency of an organic compound to be sorbed to the aquifer matrix. The higher the
distribution coefficient, the greater the potential for sorption to the aquifer matrix.
The distribution coefficient is the slope of the sorption isotherm at the contaminant
concentration of interest. The greater the amount of sorption, the greater the value
of Kd. For systems described by a linear isotherm, Kd is a constant.47 In general
46
Linear
Adsorbed Concentration Cs(g/g)
Freundlich
Langmuir
Dissolved Concentration Cw(g/mL)

Figure 2.11
Characteristic adsorption isotherm shapes.
terms the distribution coefficient is controlled by the hydrophobicity of the contaminant and the total surface areas of the aquifer matrix available for sorption. Thus
the distribution coefficient for a single compound will vary with the composition of
the aquifer matrix. Because of their extremely high specific surface areas (ratio of
surface area to volume), the organic carbon and clay mineral fractions of the aquifer
matrix generally represent the majority of sorption sites in an aquifer.
Based on literature reports, it appears that the primary adsorptive surface for
organic chemicals is the organic fraction of the aquifer matrix.47 However, there is
a critical level of organic matter below which sorption onto mineral surfaces is the
dominant sorption mechanism.47,48 This critical level of organic matter, below which
sorption appears to be dominated by mineral-solute interactions, and above which
sorption is dominated by organic carbon-solute interactions, is given by47,48
focc =
As 1
0.84
200 K ow
where
focc = critical level of organic matter (mass fraction)
As = surface area of mineralogical component of aquifer matrix
Kow = octanol-water partitioning coefficient
(2.18)
47
From this relationship it is apparent that the total organic carbon content of the
aquifer matrix is less important for solutes with low octanol-water partitioning
coefficients (Kow).47 Also apparent is the fact that the critical level of organic matter
increases as the surface area of the mineralogic fraction of the aquifer matrix
increases. The surface area of the mineralogic component of the aquifer matrix is
most strongly influenced by the amount of clay. For compounds with low Kow values
present in materials with a high clay content, sorption to mineral surfaces could be
an important factor causing retardation of the chemical.
Several researchers have found that if the distribution coefficient is normalized
relative to the aquifer matrix total organic carbon (TOC) content, much of the
variation in observed Kd values between different soils is eliminated.49 Distribution
coefficients normalized to total organic carbon content are expressed as Koc. The
following equation gives the expression relating Kd to Koc:
K oc =
Kd
foc
(2.19)
where
Koc
Kd
foc
= soil sorption coefficient normalized for total organic carbon content

= distribution coefficient
= fraction of total organic carbon (mg organic carbon/mg soil)
In areas with high clay concentrations and low TOC concentrations, the clay
minerals become the dominant sorption sites. Under these conditions, the use of Koc
to compute Kd might result in underestimating the importance of sorption in retardation calculations, a source of error that will make retardation calculations based
on the total organic carbon content of the aquifer matrix more conservative. In fact,
aquifers that have a high enough hydraulic conductivity to spread organic chemical
contamination generally have a low clay content. In these cases the contribution of
sorption to mineral surfaces is generally trivial.
Sorption coefficients also have been expressed on an organic matter basis (Kom)
by assuming that the organic matter content of a soil or sediment equals some factor,
usually between 1.7 to 1.9, times its organic carbon content on a mass basis.47,50
Often 1.724 is used as this factor, implying that the carbon content of organic matter
is 1/1.724 or 60%. However, Koc is considered a more definite and less ambiguous
measure than Kom.47
Assumptions inherent in the use of a Koc (or Kom) are that: sorption is exclusively
to the organic component of the soil, all soil organic carbon has the same sorption
capacity per unit mass, equilibrium is observed in the sorptiondesorption process,
and the sorption and desorption isotherms are identical.45 Both Koc and Kd have units
of L/kg or cm3/g.
Numerous studies have been performed using the results of batch and column
tests to determine if relationships exist that are capable of predicting the sorption
characteristics of a chemical based on easily measured parameters. The results of
48
these studies indicate that the amount of sorption is strongly dependent on the amount
of organic carbon present in the aquifer matrix and the degree of hydrophobicity
exhibited by the contaminant.47 These researchers observed that the distribution
coefficient, Kd, was proportional to the organic carbon fraction of the aquifer times
a proportionality constant. This proportionality constant, Koc, is defined as given by
Equation 2.19. Because it is normalized to organic carbon, values of Koc are dependent only on the properties of the compound (not on the type of soil). Values of Koc
have been determined for a wide range of chemicals.
By knowing the value of Koc for a contaminant and the fraction of organic
carbon present in the aquifer, the distribution coefficient can be estimated using
the relationship
Kd = Koc foc
(2.20)
The fraction of soil organic carbon must be determined from site-specific data.
Representative values of the fraction of organic carbon (foc ) in common sediments is
available in the literature. When predicting sorption of organic compounds, total organic
carbon concentrations obtained from the most transmissive aquifer zone unaffected by
contamination should be averaged and used for predictions. This is because the majority
of dissolved contaminant transport occurs in the most transmissive portions of the
aquifer. In addition, because the most transmissive aquifer zones generally have the
lowest total organic carbon concentrations, the use of this value will give a conservative
prediction of contaminant sorption and retardation. Determination of the coefficient of
retardation using sorption coefficients is described in Chapter 3.
2.3.1.2 Factors Affecting Sorption Coefficients
Many factors potentially can affect the distribution of a contaminant between an
aqueous and solid phase. These include environmental variables, such as temperature,
ionic strength, dissolved organic matter concentration, and the presence of colloidal
material, surfactants, and cosolvents. In addition, factors related specifically to the
experimental determination of sorption coefficients, such as sorbent and solid concentrations, equilibration time, and phase separation technique, can also be important. A
brief discussion of several of the more important factors affecting sorption coefficients
follows.
Temperature: The effect of temperature on sorption equilibrium is a direct
indication of the strength of the sorption process. The weaker the interaction between
sorbent and sorbate, the less the effect of temperature.47,50 While temperature can
influence sorption, the strength and direction of the effect depends on the properties
of the sorbent and sorbate and on the sorption mechanism. Adsorption processes are
generally exothermic, so the higher the temperature, the less the adsorption. Hydrophobic sorption, however, has been shown to be relatively independent of temperature. Other reviews also indicate that the influence of temperature on equilibrium
sorption and have found that, in most cases, equilibrium sorption decreases with
increasing temperature.47
49
pH: For neutral chemicals, sorption coefficients usually are unaffected by pH.
However, for ionizable organic chemicals, sorption coefficients can be affected
greatly, since pH affects not only the speciation but also the surface characteristics
of natural sorbents. Typically, for weak acids the free acid form (HA) is more strongly
sorbed than the anionic form (A). For example, pentacholorophenol (PCP) sorption
decreased with increasing pH over the entire pH range tested (2 to 12). For weak
bases the cationic form dominates at low pH and is more highly sorbed than the
free base.44
Ionic Strength: Salts can affect sorption of organic compounds by displacing
cations from the soil ion exchange matrix, by changing the activity of the sorbate
in solution, and by changing the charge density associated with the soil sorption
surface. Salt effects are most important for basic sorbates in the cation state, where
an increase in salinity can significantly lower the sorption coefficient. Salt effects
are least important for neutral compounds, which may show either increases or
decreases in sorption as salinity increases.44
Dissolved or Colloidal Organic Matter: The presence of dissolved or colloidal
organic matter has been shown to influence sorption depending on the nature of the
chemical and the organic matter. Some compounds were found to be associated
extensively with the dissolved organic matter; sorption by soil decreased significantly
in the presence of dissolved organic matter. Some have characterized several size
fractions of water soluble organic carbon and found that the effect of dissolved
organic matter on the sorption of pyrene may be limited, but the presence of colloidal
organic matter suspended in the soil solution may have significant impact on the
sorption of pyrene.44,51
Cosolvents: The effect of nonpolar cosolutes (trichloroethylene, toluene), polar
cosolutes (1-octanol, chlorobenzene, nitrobenzene, o-cresol) and polar cosolvents
(methanol and dimethyl sulfoxide) on sorption of several polycyclic aromatic hydrocarbons (PAHs) has been investigated.44,52 The nonpolar cosolutes did not significantly influence PAH sorption, while the polar cosolutes (nitrobenzene, o-cresol),
having sufficiently high aqueous solubilities, caused a significant decrease in PAH
sorption.
Miscible organic solvents, such as methanol and ethanol, have been shown to
increase solubility of hydrophobic organics and to decrease sorption. This is presumably the result of reducing the activity coefficient of the sorbate chemical in the
aqueous phase, and competition for sorbing sites.
Competitive Sorption: At concentrations normally encountered in environmental situations, sorption often has been observed to be relatively noncompetitive. For
example, it was found that there is no competition in the sorption of binary solutes
m-dichlorobenzene and 1,2,4-trichlorobenzene and between parthion and lindane.53
The sorption of methyl and dimethyl naphthalene, individually and as components
of JP-8 and synthetic jet fuel mixture, on two sediments and montomorillonite clay
in water was measured.54 The sorption coefficients of the naphthalenes generally
varied by less than a factor of two. However, there are reports of competitive sorption
taking place that is thought to be the result of site-specific sorption occurring in soil
organic matter.
50
Organic Matter Type and Origin: While the constancy of Koc values suggests
a uniformity of organic matter with regard to sorption behavior, it is becoming
increasingly apparent that organic matter type can be an important sorption variable
for some sorbent/sorbate combinations. For example, it was found that the sorption
of naproamide, a nonionic herbicide, was greater in the sediment than in soils, even
on an organic carbon basis.44 The increased sorption in sediment was attributed to
the fact that soils contained a higher percentage of cellulose and hemicellulose
material, whereas the sediments contain a higher lipid-like fraction.
Kinetic Considerations: Sorption generally is regarded as a rapid process and, in
many laboratory sorption experiments, equilibrium often is observed within several
minutes or hours. An equilibration time of 24 hours often is used for convenience.
True sorption equilibrium under natural conditions, however, may require weeks to
months to achieve depending on the chemical and environmental solid of interest. In
many instances, an early period of rapid and extensive sorption, followed by a long
slow period, is observed. Experimental determination of sorption coefficients requires
preliminary kinetic experiments to determine the time to reach equilibrium.
Two processes govern rate-limited or nonequilibrium sorption: transport of
the substance to the sorption sites and the sorption process itself.44,50 Transportrelated nonequilibrium typically results from the existence of a heterogeneous
flow domain. Sorption-related nonequilibrium, caused by rate-limited interactions
between the sorbate and sorbent, may be the result of chemical nonequilibrium
(i.e., chemisorption) or diffusive mass transfer limitations (i.e., diffusion of solute
within pores of microporous particles or molecular diffusion into macromolecular
organic matter). Sorption kinetics are likely to be environmentally important in
short contact situations such as sediment resuspension, soil erosion, and infiltrating ground water.44
In general, adsorption processes tend to be rapid and nearly instantaneous,
whereas nonsurface sorption tends to be slower. For neutral organic chemicals, the
more hydrophobic the compound, the larger the sorption coefficient, and the longer
it takes to reach equilibrium between the solid and aqueous phases. This is because
the sorbent must remove a chemical from a larger volume of water.
Generally, sorption estimates are based on equilibrium conditions only; however,
incorporation of kinetic considerations into sorption estimation techniques is likely
to be an important area of future work. For example, the assumption of equilibrium
sorption in dynamic field systems may result in calculating too much pesticide in
the sorbed state.
Ionizability: For neutral organic compounds, in soils having a low clay/organic
carbon ratio, sorption coefficients tend to increase as the hydrophobicity of the
compound increases. Aqueous solubility or octanol/water partition coefficients often
are used as indicators of a compounds hydrophobicity. An increase on polarity,
number of functional groups, and ionic nature of the chemical will increase the
number of potential sorption mechanisms for a given chemical. For ionizable compounds, pKa is of particular importance because it determines the dominant form of
a chemical at the specific environmental pH.
51
The entropy change is largely due to the destruction of the highly structured
water shell surrounding the solvated organic. The term partitioning was used to
denote an uptake in which the sorbed organic chemical permeates the network of
an organic medium by forces common to the solution, analogous to the extraction
of an organic compound from water with an organic liquid. By either description,
hydrophobic sorption or partitioning should increase as compounds become less
water soluble or more hydrophobic.
Additional characteristics typically associated with hydrophobic sorption or partitioning include sorption isotherms that are linear over a relatively wide range of
concentrations, and sorption coefficients that are not strongly temperature dependent,
and lack a competition between sorbates.44,53
2.3.2
Oxidation-Reduction Capacities of Aquifer Solids
There has been considerable research activity focused on the characterization of

REDOX-potential or intensity (Eh) conditions in groundwater systems defined as
the REDOX activity of dissolved chemical species. Early observations of significant
Eh trends along groundwater flow paths led to hypotheses of successive REDOX
zones characterized by the activity of specific thermodynamically favored electron
acceptors. These REDOX zones may be classified as oxic (i.e., detectable dissolved
O2), suboxic or postoxic (i.e., no detectable O2 or sulfide, detectable Fe2+), and
reducing (i.e., detectable Fe2+ and sulfide, no detectable O2).1 Further investigations
correctly postulated that oxidation-reduction processes were mediated by natural
microbial populations that catalyze electron-transfer reactions. More recent work
noted considerable temporal and spatial variability in measured subsurface REDOX
conditions and that the succession of electron acceptors under oxic, suboxic, or
reducing conditions was not strictly predictable by either chemical equilibrium
calculations or platinum electrode measurements.
2.3.2.1 pe and pH
A pH is the negative log (p for power) of proton (H+) activity and pe, its energy
or work analog, is the negative log of the electron potential. An electron is not a
full-fledged analog of a proton. Together, two equal but opposite charges make up
a hydrogen atom, but that is about the extent of the equality between an electron
and a proton. Without its proton, an electron is no longer an analog of H+, and it no
longer has any claim to being part of a hydrogen atom. An electron does not bounce
about by itself in the manner of an H+, and therefore it is probably not correct to
try to characterize its activity. It always is either attached to an atom or radical or
in the process of being transferred from one to another.
A proton is a cation. It can replace or be replaced by other cations and it is as
good as any other cation when it comes to balancing a chemical equation. Electrons
receive no recognition in balanced chemical equations because the donated and
accepted electrons must always cancel one another on opposite sides of an equation.
52
Electrons do not have anion status. They cannot trade places with other negatively
charged species.
Usually we see release of H+ when metals are oxidized and consumption of H+
with their reduction. Oxidation is furthered in a subsurface environment where
protons and electrons are deficient; that is, where acidity and levels of easily degraded
(labile) electron donors are low. But there must be a ready supply of available
electron acceptors. Reduction is favored by surpluses of both protons and electrons.
This means that low pH and high availability of organic substances will promote
reduction in soil. Reduction of Fe or Mn oxides, or of nitrate, uses up H+, thereby
increasing pH of the soil and, theoretically, lowering the pe. Oxidation of Fe, Mn,
or nitrate lowers the pH (measurable) and raises the pe (not measurable in most
soils). Measuring changes in concentrations of REDOX species is more reliable for
predicting these things in the subsurface than is an attempted measurement of pe
with the platinum electrode.
The farther apart the electrons, the more proportional work required to bring
them together and the higher the respective pe. A low pe system has a surplus of
electrons and, therefore, a big tendency to lose some of them and become oxidized.
A high pe system is hungry for electrons. As deficient electrons are replenished, the
tendency for reduction to occur will increase. If we substitute pe and pH for their
defined equivalents in a generic REDOX half-reaction in which activities of oxidized
and reduced species are equal, we see that the (pe + pH) sum is equivalent to the
equilibrium constant of the half-reaction:
Oxidized species + e + H+ = reduced species
(2.21)
log K = log red log ox log e log H+
(2.22)
log K = pe = pH
(2.23)
If indeed their sum is constant, then, thermodynamically, pe and pH are on

opposite ends of a seesaw. If behavior follows thermodynamic theory, when one
goes up, the other will come down, like any sound seesaw. This sum is referred to
as the REDOX parameter because, if a soil is at internal equilibrium, the (pe + pH)
represents the sums of all of the REDOX equilibrium constants in the soil.1
2.3.2.2 REDOX Poise
In the natural environment REDOX seesaws are not so simple. This seesaw-like
behavior reflects the interaction between source/sink quantities and electron/proton
intensities. If we add reducing reagents or reduced substances such as Fe(II), or
Mn(II) or Cr(III) to a soil poised so that its easily reduced substances are in balance
with its easily oxidized substances, some of the added reduced species will be quickly
oxidized. On the other hand, adding Fe(III), Mn(IV) or Cr(VI) will result in immediate reduction of a portion of the added oxidants. There appears to be a tendency
for a soil, if disturbed, to maintain a REDOX balance, that is, poise, by donating
53
electrons to surplus electron acceptors or by accepting electrons from surplus electron donors.1
A soil kept near field capacity moisture with occasional mixing, double bagged
inside a thin polyethylene bag for several months at 15 to 25C, will be close to
internal equilibrium. If this metastable equilibrium is disturbed by adding an easily
oxidized substance to it, e.g., glucose, the (pe +pH) of the overall system will tend
to remain fairly constant as the disturbed soil system moves back toward a new
metastable equilibrium. In this instance, the pe will tend to go down, and to the
extent that it does, the pH will tend to rise.1
By adding increments of Cr3+ and HCrO4 , respectively, to separate subsamples
of the same soil and then determining the amount of Cr reduced [loss of Cr(VI)]
and the amount oxidized [gain of Cr(VI)], it is possible to find a point of poise or
buffered REDOX region, where the electron donating and electron accepting tendencies cross. There the REDOX seesaw is balanced at dead-level.1
2.3.2.3 REDOX Reactions
REDOX is one of those catchy phrases invented by someone unhampered by
commitment to the use of scientifically correct terminology. The name is reversed
(RED-OX, instead of OX-RED) for the sake of easy pronunciation. The RED stands
for reduction and it signifies gain of electrons by a chemical species called electron
acceptors; the OX connotes oxidation, or electron loss by a chemical species called
electron donors. Oxidation-reduction (REDOX) reactions, along with hydrolysis and
acid-base reactions, account for the vast majority of chemical reactions that occur
in aquatic environmental systems (soils, sediments, aquifers, rivers, lakes, and many
remediation operations). This section provides a survey of the environmental and
substrate characteristics that govern REDOX transformations in aquatic systems.
The distinction between biotic and abiotic processes is a particularly important
issue in defining the scope of this section. Living organisms are responsible for
creating the conditions that determine the REDOX chemistry of most aquatic environmental systems. So, in this sense, most REDOX reactions in natural systems
ultimately are driven by biological activity. Once environmental conditions are
established, however, many important REDOX reactions proceed without further
mediation by organisms. These reactions are considered to be abiotic when it is no
longer practical (or possible) to link them to any particular biological activity.
Assigning Oxidation States: REDOX reactions involve oxidation and reduction; they occur by the exchange of electrons between reacting chemical species.2,55 Electrons (or electron density) are lost (or donated) in oxidation and
gained (or accepted) in reduction. An oxidizing agent (or oxidant) that accepts
electrons (and is thereby reduced) causes oxidation of a species. Similarly, reduction results from reaction with a reducing agent (or reductant) that donates
electrons (and is oxidized).
To interpret REDOX reactions in terms of electron exchange, one must account
for electrons in the various reacting species. Various textbooks provide simple rules,
such as the following, for assigning oxidation states for inorganic REDOX couples:2,55
54
For free elements, each atom is assigned oxidation number 0.

Monoatomic ions have an oxidation number equal to the charge of the ion.
Oxygen, in most compounds, has the oxidation number 2.
Hydrogen, in most compounds, has the oxidation number +1.
Halogens, in most environmentally relevant compounds, have the oxidation
number 1.
These rules, however, are not easily applied to organic REDOX reactions, and
this difficulty has led to a steady stream of alternative concepts for assigning oxidation states. For present purposes, familiarity with a method for assigning oxidation
states to organic molecules is sufficient. This method reflects the qualitative observations from which the historical concepts of oxidation and reduction originated:
oxidation is the gain of oxygen (O), chlorine (Cl) or double bonds, and/or the loss
of H; reduction is the gain of H, saturation of double bonds, and/or loss of O or Cl.
Thus, for example, mineralization of any hydrocarbon to CO2 and H2O involves
oxidation, and dechlorination of any chlorinated compound to hydrocarbon products
involves reduction.
Oxidations: Organic chemicals that are susceptible to oxidation and are of
concern from the perspective of contamination and environmental degradation
include aliphatic and aromatic hydrocarbons, alcohols, aldehydes, and ketones, phenols, polyphenols, sulfides (thiols), sulfoxides, nitriles, amines, diamines, nitrogen
and sulfur hetercyclic compounds, mono- and di-chlorinated aliphatics and many
others. Equations below show example half-reactions for oxidation of some of these
chemical groups.
Alkanes to alcohols
R H + H2O R OH + 2H+ + 2e (loss of H+ and e)
(2.24)
Alcohols to aldehydes
R CH2 OH RCHO + 2H+ + 2e (loss of H+ and e)
(2.25)
Aldehydes to acids
RCHO + H2O RCOOH + 2H+ + 2e (loss of H+ and e)
(2.26)
Reductions: Most interest in reductive transformations of environmental chemicals involves dechlorination of chlorinated aliphatic and aromatic compounds and
the reduction of nitroaromatic compounds. Other examples of reductive transformations that may occur abiotically in the environment include reduction of azo compounds, quinines, disulfides, and sulfoxides. An example of a half-reaction is
described by the equation:
55
Reductive dechlorination
R Cl + H+ + 2e R H + Cl (gain of H+, e and loss of Cl) (2.27)

Dechlorination can occur by several reductive pathways. The simplest results in
replacement of a C-bonded halogen atom with a hydrogen and is known as hydrogenolysis or reductive dechlorination. The process is illustrated for trichloroethene,
TCE, in Figure 2.12, where complete dechlorination by this pathway requires multiple
hydrogenolysis steps. The relative rate of each step is a critical concern because the
steps tend to become slower with each dechlorination (and DCE and VC are at least
as hazardous as TCE if not more so than with VC). Aryl halogens, such as those in
the pesticide chlophyrifos, also are subject to hydrogenolysis, but this reaction rarely
occurs abiotically. One notable exception is the rapid abiotic dechlorination of polychlorinated biphenyls (PCBs) by zero-valent iron with catalysis by Pd.2,55
H
CI
C
+H+ +2e-CI-
CI
CI
C
CI
TCE
Figure 2.12
H
+H+ +2e-CI-
C
CI
CI
C
cis-1,2-DCE
+H+ +2e-CI-
H
C
VC
H
Ethene
Reductive dechlorination or hydrogenolysis of TCE.
The other major dechlorination pathway involves elimination of two chlorines,

leaving behind a pair of electrons that usually goes to form a carbon-carbon double
bond. Where the pathway involves halogens on adjacent carbons, it is known as
vicinal dehalogenation or reductive -elimination. The major pathway for reductive
transformation of lindane involves vicinal dehalogenation, which can proceed by
steps all the way to benzene (Figure 2.13).2,55 Recently, data have shown that this
pathway not only can convert alkanes to alkenes, but also can produce alkynes from
dihaloalkenes (see Equation 2.28).
CI
CI
CI
CI
CI
CI
CI
+2e-2CI-
CI
CI
CI
CI
+2e-2CI-
CI
Lindane
Figure 2.13
+2e-2CI-
Vicinal dechlorination or reductive-elimination of lindane.
Benzene
56
Vicinal Dehalogenation
Cl R R1 Cl + 2e R = R1 + 2Cl (formation of double bond)
(2.28)
The contaminant REDOX reactions just summarized only occur when coupled
with suitable half-reactions involving oxidants or reductants from the environment.
In a particular environmental system, these REDOX agents collectively determine
the nature, rate, and extent of contaminant transformation. Under favorable circumstances, the dominant REDOX agent(s) can be identified and quantified, thereby
providing a rigorous basis for estimating the potential for, and rate of, transformation
by abiotic REDOX reactions.2,55
Such specificity is often possible with systems engineered for contaminant remediation. However, natural systems frequently involve complex mixtures of REDOXactive substances that cannot be characterized readily. The characterization of
REDOX conditions in complex environmental media is a long-standing challenge
to environmental scientists that continues to be an active area of research.
The remainder of this section summarizes what is currently known about the
identity of oxidants and reductants relevant to environmental systems, in order to
provide a basis for estimating rates of contaminant transformations by specific
pathways. With respect to natural reductants, however, a great deal remains to be
learned, so substantial developments can be expected as new research in this area
becomes available.
Oxidants: The best opportunities for predicting REDOX transformations come
from engineered systems where a known oxidant is added to achieve contaminant
remediation. Well-documented examples include the use of ozone and chlorine in
drinking water treatment. In natural systems, important oxidants are oxides of iron
and manganese, as well as molecular oxygen and various photooxidants. In engineered remediation systems oxidants used include potassium permanganate, ozone
and hydrogen peroxide.1
The presence of molecular oxygen, O2 is used widely as the defining characteristic of oxidizing environments because the overwhelming supply of molecular
oxygen makes it the ultimate source of oxidizing equivalents. However, O2 in its
thermodynamic ground-state (3O2) is a rather poor oxidizing agent and it is not
usually the oxidant directly responsible for oxidative transformations of contaminants. Instead, activated oxygen species may be involved where they are formed by
the action of light on natural organic matter (NOM), peroxides, or various inorganic
catalysts. Activated oxygen species include singlet oxygen (1O2), protonated superoxide (HO2 ) hydrogen peroxide and hydroperoxide anion (H2O2/HO2 ), hydroxyl
radical (OH), and ozone (O3).1,2,55
O2 + e + H+ = H2O (protonated superoxide)
(2.29)
O2 + 2e + 2H+ = H2O2 (hydrogen peroxide)
(2.30)
O2 + 3e + 3H+ = H2O + HO (hydroxyl free radical)
(2.31)
O2 + 4e + 4H+ = 2H2O (water)
57
(2.32)
Equations 2.292.32 are half-reactions showing reduction of O2 by single electron additions. Thus, superoxide and hydroxyl, produced by one and three odd
electron additions, are free radicals; whereas peroxide and water, with two and four
electrons added, respectively, are not. Restricting conditions of interaction between
the availabilities of soil O2 and electron donors, for example, at the interface between
oxygenated water and anaerobic soil in a wetland, tends to favor transfers of electrons
in single steps, and thus such interfaces are likely to be sites for free radical
formation. Free radical mechanisms appear to explain why kinetically slow and
seemingly unlikely REDOX transformations often occur readily at interfaces. Oxygen free radicals are much more reactive than O2 itself, and both superoxide and
the hydroxyl free radical are especially reactive with H2O2, each one capable of
being quickly transformed into the other.
Aside from oxygen and the activated oxygen species, there are several other
oxidants that cause abiotic oxidation reactions involving environmental contaminants. In engineered systems, these include chlorine, chlorine dioxide, permanganate
and ferrate. At highly contaminated sites, anthropogenic oxidants such as chromate,
arsenate, and selenate may react with co-contaminants such as phenols.
In natural anoxic environments, the major alternative oxidants are Fe(III) and
manganese (IV) oxides and hydroxides. Both are common in natural systems as
crystalline or amorphous particles or coatings on other particles. In the absence of
photocatalysis, however, iron and manganese oxides are weak oxidants. As a result,
they appear to react at significant rates only with phenols and anilines.
In the dissolved phase, few alternative abiotic oxidants are available in the neutral
environment. Nitrate, sulfate, and other terminal electron acceptors used by anaerobic
microorganisms are thermodynamically capable of oxidizing some organic contaminants, but it appears that these reactions almost always require microbial mediation.
Reductants: Abiotic environmental reductants are not well characterized as the
oxidants because, until recently, there were fewer remediation applications of reductants, and natural reducing environments are characterized by especially complex
biogeochemistry. The most familiar natural reductants are sulfide (present primarily
as HS and H2S), Fe (II) and Mn (II), and natural organic matter (NOM). The
transformation of contaminants by sulfur species in anaerobic environments can
involve both reduction and nucleophilic substitution pathways. These processes have
been studied extensively, but the complex speciation of sulfur makes routine predictions regarding these reactions difficult.1,2,55
A similar situation applies for reduced forms of iron. As with oxidations, some
of the best opportunities for reliably estimating rates of redox transformations are
afforded by engineered systems where a reductant of known composition and quantity is added to achieve contaminant remediation. In addition to zero-valent iron,
other methods for chemical reduction of contaminants involve dithionite and electrolysis (where, in effect, electrons are added directly).1,2,55
The role of natural organic reductants in environmental systems is even more
difficult to characterize than the roles of sulfur and iron because most natural organic
matter is of indeterminate composition. There are two general categories of NOM:
58
high molecular weight organic materials such as humic and fulvic acid, and low
molecular weight compounds such as acids, alcohols, etc. Specific examples of the
latter include glycolate, citrate, pyruvate, oxalate, and ascorbate. These types of
compounds have been studied extensively for their role in global cycling of carbon,
but very little work has been done on whether they act as specific reductants of
organic contaminants.1,2,55
In contrast, the possibility that high molecular weight NOM acts as a reductant
in environmental systems is widely acknowledged. Although most evidence for this
involves the reduction of metal ions, several studies have shown that the process
extends to various organic contaminants. Presumably, the reducing potential of NOM
is due to specific moieties such as complex metals or conjugated polyphenols. Often,
REDOX reactions involving these moieties are reversible, which means that NOM
may serve as a mediator of REDOX reactions rather than being just an electron
donor (or acceptor).1,2,55
In the recent past, the addition of labile electron donors such as molasses, lactate,
and methanol is gaining ground to facilitate enhanced reductive dechlorination of
chlorinated aliphatic and aromatic compounds. This technology is discussed in detail
in Chapter 4.
Demonstrating that a REDOX transformation of a contaminant involves mediated
electron transfer requires meeting several criteria: 1) the overall reaction must be
energetically favorable, 2) the mediator must have a reduction potential that lies
between the bulk donor and the terminal acceptor so that both steps in the electron
transfer chain will be energetically favorable, and 3) both steps in the mediated
reaction must be kinetically fast relative to the direct reaction between bulk donor
and terminal acceptor. Most evidence for involvement of mediators in reduction of
contaminants comes from studies with model systems, because natural reducing
media (such as anaerobic sediments) consist of more REDOX couples than can be
characterized readily. Although this is an active area of research, a variety of likely
mediator half-reactions can be identified.
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L1282_C03-A_frame Page 63 Monday, June 18, 2001 10:05 AM
CHAPTER
Monitored Natural Attenuation

CONTENTS
3.1
Introduction ....................................................................................................64
3.1.1 Definitions of Natural Attenuation ....................................................64
3.2 Approaches for Evaluating Natural Attenuation ...........................................65
3.3 Patterns vs. Protocols .....................................................................................70
3.3.1 Protocols for Natural Attenuation......................................................70
3.3.2 Patterns of Natural Attenuation .........................................................71
3.3.2.1 Various Patterns of Natural Attenuation.............................72
3.4 Processes Affecting Natural Attenuation of Compounds..............................79
3.4.1 Movement of Contaminants in the Subsurface .................................79
3.4.1.1 Dilution (Recharge) ............................................................79
3.4.1.2 Advection ............................................................................81
3.4.1.3 Dispersion ...........................................................................83
3.4.2 Phase Transfers ..................................................................................85
3.4.2.1 Sorption...............................................................................85
3.4.2.2 Stabilization ........................................................................88
3.4.2.3 Volatilization .......................................................................89
3.4.3 Transformation Mechanisms..............................................................89
3.4.3.1 Biodegradation ....................................................................90
3.5 Monitoring and Sampling of Natural Attenuation ......................................109
3.5.1 Dissolved Oxygen (DO) ..................................................................113
3.5.2 OxidationReduction (REDOX) Potential (ORP)...........................117
3.5.3 pH .....................................................................................................119
3.5.4 Filtered vs. Unfiltered Samples for Metals .....................................120
3.5.4.1 Field Filtration and the Nature of
Groundwater Particulates..................................................121
3.5.4.2 Reasons for Field Filtration..............................................122
3.5.5 Low-Flow Sampling as a Paradigm for Filtration ..........................124
3.5.6 A Comparison Study........................................................................125
References..............................................................................................................126
63
64
natural attenuation (NA) is not a no action (NA) alternative. Monitored

natural Attenuation (MNA) defines the required monitoring parameters to demonstrate that the ongoing natural processes will continue to meet the remediation
objectives
3.1
INTRODUCTION
The term monitored natural attenuation (MNA) refers to an approach to clean up

subsurface contamination, specifically in groundwater, by relying on natural processes
and monitoring. MNA is also referred to as natural degradation and intrinsic or passive
remediation. Natural attenuation processes include a variety of physical, chemical, or
biological processes that, under favorable conditions, act without human intervention
to reduce the mass, toxicity, mobility, volume, and concentration of contaminants in
groundwater. Depending on the geologic conditions, types of contaminants, and contaminant mass and distribution at a given contaminated site, MNA could emerge as
the preferred choice of remediation approach. Natural attenuation relies on the assimilative capacity of the ecosystem for the reduction of contaminant concentration and
mass. This approach has been utilized by environmental engineers for a long time to
control industrial and municipal wastewater discharges into surface waterbodies and
maintain acceptable water quality standards.
3.1.1
Definitions of Natural Attenuation
A variety of organizations have espoused the following definitions of natural

attenuation due to the emerging popularity and preference of MNA as the remediation method of choice at many contaminated sites across the country.1
Environmental Protection Agency2: This policy directive defines monitored
natural attenuation as the reliance on natural attenuation process (within the
context of a carefully controlled and monitored site cleanup approach) to achieve
site-specific remediation objectives within a time frame that is reasonable compared to that offered by other more active methods. The natural attenuation
processes that are at work in such a remediation approach include a variety of
physical, chemical, or biological processes that, under favorable conditions, act
without human intervention to reduce the mass, toxicity, mobility, volume, or
concentration of contaminants in soil or groundwater. These in situ processes
include biodegradation; dispersion; dilution; sorption; volatilization; radioactive
decay; and chemical or biological stabilization, transformation, or destruction of
contaminants.
American Society for Testing and Materials (ASTM)3: Its document titled
Standard Guide for Remediation of Groundwater by Natural Attenuation at
Petroleum Release Sites defines natural attenuation as the reduction in mass or
concentration of a compound in groundwater over time or distance from the
source of constituents of concern due to naturally occurring physical, chemical,
and biological processes, such as biodegradation, dispersion, dilution, adsorption,
and volatilization.
MONITORED NATURAL ATTENUATION
65
Air Force4: The first document, published in 1995, defines the process as resulting
from the integration of several subsurface attenuation mechanisms that are
classified as either destructive or nondestructive. Biodegradation is the most
important destructive attenuation mechanism. Nondestructive attenuation mechanisms include sorption, dispersion, dilution from recharge, and volatilization.
Army5: Its report defines natural attenuation as the process by which contamination in groundwater, soils, and surface water is reduced over time[via]
natural processes such as advection, dispersion, diffusion, volatilization, abiotic
and biotic transformation, sorption/desorption, ion exchange, complexation, and
plant and animal uptake.
In the past, the first question to be asked in consideration of the potential for
natural attenuation at a contaminated site was whether biodegradation of the chemical contaminant had been reported. Oftentimes the question was, Does the biogeochemistry exist for ongoing degradation? due to the assumption that the responsible microorganisms are ubiquitous in the subsurface. However, in this chapter the
term natural attenuation will include all the processes that contribute towards the
decrease in contaminant concentrations.
3.2
APPROACHES FOR EVALUATING NATURAL ATTENUATION
Documenting that contaminant concentration has become very low or detectable

in groundwater samples is an important piece of evidence that natural attenuation
is working. However, such documentation is not completely sufficient to show that
natural attenuation is protecting human health and the environment, for three primary
reasons:
Monitoring of contaminant concentration reductions is not always precise due to
the complex nature of groundwater systems. In some cases the total contaminant
mass may have decreased, but the contaminant may have transformed to another,
more hazardous chemical form.
In a few instances reactions that initially cause contaminants to attenuate may not
be sustainable until reasonable cleanup goals are achieved.
Another situation of concern occurs when natural biogeochemical parameters,
such as electron acceptors and electron donors that support attenuation, are used
up before the treatment of contamination is complete.
For these reasons, environmental regulators and others should not rely on simple
rules of thumb (such as maximum contaminant concentration data or trends in these
data over a relatively short time) in evaluating the potential success of natural
attenuation.
The decision to rely on natural attenuation and the confirmation that it will
continue to work depend on linking monitoring data to a site conceptual model and
footprints of the underlying mechanisms. Footprints are mappings of concentration
changes in reactants (contaminant(s), electron acceptors, and donors) or products of
the biogeochemical processes (such as Cl ion, dissolved Fe2+) that degrade or
66
immobilize the contaminants (Figures 3.1a, b, and c). Footprints can be measured
to document that these transformation or immobilization processes are active at the
site. An observation of the loss of a contaminant, coupled to observation of a few
footprints, helps to establish which processes are responsible for the decrease in
contaminant mass and concentrations. The three basic steps to document natural
attenuation are as follows:
1. Develop a conceptual model of the site: The model should show where and how
fast the groundwater flows, where the contaminants are located and at what
concentrations, and which types of natural processes could theoretically affect the
contaminants (Figures 3.2a and b).
2. Analyze site measurements: Samples of groundwater should be analyzed chemically to look for footprints of the natural attenuation processes and to determine
whether these processes are sufficient to control the contamination.
3. Monitor the site: The site should be monitored until regulatory requirements are
achieved to ensure that documented attenuation processes continue to occur.
Figures 3.1a
Initial vinyl chloride plume at a landfill site in Maryland with radial groundwater
flow from the center of the landfill.
Although the basic steps are the same for all sites, the level of effort needed to
carry out these steps varies substantially with the complexity of the site. When site
characteristics or the controlling mechanisms are uncertain, it will be difficult to
develop the site conceptual model; thus, a large amount of data will be required to
document natural attenuation. In these complex situations, computer modeling may
be necessary, and data on footprints and site characteristics will have to be more
than adequate to develop the model.
1200
1000
67
Three-dimensional perspective plot

of observed vinyl choride concentrations
in groundwater -1996
800
600
500
400
Landfill
boundary
200
200
150
100
20
5
1
0
Figures 3.1b
Natural attenuation effects on the vinyl chloride plume. Note: The significant
reduction in vinyl chloride concentration and mass due to natural attenuation.
Dissolved Oxygen
Redox
Fe 2+
Manganese
Vinyl Chloride
Landfill
Saprolite
Sand/Gravel
Bedrock
Dissolved Oxygen, Redox, and

Vinyl Chloride Distribution
Figures 3.1c
Effects of the primary electron acceptor dissolved oxygen on the attenuation of

VC and Mn along a North-South transect through the middle of the landfill.
Figures 3.2a
Abandoned Well?
A general site conceptual exposure model (adapted from ASTM, 1997).
Confining Layers?
Confining Layers?
Future Domestic
Water Supply Well
Current Municipal
Water Supply Well
Confining Layers?
Shallow Water Table
Current Domestic
Water Supply Well
68
Dissolved Plume
Residual NAPL
Utilities
Utilities
Figures 3.2b
Dissolved
Groundwater
Plume
Dissolved
Groundwater
Plume
Mobile
NAPL
Migration
Stormwater/
Surface
Water
Transport
Non-Aqueous
Phase Liquid
(NAPL)
Affected
Surface Soils,
Sediments or
Surface Water
Leaching and
Groundwater
Transport
Volatilization
and
Atmospheric
Dispersion
Wind
Erosion and
Atmospheric
Dispersion
Transport
Mechanisms
Affected
Subsurface
Soils
(>3 ft depth)
Affected
Surface
Soils
(<3 ft depth)
Secondary
Sources
Site conceptual exposure models.
Chemical Storage
Piping / Distribution
Operations
Waste Management Unit
Soil or Waste Piles
Lagoons or Ponds
Other
Primary
Sources
Recreational Use/
Relevant Habitat
SURFACE WATER
Potable Water Use
GROUNDWATER
Inhalation of Vapor
or Particulates
AIR
Dermal Contact
or Ingestion
SOIL
Exposure
Routes
Residential
Commercial/Industrial
Relevant Ecological Receptor
Residential
Residential
Construction Worker
Residential
Construction Worker
Receptors
L1282_C03-A_frame Page 69 Tuesday, June 19, 2001 12:59 PM

69
70
3.3
3.3.1
PATTERNS VS. PROTOCOLS
Protocols for Natural Attenuation
Within the past few years, many organizations have issued documents providing
guidance on evaluating natural attenuation.1 Among the 14 documents developed by
a range of organizations from federal and state agencies to private companies and
industry associations, the available technical protocols address two classes of organic
contaminants only: fuel hydrocarbons and chlorinated solvents (with the exception
of the Department of Energy (DOE) document). A large body of empirical evidence
and scientific and engineering studies in recent years has been developed to support
understanding of natural attenuation of these contaminants mostly fuel hydrocarbons under certain conditions. However, the natural attenuation of polycyclic
aromatic hydrocarbons, polychlorinated biphenyls, explosives, and other classes of
persistent organic contaminants is not addressed in any protocol.1 Furthermore,
although the DOE document proposes a method for assessing natural attenuation
processes for inorganic contaminants such as metals, such processes are extremely
complex, and this document does not adequately reflect this complexity.6
A recent effort was made to compare the guidelines currently available on natural
attenuation against a list of characteristics of a comprehensive protocol.1 The consensus was that a comprehensive protocol should cover three broad areas:
Community concerns: The protocol should describe a plan for involving the
affected community in decision making, maintaining institutional controls to
restrict use of the site until cleanup goals are achieved, and implementing contingency measures if natural attenuation fails to continue as expected.
Scientific and technical issues: The protocol should describe how to document
which natural attenuation processes are responsible for observed decreases in
contaminant concentrations, how to assess the site for contaminant source and
hydrogeologic characteristics that affect natural attenuation, and how to assess the
sustainability of natural attenuation over the long term.
Implementation issues: The protocol should be easy to follow and should describe
the monitoring frequency and various monitoring procedures, in addition to the
training and expertise required for the personnel carrying out the field implementation.
None of the current documents fulfills all the criteria defined above.1 To some
extent, this reflects the various, and sometimes limited, purposes for which these
documents were prepared. Some are detailed technical guides; others are intended
to help ensure consistency in site evaluation within a particular organization (such
as a private corporation or a branch of the military), and others are intended to guide
policy. Nonetheless, key gaps in the existing body of protocols have to be addressed.
The existing protocols provide little or no discussion of when and how to involve
the public in site decisions and when and how to implement institutional controls.
In the few instances where these matters are mentioned, the discussion is typically
brief, almost in passing. Although most environmental regulatory agencies have
separate policies that specify procedures for community involvement and
71
institutional controls, these procedures may be inadequate in cases where natural

attenuation is selected as the remedy. Discussion of when and how to implement
contingency plans in case natural attenuation does not work is also inadequate in
many of the protocols. Further, the protocols do not provide sufficient guidance on
when and how engineered methods to remove or contain sources of contamination
benefit natural attenuation.
A major shortcoming of some of the protocols relates to scoring systems used for
initial screening to determine whether a site has potential for treatment by natural
attenuation. Such scoring systems yield a numeric value for the site in question. If this
value is above a certain level, the site is judged an eligible candidate for natural
attenuation. Frequently, such scores are used inappropriately as the key factor in
deciding whether natural attenuation can be a successful remedy at the site. Moreover,
these scores often lead to erroneous conclusions about whether natural attenuation will
or will not succeed, due to the complexity of the processes involved and the tendency
of scoring systems to oversimplify them. In addition, the scoring systems developed
for evaluating natural attenuation at petroleum sites are erroneously used to evaluate
sites with chlorinated solvents by many practitioners of remediation.
In summary, the existing body of natural attenuation protocols is limited in
several important areas.1 Where and how existing protocols can be used to meet
regulatory requirements for documenting site cleanup and whether such protocols
are required at all is also unclear. Guidance on the use of natural attenuation for
remediation has to be developed to cover topics not addressed in existing protocols
and to provide for the use of protocols in regulatory programs.
3.3.2
Patterns of Natural Attenuation
Instead of relying on protocols and scoring systems, an educated screening tool

should be to observe the patterns in reduction of contaminant concentrations. Naturally attenuating contaminant plumes can take a variety of forms: they might be
expanding, stable, or shrinking, depending on the trends in the spatial variations of
contaminant concentrations with time (Figures 3.3a, b, and c). Common patterns in
all attenuating plumes are a decline in the dissolved contaminant mass with time,
and a decline in contaminant concentrations downgradient from the source. Once
these patterns are observed initially, the following list of questions should be developed to collect additional data to develop a platform demonstrating that MNA is an
ongoing and continuing process to meet the site cleanup objectives:
What chemical, physical, and biological processes are in effect to support natural
degradation of the site-specific contaminants?
What site biogeochemical conditions are needed for these chemical, physical, and
biological processes to work? Which types of site conditions are optimal? Which
conditions inhibit natural attenuation?
What level of information is needed to characterize the site fully?
What breakdown products that may be more toxic, persistent, or mobile are created
when the contaminants degrade? How does one prove that contaminants are
degrading into harmless substances?
72
Contaminated
Zone
Monitoring
Well
Cross Sectional View
MW-2
MW-1
MW-3
t0
t1
t2
Plan View
"Contaminant plume is continuing to grow and move downgradient from the source area"
Figures 3.3a
Expanding plume.
What kinds of specific monitoring and testing are needed to determine that the
site and the contaminants are suitable for natural attenuation? Is extensive monitoring necessary?
How long is it reasonable to monitor to ensure that natural attenuation is working?
How viable are institutional controls? Can they be enforced?
Is stabilization by natural attenuation irreversible for metals or other substances?
3.3.2.1 Various Patterns of Natural Attenuation

Removal of Contaminant Sources: At most contaminated sites, the bulk of the
contaminant mass is in what remediation professionals call source zones. Examples
of source zones include landfills, areas of chemical spills, buried tanks that contain
residual chemicals, deposits of tars, etc. Some of these sources can be easily located
73
Contaminated
Zone
Monitoring
Well
t2
MW-3
MW-2
t0
t1
MW-1
Plan View
Contaminant plume is almost stationary over time and concentrations at points

within the plume are relatively constant over time with a slight declining trend.
Figures 3.3b
Stable groundwater plume.
and complete or partial removal or containment may be possible. However, other

common types of sources often are extremely difficult to locate and remove or
contain. One example of a source in this category is chemicals that have sorbed to
soil particles but have the potential to dissolve later into groundwater that contacts
the soil. Another extremely important example is the class of organic contaminants
known as nonaqueous-phase liquids (NAPLs). There are two types of NAPLs:
those that are more dense than water (dense nonaqueous-phase liquids, or DNAPLs),
and those that are less dense than water (light nonaqueous-phase liquids, or
LNAPLs). When released to the ground, these types of fluids move through the
subsurface in a pattern that varies significantly from that of the water flow because
NAPLs have different physical properties than water. As shown in Figure 3.4a, b,
and c, LNAPLs can accumulate near the water table, DNAPLs can penetrate the
water table and form pools along geologic layers, and both types of NAPLs can
become entrapped in soil pores. These NAPL accumulations contaminate the
74
Contaminated
Zone
Monitoring
Well
MW-2
MW-1
MW-3
t2
t1
Plan View
t0
Contaminant plume is receding back toward the source area over time and the
concentrations at points within the plume are declining over time.
Figures 3.3c
Shrinking groundwater plume.
groundwater that flows by them by slow dissolution. Common LNAPLs include

fuels (gasoline, kerosene, and jet fuel) and common DNAPLs include industrial
solvents (trichloroethene, tetrachloroethene, and carbon tetrachloride) and coal tar.
Once they have migrated into the subsurface, NAPLs are often difficult or impossible
to locate in their entirety. Normally, the total mass of a contaminant within source
zones is significantly larger compared to the mass dissolved in the plume. Therefore,
the source usually persists for a very long time. The rate at which contaminants
dissolve from a typical NAPL pool is so slow that many decades to centuries may
be needed to dissolve the NAPL completely by dissolution without any intervention.
The potential for success of natural attenuation of various dissolved organic and
inorganic compounds is presented in Table 3.1.
Given the persistent nature of contaminant sources, removing them would seem
like a practical way to speed natural attenuation of the contaminant plume (Figure
3.4). In many cases, environmental regulators require source removal or containment
75
Table 3.1 The Potential for Success of Natural Attenuation for Various Compounds
(adapted from NCR, 2000)
Contaminant Type
Dominant Attenuation Processes
Likelihood of
Success
Organic
Hydrocarbons
BTEX
Gasoline, fuel oil
Nonvolatile aliphatic compounds
PAHs
Creosote
Biotransformation
Biotransformation
Biotransformation, immobilization
High
Moderate
Low
Low
Low
Biotransformation
High
Biotransformation
Moderate
Methylene chloride
Vinyl chloride (VC)
Biotransformation
Biotransformation, abiotic
transformation
Biotransformation
Biotransformation
Dichloroethene (DCE)
Biotransformation
Moderate
Moderate to
High
High
Moderate to
High
Moderate
Low
Biotransformation
Biotransformation
Low
High
Biotransformation, abiotic
transformation, immobilization
Low
Oxygenated Hydrocarbons
Low-molecular-weight
Alcohols, ketones, esters
MtBE
Chlorinated Aliphatics
PCE, TCE, carbon tetrachloride
Trichloroethane (TCA)
Chlorinated Aromatics
Highly chlorinated PCBs,
pentachlorophenol,
multichlorinated benzenes
Less chlorinated PCBs, dioxins
Monochlorobenzene
Nitroaromatics
TNT, RDX
Inorganic
Metals
Ni
Cu, Zn
Cd
Pb
Cr
Immobilization
Immobilization
Immobilization
Immobilization
Hg
Moderate
Moderate
Low
Moderate
Low to
Moderate
Low
76
Table 3.1 The Potential for Success of Natural Attenuation for Various Compounds
(adapted from NCR, 2000) (continued)
Contaminant Type
Dominant Attenuation Processes
Likelihood of
Success
Low
Low
Biotransformation
Biotransformation
Moderate
Moderate
Nonmetals
As
Se
Oxyanions
Nitrate
Perchlorate
Not Enough Mass Spilled to Form an NAPL

a)
t4
t1
t2
t3
LNAPL Release
b)
t1
MNAPL
t2
MDISS
t3
t4
MN > M D
DNAPL Release
c)
t1
t2
Adsorbed
DNAPL
MNAPL
DNAPL Pool
Figures 3.4
t4
t3
MDISS
MN > M D
Various possibilities of source zone contamination.
as part of a natural attenuation remedy. Although requiring source control or removal

is good policy for many sites, expert opinions conflict on whether source removal
is advisable when using natural attenuation as a remedy, even when such removal
is technically feasible.
77
Goals of source removal should be the following:

Remove as much contaminant mass as practical to reduce the mass flux of contaminants emanating from the source zone, thus reducing the concentration of the
contaminant plume rapidly and also reducing the longevity of the required monitoring period; and
Avoid any changes that would reduce the effectiveness of natural attenuation, such
as disturbing the natural dissolution equilibrium from an NAPL source by drilling
through it and thus increasing the mass flux.
In theory, if one can delineate the source completely and succeed in removing most
of the mass, then a significant benefit may be achieved. There are many case studies
available in the literature even for compounds like polycyclic aromatic hydrocarbons
(PAHs) plumes in which it appears that, after removal of the source, the plumes
attenuated rapidly. However encouraging this example might be, this kind of success
may not always be realized. Particularly, DNAPL sources in fractured bedrock environments cannot be delineated completely and/or cannot be removed to any significant
degree at a reasonable cost. Hence, source removal options may be rejected because
none are anticipated to be able to warrant the expense and risks of the removal effort
by removing all of the source mass without leaving a significant level of residual mass.
In some cases, source removal efforts may directly and adversely affect natural
attenuation. Most of the negative impacts will be caused mainly by the disturbance
of the equilibrium between the moving groundwater and the quiescent mass of
NAPL, particularly DNAPL. As a precautionary measure, an outside-in approach to
investigating the source zone is recommended in contrast to an inside-out approach.
Consideration should be given when looking at removal of the source of one
type of contaminant which may adversely affect natural attenuation of another type
and thus result in minimal or no overall benefit. A good example is the removal of
a petroleum hydrocarbon source zone serving as a nutrition source for microbes
involved in degrading a chlorinated solvent plume. Such an action could slow down
or completely shut off natural attenuation of the chlorinated solvent.
Natural Attenuation Capacity (NAC): The manner in which natural attenuation
and active remediation measures (such as source removal, pump and treat, chemical
oxidation, or enhanced bioremediation) are combined depends on the natural attenuation capacity (NAC) of the system. If the NAC is small, for example, active
remediation measures will need to remove or degrade a high proportion of the
contaminant source to protect downgradient receptors. Conversely, if the NAC is
large, less source removal may be required to protect downgradient receptors. In
either case, it is necessary to quantify the NAC of the biogeochemical system to
combine contaminant source-removal methods with natural attenuation effectively.
Natural attenuation capacity is a concept that refers to the capacity of a biogeochemical system to lower contaminant concentrations along aquifer flow paths.
The NAC of groundwater systems depends on hydrogeologic (dispersion and advection) and biological (biodegradation rates) factors for organic contaminants and
precipitation potential also for heavy metals.
78
The concept of NAC is useful because it illustrates those characteristics and

parameters of a groundwater system that affect the efficiency of natural attenuation.7
For example, if the biodegradation rate constant is small ( 0.001 d1) relative to
the groundwater velocity (~3 ft/day) and aquifer dispersivity (30 feet), the NAC of
the system also will be small. Because of this small NAC, contaminants will be
transported relatively long distances downgradient of the source area (Figure 3.5a).
Conversely, if the biodegradation rate is high relative to groundwater velocity and
aquifer dispersivity, the NAC will be proportionally higher, and the transport of
contaminants will be restricted closer to the source area.
Very Low NAC
Concentration
Moderate NAC
High NAC
Distance Along Flow Path

Figure 3.5a
The effect of natural attenuation capacity on contaminant transport.7
Quantitative mathematical techniques in addition to empirical methods are available to estimate NAC. In addition to NAC, the distance that contaminants are
transported in a groundwater system also depends on the contaminant concentrations
at the source area (Figure 3.5b).
High concentration, low NAC
High concentration, higher NAC
Concentration
Lower concentration, low NAC

Lower concentration, higher NAC
Cleanup Standards
Distance Along Flow Path
Figure 3.5b
The effect of source area concentrations on the distance required to reach

cleanup standards.
3.4
3.4.1
79
PROCESSES AFFECTING NATURAL ATTENUATION OF

COMPOUNDS
Movement of Contaminants in the Subsurface
Even in the absence of biotic and/or abiotic transformations of a contaminant,

the contaminant always is subject to transport processes meaning that physical
processes cause it to move. All important transport processes for subsurface contaminants can be categorized as dilution, advection, dispersion, or phase transfer
(from one type of physical medium to another, such as from an NAPL to groundwater
or from water to the soil matrix).
3.4.1.1 Dilution (Recharge)
Recharge is the amount of water entering the saturated zone of the water table
at the water table surface, made available mainly by precipitation events. In recharge
areas, flow near the water table is generally downward. Recharge defined in this
manner may therefore include not only precipitation that infiltrates through the
vadose zone, but also water entering the groundwater system via discharge from
surface water bodies. Where a surface water body is in contact with or is part of the
groundwater system, the definition of recharge is stretched slightly. However, such
bodies often are referred to as recharging lakes or streams.8 The recharge of the
water table aquifer has two effects on the natural attenuation of a dissolved contaminant plume: 1) additional water entering the system due to infiltration of precipitation or from surface water will contribute to dilution of the plume and 2) the influx
of relatively fresh, electron-acceptor-charged water will alter the geochemical processes and in some cases, facilitate additional biodegradation.8,9
Recharge from infiltrating precipitation is the result of a complex series of
processes in the unsaturated zone. Description of these processes is beyond the scope
of this chapter; however, it is worth noting that the infiltration of precipitation through
the vadose zone brings the water into contact with the soil and thus may allow the
introduction of electron acceptors (such as NO3 and SO42 ) in addition to the DO in
the recharge water and also dissolved organic carbon (electron donor). Infiltration
therefore provides fluxes of water, inorganic species, and possibly organic species
into the groundwater. In the case of surface water it may be connected as part of
the groundwater system, or it may be perched above the water table. In either case,
the water entering the groundwater system will not only aid in dilution of a contaminant plume, but it may also add electron acceptors and possible electron donors
to the groundwater.
An influx of electron acceptors will tend to increase the overall assimilation
capacity of the groundwater system. In addition to the introduction of electron
acceptors that may be dissolved in the recharge (e.g., dissolved oxygen, nitrate, or
sulfate), the infiltrating water may also foster biogeochemical changes in the aquifer.
For example, Fe2+ will be oxidized back to Fe3+ and will be precipitated out. This
reprecipitation of Fe3+ could be again available for reduction by microorganisms.
Such a shift may be beneficial for biodegradation of contaminants utilized as electron
L1282_C03-A_frame Page 80 Thursday, March 6, 2003 11:35 AM
80
donors, such as fuel hydrocarbons or vinyl chloride. However, these shifts can also
make conditions less favorable for reductive dechlorination.
Evaluating the effects of recharge can be difficult. The effects of dilution might
be estimated if one has a detailed water budget for the system in question. However,
if a plume has a significant vertical extent, it cannot be known with any certainty
what proportion of the plume mass is being diluted by the recharge. In addition,
separating the effects of dilution from other processes of mass reduction may be
difficult. After recharge, the effects of the addition of electron acceptors may be
apparent due to elevated electron acceptor concentrations, differing patterns in electron acceptor consumption, or by-product formation in the area of recharge. However, the effects of short-term variations in such a system (which are likely due to
the intermittent nature of precipitation events in most climates) may not easily be
quantified. Where recharge is from surface water, the influx of mass and electron
acceptors is more steady over time. In this scenario, quantifying the effects of dilution
may be less uncertain, and the effects of electron acceptor replenishment may be
more easily identified (although not necessarily quantified).
In some cases the effects of recharge-diluting contaminant plumes can be estimated with a simple relationship based on the specific discharge of groundwater
passing through the point of interest and the amount of recharge entering the plume
area. It is imiportant to note that at most sites, recharge will not actually mix with
groundwater in an aquifer but will form a stratified layer on top due to the very low
amount of vertical dispersion characteristic of aquifer systems. Mixing can be
assumed in some cases, such as a very thin, unconfined aquifer: the aquifer discharges into a surface water body, and the groundwater associated with the recharge
is assumed to be mixed with the original groundwater flowing past a source zone.8-10
The relationship for estimating the amount of dilution caused by recharge is
RWL VD
C L = C 0 exp
WTh VD
(3.1)
Eliminating the width and rearranging gives:
RL
C L = C 0 exp T (V )2
D
h
(3.2)
where
CL
C0
R
W
L
= concentration at distance L from origin assuming complete mixing of

recharge with groundwater (mg/L)
= concentration at origin or at distance L = 0 (mg/L)
= recharge mixing with groundwater (ft/yr)
= width of area where recharge is mixing with groundwater (ft)
= length of area where recharge is mixing with groundwater (ft)
VD
Th
81
= Darcy velocity of groundwater (ft/yr)

= thickness of aquifer where groundwater flow is assumed to mix completely with recharge (ft)
3.4.1.2 Advection
Transport of a contaminant molecule occurring with the groundwater movement
is called advection or convection or bulk flow. Advection occurs in any moving fluid.
Thus, contaminants can advect when they are in air in soil pores or in a moving
NAPL, as well as in water. Advection transport is illustrated simply by considering
a contaminant that does not react biotically or abiotically (also known as conservative
compound or tracer) in the subsurface and that moves at the average velocity of the
groundwater. Figures 3.6a and b describe this phenomenon. The contaminant moves
at exactly the same velocity as the water and does not change from its initial
concentration of C0 at the injection point.9
time=
t0
Concentration (C)
time=
t1
time=
t2
t1
t2
Distance (x)
Figure 3.6a
Dispersion of a pulse of a tracer substance in a sand column experiment.
1.0
Initial
Contaminant
Slug
Advection
Only
Advection
Only
Advection,
Dispersion,
and Sorption
C/
C 0.5
O
Advection and
Dispersion
Distance From Source
Figure 3.6b
Concentration curves showing plug flow with an instantaneous source from

advection only and from a combination of advection, dispersion, and sorption.
82
The mass flux rate at which a dissolved contaminant moves across a vertical
plane in the subsurface is the product of the contaminant concentration and the
velocity of groundwater. Groundwater velocity is governed by three key factors
specific to each site:
The hydraulic gradient includes gravity and pressure components and is the
driving force for water movement. Water always moves in the direction of higher
hydraulic head (which can be thought of qualitatively as elevation) to lower head.
Hydraulic conductivity is the ability of porous rocks or soil sediments to transmit
fluids and is measured from field tests or samples. Hydraulic conductivity values
for common rocks and sediments vary over ten orders of magnitude from almost
impermeable crystalline rocks to highly permeable gravels; the hydraulic conductivity values for fractured rocks, sand, and clay are between these extremes. A
contaminant plume moving with the groundwater will travel faster through sand
layers, which have high hydraulic conductivity, than through clays of low hydraulic conductivity, under the same hydraulic head gradient.
Porosity is a measure of the volume of open spaces in the subsurfaces relative to
the total volume. Like hydraulic conductivity, it depends on the type of geologic
material present and can be determined from field tests or samples.
The equation for describing the rate of groundwater flow from one location to
another is known as Darcys equation:
VD = K H
h
X
(3.3)
where
KH
h
X
VD
= hydraulic conductivity (in units of distance per time)

= hydraulic gradient
= Darcy velocity (in units of distance per time)
To determine the seepage velocity of a contaminant that travels at the same speed
as the groundwater, the Darcy velocity must be divided by the effective porosity :
V=
VD
(3.4)
KH and can be estimated using various field test methods or laboratory evaluations
of cores taken from the subsurface. Uncertainty is inherent in all such measurements,
and this uncertainty must be acknowledged by developing a range of possible flow
scenarios.
83
3.4.1.3 Dispersion
Spreading of contaminants from the main direction of groundwater flow takes
place as the groundwater moves, altering concentrations from those that would occur
if advection were the only transport mechanism. This mixing is called hydrodynamic
dispersion. The mechanisms causing dispersion within the plume include molecular
diffusion, different water velocities within individual pores, different water velocities
between adjacent pores, and tortuosity of the subsurface flow path (Figure 3.7).
Mixing caused by local variations in velocity is also known as mechanical dispersion.
Groundwater scientists quantify the combined mixing effect using a hydrodynamic
dispersion coefficient DH. Except at very low water velocities, DH increases linearly
with the average speed of groundwater.
A'
A
B'
Average Water
Flow Direction
C'
B
C
Figure 3.7
Seemingly random variations in the velocity of different parcels of groundwater

are caused by the tortuous and variable route the water must follow.
The curve labeled dispersion in Figure 3.6 a and b illustrates the effects of
dispersion for a conservative contaminant that travels precisely with the water molecules. The solute is detected at the observation well before it would be if advection
were the only process affecting its movement. Dispersion causes the solute to spread,
rather than moving as an unchanged plug.
Molecular Diffusion: Molecular diffusion takes place as a result of the contaminant gradients created within the zones of contamination. It is significant only when
the groundwater velocities are low, and the diffusive flux of a dissolved contaminant,
at steady state, can be described by Ficks first law.
F = D
dc
dx
where
F
D
C
= mass flux of solute per unit area of time

= diffusion coefficient
= solute concentration
dc
dx
= concentration gradient
(3.5)
84
For systems where the dissolved contaminant concentrations are changing with
time, Ficks second law must be applied. The one-dimensional expression of Ficks
second law is
d2
dc
= D c2
dt
dx
(3.6)
dc
is the change in concentration with time.
dt
The process of diffusion is slower in porous media than in open water because
the contaminant molecules must follow more tortuous flow paths. To account for
this, an effective diffusion coefficient D* is used. Fetter estimates a range of 1
109 to 2 109 m2/S for D* has been estimated.9(a)
The effective diffusion coefficient is expressed quantitatively as
where,
D* = wD
(3.7)
where w is the empirical coefficient determined by laboratory experiments. The

value of w ranges greatly from 0.01 to 0.5.9
Mechanical Dispersion: Mechanical dispersion occurs due to variations in flow
velocity because of varying pore throat sizes and tortuosity caused by variations in
flow path lengths. An additional cause of mechanical dispersion is variable friction
within an individual pore, thus allowing the groundwater flowing in the center of
the pore to move faster than groundwater flowing next to the soil particle itself.
The component of hydrodynamic dispersion contributed by mechanical dispersion can be described as:
mechanical dispersion = x V
(3.8)
where
x
V
= dispersivitiy
= seepage velocity
Advection dispersion equation: The advection-dispersion equation, which

includes hydrodynamic dispersion, can be described as:8,9
c
2c
c
= DH
V
t
Ox 2
x
where
c
t
DH
x
V
=
=
=
=
=
contaminant concentration
time
hydrodynamic dispersion
distance along flow path
seepage velocity
(3.9)
3.4.2
85
Phase Transfers
Contaminants will be added or removed from the groundwater when they transfer
between phases. The relevant phases in the subsurface are groundwater (dissolved),
soil grains (adsorbed), NAPLs (liquid), and soil gas (air) in the vadose zone. Phase
transfers can increase or decrease the contaminant concentration within the groundwater plume, depending on the transfer mechanism, the contaminant, and the
geochemistry. Although the basic concepts of phase transfer are straightforward,
quantification of these transfers often is not easy.
3.4.2.1 Sorption
Many contaminants, including chlorinated solvents, BTEX and dissolved metals,
are removed from solution by sorption onto the aquifer matrix, thus slowing the
movement of contaminants. This slowing of contaminant transport is called retardation
of the contaminant relative to the average seepage velocity of groundwater and results
in a reduction in dissolved organic concentrations in groundwater. Sorption can also
influence the relative importance of volatilization and biodegradation. Figure 3.6b
illustrates the effects of sorption on an advancing dissolved contaminant front.
Sorption is a dynamic and reversible reaction; thus, at a given solute concentration,
some portion of the contaminant is partitioning out of solution onto the aquifer matrix,
and some portion is desorbing and reentering solution. As solute concentrations change,
the relative amounts of contaminant that are sorbing and desorbing will change. For
example, as solute concentrations decrease due to other factors such as biodegradation
and dilution, the amount of contaminant reentering solution will probably increase.
The affinity of a given compound for the aquifer matrix will not be sufficient to isolate
it permanently from groundwater, although for some compounds the rates of desorption
may be so slow that the adsorbed mass may be considered as permanent residual
within the time scale of interest. Sorption, therefore, does not permanently remove
solute mass from groundwater; it merely retards migration.
The various mechanisms that cause sorption effects to take place within the
aquifer matrix are described in detail in Chapter 2. Because of their nonpolar
structure, hydrocarbons most commonly exhibit sorption through the process of
hydrophobic bonding. When the surfaces comprising the aquifer matrix are less
polar than the water molecule, as is generally the case, there is a strong tendency
for the nonpolar contaminant molecules to partition from the groundwater and sorb
to the aquifer matrix. This phenomenon, referred to as hydrophobic bonding, is an
important factor controlling the fate of many organic pollutants in soils. As described
in Chapter 2, two components of an aquifer have the greatest effect on sorption:
organic matter and clay minerals. In most aquifers, the organic fraction tends to
control the sorption of organic contaminants.
Sorption Models and Isotherms: Regardless of the sorption mechanism, it is
possible to determine the amount of sorption to be expected when a given dissolved
contaminant interacts with the materials comprising the aquifer matrix. Bench-scale
experiments are performed by mixing water-contaminant solutions of various concentrations with aquifer materials containing various amounts of organic carbon and
86
clay minerals. The solutions are then sealed with no headspace and left until equilibrium between the various phases is reached. (True equilibrium may require hundreds of hours of incubation, but 80 to 90% of equilibrium may be achieved in one
or two days.) The amount of contaminant left in solution is then measured.
The results are commonly expressed as a plot of the concentration of chemical
sorbed (g/g) vs. the concentration remaining in solution (g/L). The relationship
between the concentration of chemical sorbed (Ca ) and the concentration remaining
in solution (Cs ) at equilibrium is referred to as the sorption isotherm because the
experiments are performed at constant temperature (Figure 2.11). Sorption isotherms
generally exhibit one of three characteristic shapes, depending on the sorption
mechanism: the Langmuir isotherm, the Freundlich isotherm, and the linear isotherm
(a special case of the Freundlich isotherm).
Retardation: As mentioned earlier, sorption tends to slow the transport velocity
of contaminants dissolved in groundwater. When the average velocity of a dissolved
contaminant is less than the average seepage velocity of the groundwater, the contaminant is said to be retarded. The coefficient of retardation, R, is used to estimate
the retarded contaminant velocity. The variation between the velocity of the groundwater and that of the contaminant is caused by sorption and is quantified by the
coefficient of retardation, defined as:
R=
V
Vc
(3.10)
where
R
V
Vc
= coefficient of retardation
= average seepage velocity of groundwater parallel to groundwater flow
= average velocity of contaminant parallel to groundwater flow
The ratio (V/Vc) describes the relative velocity between the groundwater and the
dissolved contaminant. When Kd = 0 (no sorption), the transport velocities of the
groundwater and the solute are equal (V/Vc). If it can be assumed that sorption is
described adequately by the distribution coefficient (valid when the fraction of
organic carbon (foc) > 0.001), the coefficient of retardation for a dissolved contaminant is described by the following equation:9
R = 1+
where
R
b
Kd
n
=
=
=
=
coefficient of retardation
bulk density of aquifer
distribution coefficient
porosity
b K d
n
(3.11)
87
The bulk density, b, of a soil is the ratio of the soil mass to its field volume.
Bulk density is related to particle density by the following equation:
b = (1 n)s
(3.12)
where n is the total porosity and s is the density of soil grains comprising the
aquifer. In sandy soils, b can be as low as 1.81g/cm3. In aggregated loams and
clayey soils, b can be as low as 1.1g/cm3.
The sorption relationship shown above expresses the coefficient of retardation
in terms of the bulk density and effective porosity of the aquifer matrix and the
distribution coefficient for the contaminant. Substitution of this equation into Equation 3.10 gives
K
V
= 1+ b d
Vc
n
(3.13)
Solving for the contaminant velocity, Vc , gives

Vc =
Vx
1 + b K d n
(3.14)
Retardation factors can be calculated for several fuel and chlorinated solventrelated chemicals as a function of the fraction of organic carbon content of the soil.
The value of R can vary over two orders of magnitude at a site, depending on the
chemical in question and the estimated value of porosity and soil bulk density. Earlier
investigations reported distribution coefficients normalized to total organic matter
content (Kom ). The relationship between fom and foc is nearly constant, and assuming
that the organic matter contains approximately 58% carbon:9
Koc = 1.724 Kom
(3.15)
Two methods are used to estimate the distribution coefficient and amount of
sorption (and thus retardation) for a given aquifer-contaminant system. The first
method involves estimating the distribution coefficient by using Koc for the contaminants and the fraction or organic carbon comprising the aquifer matrix. The second
method involves conducting batches of column tests to determine the distribution
coefficient. Because numerous authors have conducted experiments to determine Koc
values for common contaminants, literature values are reliable, and it generally is
not necessary to conduct laboratory tests.9
88
3.4.2.2 Stabilization
The transfer of an organic compound from an NAPL source to the surrounding
water increases the contaminant concentration in groundwater. The rate of transfer
varies depending on the type of NAPL. Computation of this transfer rate can be
complex because the transfer rate depends on chemical properties of the contaminant
and the NAPL, as well as on resistance at the interface between the water and the
NAPL.11 Diffusion of the contaminant within the NAPL itself also can affect the
transfer rate for viscous NAPLs.
DNAPLs: Dense nonaqueous phase liquids (DNAPLs) present in the form of
residual (held under capillary forces) or free phase (mobile) product may result in
continued long-term contamination of the surrounding groundwater. The marginally
soluble organic contaminants can partition into the aqueous phase at rates slow
enough to continue to exist as a nonaqueous phase, yet rapid enough to cause
significant groundwater contamination. DNAPLs can migrate to depths well below
the water table. As they migrate, they can leave behind trails of microglobules in
the pore spaces of the soil matrix, which effectively serve as long-term sources of
groundwater contamination.
Current conceptual DNAPL transport models suggest that, when sinking free
phase DNAPL encounters a confining layer (e.g., competent clay or bedrock zone),
it can accumulate, or pool, and spread laterally until it encounters a fracture or an
alternative path of relatively low flow resistance towards deeper zones.11 In addition,
globules can enter pores and be held as a residual phase in capillary suspension.
This complex mode of subsurface transport results in unpredictable heterogeneous
distribution of nonaqueous product that is difficult to delineate.
The current lack of appropriate methods for detecting and delineating widely
dispersed microglobules of DNAPL has been identified as one of the most significant
challenges today. Investigative techniques that have been used to identify DNAPL
source zones are listed below. It should be noted that some of those techniques are
well proven and extensively field tested, while others are considered relatively new.12
Soil gas surveys

Visual evidence of soil, rock and/or groundwater samples
Chemical analyses of soil, rock and/or groundwater samples
Enhanced visual identification shake tests
Enhanced visual identification UV fluorescence with portable light, dye addition with Sudan IV or Oil Red O
Accumulation within monitoring wells at target locations
Partitioning interwell tracer tests
Backtracking using dissolved concentrations in wells (the 1% rule)
Surface geophysics
Subsurface geophysics
Cone penetrometer testing (CPT) methods:
Permeable membrane sensor, membrane interface probe (MIP)
Hydrosparse
Laser induced fluorescence (LIF) techniques
GeoVis
89
Raman spectroscopy
Electrochemical sensor probe
Cosolvent injection/extraction technique
Precision injection/extraction (PIX) technique
Flexible liner underground technologies everting (FLUTE) membrane technique
It is important to recognize that each of the methods listed presents specific

advantages and disadvantages and applicability will be determined by technical and
economic challenges encountered at each site. Several methods can be complementary in an overall site management plan, and a hybrid approach could be developed
to exploit the strengths of the different techniques at the most appropriate and logical
times in the site management process. For example, one can initially screen a site
with a laser induced fluoroscence (LIF) technique or with geophysical techniques,
then analyze confirmation soil samples in the field visually, with Sudan IV dye, and
in the laboratory for chemical constituents. After determining the location of the
DNAPL source zone, discreetly screened or multilevel wells can be installed for
monitoring and remediation.
CPT and/or geophysical techniques, integrated with minimally intrusive direct
push technologies, can provide the framework for development of the conceptual
site model. Then the refined conceptual site model integrated with hydrogeologic
considerations can be used for guidance on a sampling plan to define the spatial
extent of the contamination.
3.4.2.3 Volatilization
Volatilization reduces the total mass of the contaminant in the groundwater
system. The potential for volatilization is expressed by the contaminants Henrys
Law Constant and described in detail in Chapter 2. Henrys Law Constants are
widely available for common volatile contaminants (see Appendix A). Although not
a destructive mechanism, volatilization does not remove contaminants from groundwater. In addition to Henrys Law Constant, other factors affecting the volatilization
of contaminants from groundwater include the contaminant concentration, the
change in contaminant concentration with depth, diffusion coefficient of the compound, temperature, and sorption. Because the soil gas often advects and dispersion
also occurs in the gas phase, contaminants transferred to the soil gas often migrate
away from the location at which they volatilize. Volatilization itself does not destroy
contaminant mass or permanently immobilize it. Volatilized contaminants can biodegrade in some circumstances but also can redissolve in infiltrating groundwater
or be transported to the surface, where humans may be exposed to the vapors.
3.4.3
Transformation Mechanisms
A variety of reactions transform contaminants. The possible reactions are called

biogeochemical: all are chemical (prefix chem) and occur in a geological setting
(prefix geo), but some are catalyzed by microorganisms (prefix bio). Some biogeochemical reactions can degrade or transform a contaminant into benign and
90
harmless end products or immobilize it permanently. A contaminant transformed or

immobilized in these ways no longer contributes to groundwater contamination.
Although other reactions do not directly lead to such positive results, they can control
whether or not the transformation or immobilization reactions take place. Often, a
suite of chemical reactions (termed a reaction network) leads to contaminant transformation or immobilization. In other instances, the reaction network prevents the
contaminants from being transformed or immobilized and may make natural attenuation an ineffective remediation strategy.
3.4.3.1 Biodegradation
Microorganisms can cause major changes in the chemistry of groundwater. Their
small size and adaptability, as well as the diversity of nutritional requirements for
different microbes, enable them to catalyze a wide range of reactions that often are
the basis for natural attenuation. Chemical changes brought about by microorganisms
can directly or indirectly decrease the concentrations of certain groundwater contaminants. Microorganisms use enzymes to accelerate the rates of certain biochemical reactions. The most important reactions are reductions and oxidations, together
known as REDOX reactions. The reactions involve transfer of electrons from one
molecule to another, which allow the microorganisms to generate energy and grow
(Figure 3.8). More discussions on REDOX reactions and microbial electron transfers
are provided in Chapters 2 and 4.
s and
tron
Elec
Organic
Contaminant
New
Cells
Energy
Elec
trons
Figure 3.8
n
arbo
Electron
Acceptor
(e.g., O2)
Conceptual description of microorganisms gaining energy and utilizing the substrate for growth.
Microorganisms reproduce by organizing chemical reactions that create daughter

cells composed of cellular components (e.g., membranes, proteins, deoxyribonucleic
acid [DNA], cell walls) derived from building blocks that they synthesize or scavenge
from the environment.1 The chemical reactions are made possible by enzymes
protein molecules that bring together the chemicals in a way that allows them to
react quickly (Figure 3.9). The reactions are driven to completion by the expenditure
of cellular energy in the form of a chemical known as adensoine triphosphate (ATP),
91
Oxidized Donor Product
Unicellular
Microorganism
NADH2
Electron
Donor
NADH2
Synthesis
and
Maintenance
ATP
NAD
ADP+Pi
NAD
Electron
Acceptor
Respiration
Reduced Acceptor
Product
Figures 3.9
Conceptual diagram of microbial activity to derive energy for growth and

multiplication (adapted from NRC, 2000).
which can be thought of as a cellular fuel. Like all living organisms, microorganisms
generate ATP by catalyzing redox reactions: they transfer electrons from electronrich chemicals to electron-poor chemicals. The technical term for the electron-rich
chemical is electron donor substrate. As an analogy, human metabolism involves
transfer of electrons from chemicals derived from ingested food (the donor substrate)
to oxygen (the acceptor substrate) inhaled from the air.1
When cells remove electrons from the donor substrate, they do not transfer the
electrons directly to the acceptor substrate. Instead, they transfer the electrons to
internal electron carriers as shown in Figure 3.9. Although electrons held by the
carriers can be used for many purposes, the major purpose is to generate ATP through
a process called respiration. In respiration, the electrons are passed from carrier to
carrier until they reach the electron-acceptor substrate. Since this is the last molecule
to receive the electrons, it is called the terminal electron acceptor. The need for ATP
production forces all microorganisms to have one or more electron-donor and electron-acceptor pairs, and these materials largely define the metabolism of individual
microorganisms. The amount of energy yielded varies depending on the electron
donor and electron acceptor used.
92
Ideally, all biologically mediated reactions produce energy for microbial growth
and reproduction. Biologically mediated electron transfer results in oxidation of the
electron donor, reduction of the electron acceptor, and the population of usable
energy (quantified by the Gibbs free energy of the reaction Gvo ). Table 3.2 presents
a few select electron acceptor and electron donor reactions and calculated Gyo
values.9 Negative values indicate an energy-producing reaction, otherwise called an
exothermic reaction, and will proceed from left to right. The value of Gyo can be
used to estimate how much free energy is consumed or produced during the reaction.
Positive values indicate an endothermic reaction; for the reaction to proceed from
left to right energy must be put into the system. Microorganisms will not invest
more energy into the system than can be released and must couple an endothermic
with an exothermic reaction to derive energy and grow.
Collectively, microorganisms can use a wide range of electron donors, including
both organic and inorganic chemicals. Electron acceptors are more limited. Common
electron acceptors include O2, NO3 , NO2 , SO42 , CO2, Fe(III), and Mn(IV). Oxygen
has a special status because of its importance in many environments and reactions.
Microbial use of oxygen as an electron acceptor is called aerobic metabolism; microbial use of electron acceptors other than oxygen is called anaerobic metabolism.
When biotransformation of a particular contaminant leads directly to energy
generation and the growth of more microorganisms, the contaminant is known as a
primary substrate (see Figure 3.8). However, the reactions that lead to microbial
metabolism of contaminants may not be part of cell-building or energy-generating
reactions. An important category of such biotransformations is cometabolism. Cometabolism is the fortuitous degradation of a contaminant when other materials are
available to serve as microorganisms primary substrates. Cometabolic reactions
often occur because the enzymes designed for metabolizing primary substrates
fortuitously transform the cometabolic substrate.
It is important to note the historic debate on the use of the word cometabolism for
the microbially catalyzed process described above.13,14 One school of thought, propagated by classical microbiologists, insists that usage of either the term cometabolism
or the term cooxidation to describe conversions of nongrowth substrates by nonproliferating microbial populations in the absence of a metabolizable cosubstrate would
be inappropriate. The enzymatic conversion of a substrate by a nonproliferating microbial population because an enzyme of broad specificity and conversion capability is
in proximity to the substrate might at best be described as bioconversion. There is no
co- (with or together) activity concerned with such an event.
First-Order Decay Model: One of the most commonly used expressions for
representing the biodegradation of an organic compound involves the use of an
exponential decay relationship:
C = C0 ekt
where
C
C0
k
= biodegraded concentration of the chemical at time t

= initial concentration
= rate of decrease of the chemical (units of 1/time) [T1]
(3.16)
93
Table 3.2 Half-Cell Reactions for Some of the Common

Electron Acceptors and Donors (adapted from
Wiedemeier et al., 1999)
Half-Cell Reaction
Gro
(kcal/mol e)
4e + 4H+ O2 2H2O
Aerobic respiration
18.5
5e + 6H+ + NO3 0.5N2 + 3H2O

Denitrification
16.9
2e + 4H+ + MnO2 Mn2+ + 2H2O

Manganese reduction
8.6
e + Fe3+ Fe2+
Fe(III) reduction
17.8
8e + 9.5H+ + SO42 0.5HS + 0.5H2S + 4H2O

Sulfate reduction
5.3
8e + 8H+ + CO2 CH4 + 2H2O

Methanogenesis
5.9
C2Cl4 + H+ + 2e C2HCl3 + Cl
PCE reductive dechlorination
9.9
C2HCl3 + H+ + 2e C2H2Cl2 + Cl
TCE reductive dechlorination
9.6
C2H2Cl2 + H+ + 2e C2H3Cl + Cl
cis-DCE reductive dechlorination
7.2
C2H3Cl + H+ + 2e C2H4 + Cl
VC reductive dechlorination
8.8
C2H3Cl3 + H+ + 2e C2H4Cl2 + Cl
TCA reductive dechlorination
/2 H 2 H+ + e
Hydrogen oxidation
10.3
9.9
/4 CH2O + 1/4 H2O 1/4 CO2 + H+ + e

Carbohydrate oxidation
10.0
12H2O + C6H6 6CO2 + 3O H+ + 3Oe

Benzene oxidation
7.0
14 H2O + C6H5CH3 7CO2 + 36H+ + 36e

Toluene oxidation
6.9
20H2O + C10H8 10CO2 + 48H+ + 48e

Naphthalene oxidation
6.9
4H2O + C2H3Cl 2CO2 + 11H+ + 10e + Cl

Vinyl chloride oxidation
11.4
12H2O + C6H5Cl 6CO2 + 29H+ + 28e + Cl

Chlorobenzene oxidation
8.0
94
First-order rate constants are often expressed in terms of half-life for the
chemical:
t1 2 =
0.693
k
(3.17)
The first-order decay model shown in Equation 3.16 assumes that the solute
degradation rate is proportional to the solute concentration. The higher the concentration, the higher the degradation rate. This method is usually used to simulate
biodegradation of contaminants dissolved in groundwater. Modelers using the firstorder decay model typically use the first-order decay coefficient as a calibration
parameter and adjust the decay coefficient until the model results match the field
data. With this approach, uncertainties in a number of parameters (e.g., dispersion,
sorption, biodegradation) are lumped together in a single calibration parameter.
Regression methods are commonly used to obtain approximations of site-specific
degradation rates (first-order) from log-linear plots of concentration vs. time. This
involves fitting an exponential regression to approximate the trend in the data. This
type of approximation can be used to evaluate trends at an individual well or for
several wells along a flow path. When individual wells are being evaluated, the
analytical data should be used from multiple sampling events, and the time element
in the plot represents the temporal arrangement of the data. When multiple wells
along a flow path are being evaluated, the analytical data from a single sampling
event can be used; the time element in the plot represents groundwater travel time
between the wells.15
Electron-Acceptor-Limited or Instantaneous Reaction Model: The electronacceptor-limited model (traditionally called the instantaneous reaction model) was first
proposed in 1986 for simulating the aerobic biodegradation of petroleum hydrocarbons.9,16 It was observed that microbial biodegradation kinetics are fast in comparison
with the transport of oxygen and that the growth of microorganisms and utilization of
oxygen and organics in the subsurface can be stimulated as an electron-acceptor-limited
or instantaneous reaction between the organic contaminant and oxygen.
From a practical standpoint, the instantaneous reaction model assumes that the
rate of utilization of the contaminant and oxygen by the microorganisms is very
high, and that the time required to biodegrade the contaminant is very short, almost
instantaneous, relative to the seepage velocity of the groundwater. Using oxygen as
an electron acceptor, for example, biodegradation is calculated using the expression:
C R =
O
F
(3.18)
where
CR = change in contaminant concentration due to biodegradation
O
= concentration oxygen
F
= utilization factor, the ratio of oxygen to contaminant consumed
95
The variable F is obtained from the oxidation-reduction reaction involving the

organic and the given electron acceptor.
Biodegradation of Organic Contaminants: Organic contaminants vary widely
in their susceptibility to transformation by microorganisms. Some contaminants are
highly biodegradable, while others resist degradation. In general, the more degradable contaminants have simple molecular structures (often similar to the structures
of naturally occurring organic chemicals), are water soluble and nontoxic, and can
be transformed by aerobic metabolism (Figure 3.10). In contrast, organic contaminants that resist biodegradation may have complex molecular structures (especially
structures not commonly found in nature), low water solubility or an inability to
support microbial growth, or they may be toxic to the organisms.
Not Accessible
Accessible
Gaseous
Sorbed
Dissolved
Nonaqueous
Figure 3.10
Schematic diagram describing the mechanisms by which a contaminant

becomes available for biodegradation.
Microorganisms can completely convert some organic contaminants to carbon

dioxide and water, while they are capable of only partial conversions of others.
Complete conversion to carbon dioxide is called mineralization. In some cases,
the products of partial conversion are more toxic than the original contaminant. Vinyl
chloride is an example of a highly toxic chemical that results from incomplete
biodegradation of chlorinated solvents.
The following discussion explains how microbial transformations occur for various organic contaminant classes. It describes all of the elements of some metabolic
pathways because these illustrate the core concepts of biodegradation. Biodegradation pathways for most contaminants are extremely complex, so these pathways are
not described in detail.
Petroleum hydrocarbons are a highly varied class of naturally occurring chemicals
used as fuels in a variety of commercial and industrial processes. Biodegradation
potential varies depending on the type of hydrocarbon.
Benzene, Toluene, Ethylbenzene, and Xylene (BTEX): Benzene, Toluene,
Ethylbenzene, and Xylene are components of gasoline. Because of their widespread
use and because BTEX storage tanks commonly leaked in the past, BTEX are
common groundwater contaminants. A large body of scientific research exists on
the biodegradation and natural attenuation of BTEX. However, the effectiveness of
96
MNA via intrinsic bioremediation, as with any other contaminant, depends on the
relationship between the contaminant biodecay rate and the groundwater velocity.
BTEX are easily biodegraded to carbon dioxide by aerobic microorganisms and
can also biodegrade under anaerobic conditions. When the volume of BTEX is small
enough and/or the supply of oxygen is large enough, microbes can degrade all of
the BTEX components within the aerobic zones of a contaminated site. When oxygen
is depleted in an advancing contaminant plume, anaerobic conditions can develop
and lead to the formation of as many as five different downgradient zones, each with
a different terminal electron acceptor (Figure 3.11). In these zones, BTEX degradation processes are slower and less reliable than when oxygen is present.
Source Area
Methanogenic 5
SO4 2-
Fe3+/Mn4+ NO3
Reduction Reduction
4 Reduction
3
Aerobic
Zone
O2
1
Groundwater
Flow Direction
1
Figure 3.11
Encroachment of the
Aerobic Fringe
- Aerobic Zone
2 and 3
- Transient Anaerobic Zones
4 and 5
- Core Anaerobic Zones
Conceptualization of the dominant terminal electron acceptor process (TEAP)

in advancing BTEX plume.
Of the possible electron acceptors, oxygen yields the most energy. Once oxygen
is depleted, nitrate is next as the most energy-yielding terminal electron acceptor.
If nitrate is abundant in groundwater, zones in which microbes use nitrates as the
electron acceptor will develop. A Mn(IV)-reducing zone may develop next if Mn(IV)
is present in the subsurface mineral matrix (although the coupling of Mn reduction
to BTEX degradation has not been well studied). Upon depletion of the Mn(IV),
Fe(III) reduction will prevail if iron oxide minerals are present. In the next zones,
sulfate and CO2 will serve as electron acceptors.
Based on electron acceptor abundance, Fe3+, Mn4+, and SO2
4 reduction by bacteria
may play a dominant role in intrinsic bioremediation under certain geologic conditions.
Both Fe3+ and SO42 reduction processes involve mineral phases and may not be properly understood by evaluating only groundwater concentrations. Fe and S mineral
analyses, from soil samples, should be incorporated in natural attenuation studies,
when the geologic conditions are appropriate. Fe and S mineral analyses may not be
widely utilized in natural attenuation studies because of the inherent difficulty in solid
sample collection, preservation, and analysis of bioavailable minerals.17
L1282_C03-B_frame Page 97 Monday, June 18, 2001 10:07 AM
97
Many field studies of BTEX biodegradation in the subsurface have been carried
out. For example, several lines of evidence indicated that all BTEX components
were biodegrading mainly in the Fe(III)-reducing zone of an aquifer in Bemidji,
Minnesota, that was contaminated with crude oil.18-20 At a petroleum spill site in
South Carolina, toluene, but not benzene, was metabolized as it moved through a
sulfate-reducing zone.1,21 In a recent study of an anaerobic gasoline-contaminated
aquifer in California, researchers injected BTEX components (along with bromide
as a tracer) and either sulfate or nitrate into a sandy aquifer. Periodic withdrawal of
samples from the injected zones showed that under nitrate-reducing conditions,
toluene, ethylbenzene, and m-xylene, (but not benzene) were transformed in less
than ten days. Under sulfate-reducing conditions, toluene, m-xylene, and o-xylene
were completely transformed in 72 days, while benzene loss was uncertain.1,22
During a recent study24 in short term (< 2 weeks) incubations, addition of sulfate
slightly stimulated benzene degradation and caused a small decrease in the ratio of
methane to CO2 production from benzene. However, in long term (>100 days)
incubations, sulfate significantly stimulated benzene degradation with a complete
shift to CO2 as the end product of benzene degradation. The addition of Fe(III) and
humic substances had short- and long-term effects that were similar to the effects
of sulfate amendments.
A novel in situ respiration technique was reported recently to measure and predict
natural attenuation of petroleum compounds in the subsurface. Monitoring CO2 and
CH4 produced in situ, and their radiocarbon (14C), stable carbon (13C), and deutrium
(D) signatures provides a novel method to assess anaerobic microbial processes. The
in situ anaerobic respiration test was conducted by injecting a large volume of
industrial grade Argon, an inert gas, into the subsurface to replace CO2 and CH4,
followed by monitoring the production of CO2 and CH4.23 Figures 3.12a and b show
the formula of BTEX compounds.
H
C
HC
CH
HC
CH
OR
OR
C
H
Figures 3.12a
Benzene formula and simplified representations.
CH 3
CH 3
CH 3
CH 3
Benzene
Figures 3.12b
Toluene
m-Xylene
Structures of single-ring aromatic hydrocarbons.
Ethylbenzene
98
Polycyclic Aromatic Hydrocarbons: In contrast to BTEX, Polycyclic Aromatic

Hydrocarbons (PAHs) biodegrade very slowly. PAH contamination comes mostly
from fossil fuel use and the manufactured-gas industry.1 Groundwater contamination
at manufactured gas plants has persisted for decades because of the slow, continuous
dissolution of PAHs from subsurface coal tar. PAHs are compounds that have
multiple rings in their molecular structure. These compounds have complex molecular structures and low water solubility, and they tend to sorb strongly to solids in
the subsurface. However, because PAHs dissolve slowly, natural attenuation could
control the contamination even if biodegradation is slow, as long as it occurs at the
same rate as or faster than dissolution.
The fate of PAHs in subsurface systems is governed largely by their hydrophobic
nature (the reason for their low solubility and tendency to attach to surfaces). PAH
molecules held within NAPLs or adsorbed to surfaces cannot be biodegraded. Consequently, understanding dissolution and the sorption processes for PAHs often is
the key to understanding biodegradation and natural attenuation potential.
Biodegradation of PAHs depends on the complexity of the chemical structure
and the extent of enzymatic adaptation. In general, PAHs that contain two or three
rings such as napthtalene, anthracene, and phenanthrene are degraded at reasonable
rates when O2 is present. Studies have shown that some microorganisms can metabolize dissolved PAHs composed of up to five benzene rings. Microorganisms generally use oxygenase enzymes to initiate the biodegradation; these reactions require
the presence of oxygen. However, microbial degradation of PAHs with lower molecular weights (fewer benzene rings) can occur under nitrate-reducing and sulfatereducing conditions.28,29
Oxygenated Hydrocarbons: Microbiologists and remediation engineers have
long known that low molecular weight alcohols, ketones, esters and ethers biodegrade readily particularly under aerobic conditions. The polar oxygen atom in MtBE
(CH3OC(CH3)3) causes the molecule to be much more hydrophilic than other
gasoline constituents. However, one prominent oxygenated hydrocarbon methyl tertbutyl ether (MtBE) was thought to be resistant to biodegradation because of its stable
molecular structure and its reactivity with microbial membranes. MtBE has been
used as an octane enhancer in gasoline since the late 1970s and recently has been
used up to 15% by volume.
MtBE has relatively high water solubility (43,00054,000 ppm in comparison
to 1780 ppm for benzene), a very low Henrys Law Constant (0.022 in comparison
to 0.22 for benzene), and very weak sorbtion to soil (log Koc = 1 to 1.1 in comparison
to about 1.52.2 for benzene). Until very recently, MtBE was considered nonbiodegradable in the subsurface; a prestigious state of the science report by the National
Research Council, in the year 2000, stated that present knowledge on MtBE biodegradation is limited . The report further pointed out that the process was not
well understood and therefore the likelihood of success for natural attenuation as a
remediation solution for MtBE contaminated sites was low.1
However, a number of recent studies have demonstrated natural MtBE biodegradation in the field.1,30-34 It is still unclear how prevalent this biodegradation is and
whether the rates are rapid enough to restrict and eventually shrink groundwater
99
plumes. Also, it is unknown if the potential for natural MtBE biodegradation could
be reasonably predicted using some indicator parameters.
A recent study, which included many field sites, suggested that natural biodegradation of MtBE and TBA under anaerobic subsurface conditions at some sites
may control migration of MtBE and TBA plumes. There appeared to be a good
correlation between strongly anaerobic plume biogeochemistry and natural biodegradation of MtBE.35 To date no one has shown MtBE biodegradation in the laboratory
under sulfate reducing conditions. It is important to note from this study that MtBE
and TBA naturally biodegrade only under strongly anaerobic conditions (preferably
under methanogenic conditions) and the rates of biodegradation (at the sites where
this happens) are comparable to those of benzene.35
Chlorinated Aliphatic Compounds: The chlorine atoms added to aliphatic
organic molecules to produce these chemicals significantly change many properties,
including solubility, volatility, density, hydrophobicity, stability, and toxicity. These
changes are valuable for commercial products, but also can make the compounds
less biodegradable. Several good reviews have been published on the biodegradation
of the small (one- and two-carbon) chloroaliphatic compounds.25 The biodegradation
potentials of many chlorinated aliphatics are discussed extensively in Chapter 4.
Researchers first demonstrated the potential for anaerobic biotransformation of
chlorinated aliphatic hydrocarbons during the early 1980s.36 Subsequent studies have
shown that these compounds can biotransform under a variety of environmental
conditions in the absence of oxygen. In general, the biotransformation rates, particularly for chlorinated compounds with more than two chlorine atoms in the molecule,
are higher under anaerobic conditions.
Exceptions to the general rule that chlorinated aliphatic hydrocarbons require
special environmental conditions for biodegradation to occur are methylene chloride,
known also as dichloromethane, and vinyl chloride. Methylene chloride and vinyl
chloride can support the growth of a wide range of microorganisms (both aerobic
and anaerobic) under a range of environmental conditions. Methylene chloride and
vinyl chloride therefore are likely to be treated successfully by natural attenuation
at a much broader range of sites than other chlorinated aliphatics compounds. In
addition to methylene chloride and VC, there are a few other chloroaliphatic compounds which will degrade under aerobic conditions as growth substrates or as
cometabolic substrates.
Natural biotransformation of chloroaliphatics is most likely where excess organic
material is available to serve as an electron donor and biogeochemical conditions
support a reducing environment. Successful intrinsic reductive dechlorination has
been found to occur in the presence of other electron-donating organic pollutants,
such as those from leaking sewage systems, BTEX, and phenol. Reductive dechlorination to VC and ethene appeared to be driven by fuel hydrocarbon co-contaminants
in the center of many mixed contaminant plumes. Down gradient, where carbon
sources became depleted, VC was oxidized further by iron and aerobic oxidation.
When soil organic matter serves as electron donor, reductive dechlorination may
also be observed down gradient of the plume and dechlorination products may
accumulate.
100
Chlorinated Aromatic Compounds: Bacteria able to degrade all but the most
complex chloroaromatic compounds have been discovered during the past 20 years.1,25
Chlorobenzenes including hexachlorobenzene can be sequentially dechlorinated to
chlorobenzene under methanogenic conditions in soil slurries37 (Figure 3.13). Reductive dechlorination of chlorobenzene has not been reported, but chlorotoluenes are
dechlorinated to toluene in the preceding methanogenic systems and it seems likely
that chlorobenzene could serve as a substrate for reductive dechlorination.
Cl
Cl
Cl -
Cl -
Cl -
Cl -
Cl
Cl
Cl
Cl
Cl
Figure 3.13
Cl -
Methanogenic Conditions
Reductive dechlorination of hexachlorobenzene under anaerobic conditions.
Chlorobenzenes up to and including tetrachlorobenzene are readily biodegraded

under aerobic conditions. Bacteria able to grow on chlorobenzene,25,38 1,4-dichlorobenzene,25,38 1,3-dichlorobenzene,25 1,2-dichlorobenzene,25 1,2,4-trichlorobenzene,25 and
1,2,4,5-tetrachlorobenzene25 have been isolated and their metabolic pathways identified. The pathways for aerobic degradation are remarkably similar and lead to the
release of the chlorine as HCl. Chlorobenzenes are very good candidates for natural
attenuation under either aerobic or anaerobic conditions. Aerobic bacteria able to grow
on chlorobenzene have been detected at a variety of chlorobenzene-contaminated sites
but not at adjacent uncontaminated sites,25,39 providing strong evidence that they are
selected for their ability to derive carbon and energy from chlorobenzene degradation
in situ. Removal of multiple chlorines as HCl consumes a large amount of alkalinity
and produces a considerable drop in the pH of unbuffered systems which could lead
to a loss of microbial activity at some sites.
Although the benzene ring that is the nucleus of chlorinated aromatic compounds
is relatively easy for microorganisms to biodegrade, the addition of chlorine atoms
completely alters the biodegradability of benzene. The number and position of
chlorine atoms on the benzene ring determine how biodegradable the compound
will be. Compounds with many chlorine atoms may not be biodegradable at all under
aerobic conditions; however, under special environmental conditions, these compounds can be reductively dechlorinated by the same type of microbial dechlorination process that can occur for chlorinated aliphatic compounds.25,40-42 As the reductive dechlorination process removes chlorine atoms from the benzene ring, the
molecules become more susceptible to biodegradation by aerobic microbes. When
environmental conditions are right, natural attenuation may be able to control halogenated aromatic compounds, but these conditions generally are uncommon.
Chlorophenols and chlorobenzoates are dechlorinated under anaerobic conditions
in sediments and subsurface material.25,43,44 In some instances the dechlorination clearly
yields energy for the growth of the specific bacteria. In other examples the dechlorination is specific and enriched in the community, but has not been rigorously linked
101
to energy production. Addition of small fatty acids or alcohols as electron donors or

sources of carbon can enhance the process of reductive dechlorination.
Aerobic pathways for the degradation of chlorophenols and chlorobenzoates are
initiated by oxygenase-catalyzed attack on the aromatic ring and subsequent removal
of the chlorine after ring fission or hydrolytic replacement of the chlorine with a
hydroxyl group. Bacteria able to grow on chlorophenols and chlorobenzoates are
widely distributed and readily enriched from a variety of sources, indicating a high
potential for natural attenuation. Chlorophenols are unusual among the synthetic
compounds discussed here in that they can be very toxic to microorganisms. They
are often used as biocides; therefore, high concentrations can dramatically inhibit
biodegradation. Inoculation with specific bacteria has been helpful in overcoming
toxicity and stimulating degradation of chlorophenols.25,43
Pentachlorophenol deserves special consideration because it has been widely
used as a wood preservative and has been released into the environment throughout
the world. Reductive dechlorination under methanogic conditions can lead to mineralization.25,43 Aerobic bacteria catalyze the replacement of the chlorine in the 4
position by a hydroxyl group to form tetrachlorohydroquinone. Subsequent reductive
dechlorinations lead to the formation of ring fission substrates. Bacteria able to
degrade pentachlorophenol are widely distributed, and both experimental and fullscale bioremediation projects have been successful in field applications43 (Figure
3.14). Adding selected strains has been helpful in some instances; in others, indigenous strains have been used. Wood treatment facilities typically are contaminated
with complex mixtures of organic compounds; therefore, investigations of toxicity
must be conducted for each site under consideration. Natural attenuation of pentachlorophenol has been reported, because specific bacteria able to use it as a growth
substrate are enriched at contaminated sites. However, rates seem to be low at many
sites due to toxicity and bioavailability of the pentachlorophenol.
Although polychlorinated biphenyl (PCB) use has been banned, these chemicals
are still present in the environment, especially in sediment and aquatic systems, and
their persistence is due in part to their resistance to biodegradation.1,45 PCBs consist
of up to ten chlorine and hydrogen atoms attached to a structure consisting of two
benzene rings attached by a bond between carbon atoms. Chemical synthesis can
create various possible combinations called congeners of chlorine and
hydrogen atoms in the ten positions (Figure 3.15). PCBs were marketed as mixtures
of congeners called Aroclors (the Monsanto Corporation trade name), characterized
according to average chlorine content.
PCBs have been studied extensively because of their stability, toxicity, and
bioaccumulation potential.1,46 Anaerobic transformation of PCBs is catalyzed by
bacteria in aquatic sediment from a wide range of contaminated and uncontaminated
sites. Higher activities in contaminated sites suggest that the dechlorination reactions
provide a selective advantage to the microbial population, indicating the potential
for significant natural attenuation. A number of studies have clearly demonstrated
that natural attenuation of PCB is taking place in anaerobic sediments at significant
rates. Methanogenic conditions in freshwater sediments seem to provide the highest
rates of reductive dechlorination.
Figure 3.14
Cl
Cl
Cl
Cl
Cl
OH
Cl
Cl
Pathways of pentachlorophenol (PCP) degradation.
Cl
Cl
OCH 3
Cl
Cl
OH
Cl
Cl
Cl
Cl
Cl
OCH 3
Cl
Cl
Cl
Cl
Cl
OH
Cl
OH
Cl
OH
Cl
Cl
Cl
Cl
Cl
Cl
Cl
OH
Cl
OH
Cl
OH
Cl
Cl
Cl
HOOC
Cl
OH
Cl
Cl
Cl
Cl
Cl
Cl
Cl
Cl
Cl
Cl
Cl
Ring
Cleavage
COOH
Cl
OH
OH
102
OCH 3
Cl
Cl
OH
Cl
Cl
OCH 3
Ring
Cleavage
CIm
m=1
Figure 3.15
103
CIn
5
n=1
Structure of PCB.
Dechlorination converts the more highly chlorinated congeners to less chlorinated products containing one to four chlorines. Complete dechlorination does not
occur, but the depletion of the more highly chlorinated congeners dramatically
reduces not only the toxic and carcinogenic potential, but also the bioaccumulation
potential. A variety of dechlorination patterns have been identified as a function of
the microbial community involved. The patterns are constant within a given microbial community or enrichment, supporting the premise that dechlorination provides
a selective advantage to the organisms involved. The electron donors for the dechlorination in sediment are unknown. Addition of exogenous carbon sources does not
stimulate the reaction. In contrast, priming the mixtures with low levels of bromobiphenyl or specific isomers of tetrachlorobiphenyl1,46,47 seems to selectively
enrich a population of PCB-dechlorinating bacteria and dramatically stimulate the
dechlorination of other congeners.
The lower chlorinated PCB congeners, whether part of the original Arochlor
mixture or derived from reductive dehalogenation, are biodegraded by aerobic bacteria.25,48 The initial attack is catalyzed by a 2,3- or 3,4-dioxygenase followed by a
sequence of reactions that leads to ring cleavage and accumulation of chlorobenzoates readily degraded by a variety of bacteria. The enzymes that oxidize PCBs
are produced by bacteria growth or biphenyl, and addition of biphenyl to slurryphase reactors stimulates the growth and activity of PCB degraders. Such stimulation
has been shown to be effective in the field. There is also good evidence that aerobic
PCB degradation is taking place in contaminated river sediments.48
It seems clear that reductive dechlorination is ongoing at a wide range of PCBcontaminated sites. The strategy of anaerobic dechlorination followed by aerobic
degradation seems to be particularly effective with PCB whether in an engineered
system or in natural systems occurring during resuspension of anaerobic sediments.
To date, the complete biodegradation of PCB is slow and difficult to predict or
control in the field. Several new strategies, including construction of novel strains,
may increase the potential for effective PCB biodegradation.
Nitroaromatic Compounds: The literature on biodegradation of nitroaromatic
compounds has been reviewed recently.25,49,50 These compounds are subject to reduction of the nitro groups in the environment under either aerobic or anaerobic conditions. Reduction does not lead to complete degradation in most instances and could
104
be considered nonproductive for purposes of natural attenuation. In contrast, aerobic

bacteria able to grow in nitrobenzene, nitrotoluenes, dinitrotoluenes, dinitrobenzene,
nitrobenzoates, picric acid, and other nitrophenols have been isolated from a variety
of contaminated sites, suggesting that natural attenuation is taking place. Mineralization of dinitrotoluenes in aquifer material from a dinitrotoluene-contaminated site
was measured recently.51 It was concluded that the indigenous microorganisms
provide a significant degradative capacity for the contaminant.
The simple nitroaromatic compounds can be considered excellent candidates for
natural attenuation as long as the degradation process yields a selective advantage.
Some of the compounds, including 3-nitrophenol, nitrobenzene, 4-nitrotoluene, and
4-nitrobenzoate, are degraded via catabolic pathways that minimize the use of
molecular oxygen and are particularly well suited for operation in the subsurface
where oxygen is limiting. The pathways all involve a partial reduction of the molecule prior to oxygenative ring fission. For example, the first three steps in the
pathway for degradation of nitrobenzene can take place in the absence of oxygen,49
which is required only for ring fission and subsequent metabolism.
Mixtures of the isomeric nitro compounds can be problematic for microbial
degradation. For example, the industrial synthesis of polyurethane produces large
amounts of 2,4- and 2,6-dinitrotoluene in a ratio of 4:1. Bacteria able to grow on
2,4-dinitrotoluene have been studied extensively. Unfortunately, 2,6-dinitrotoluene
inhibits the degradation of 2,4-dinitrotoluene and may prevent natural attenuation.
Bacteria able to grow on 2,6-dinitrotoluene have been isolated recently, and insight
about the metabolic pathway might allow better prediction of degradation of the
mixture.25
Nitroaromatic organic contaminants are associated uniquely with military activities and include the explosives trinitrotoluene (TNT), royal Dutch explosive (RDX
or hexahydro-1,3,5-trinitro-1,3,5-triazine), and octahydro-1,3,5,7-tetranitro-1,3,5,7tetrazocene (HMX).25 Manufacturing, loading, storage, and decommissioning operations have generated large quantities of explosive wastes, some of which were
deposited in soils and unlined lagoons and subsequently leached to groundwater.
Despite the number of sites contaminated with explosives, only a few rigorous
field studies have been conducted to determine the transport, fate, and influence of
microbial activity on explosives. Furthermore, the field studies carried out to date
are inconclusive in establishing the role of biodegradation in the fate of nitroaromatics.25,51 Laboratory studies clearly show the potential for microorganisms to
metabolize nitroaromatic compounds.2,49,51,52 However, microbes apparently cannot
readily use TNT, RDX, or HMX as primary substrates for sources of the carbon and
energy needed for their growth. Instead, cometabolic reactions generally prevail.1,49
Under aerobic and anaerobic conditions, microorganisms routinely reduce the nitro
groups on nitroaromatics to amino nitro groups. These changes can increase toxicity
of the molecules and cause them to form polymers, and/or strongly sorb onto soils.1,52
Recent reports have shown that aerobically and anaerobically grown bacteria can
use TNT and RDX as nutritional nitrogen sources,2,53,54 but metabolic byproduct
accumulation is common. The possibility of natural attenuation of nitroaromatics
cannot be precluded, but the kinds of conditions needed are not clearly understood.
105
Nitrate Esters: A variety of nitrate esters including glycerol trinitrate, pentaerythritol tetranitrate, and nitrocellulose have been used extensively as explosives.
Recent studies have indicated that the nitrate esters can be degraded by bacteria
from a variety of sources.25,55,56 Bacterial metabolism releases nitrite which can serve
as a nitrogen source and yield a selective advantage for the organisms. The biodegradation of nitrate esters has only recently been studied extensively and little is
known about degradation in the environment. The recent laboratory results show
considerable promise that natural attenuation is possible, but more information is
needed on the bioavailability, toxicity, and kinetics of the process.
Pesticides: Most pesticides used in the past 20 years in the U.S. have been
formulated to degrade in the environment, and a considerable amount of information
is available on degradation kinetics in soil and water. The U.S. Environmental
Protection Agency Risk Reduction Engineering Laboratory in Cincinnati, OH has
developed an extensive Pesticide Treatment Database that contains information on
a variety of compounds.25 Many pesticides hydrolyze and yield compounds that
serve as growth substrates or sources of nitrogen or phosphorus for bacteria.
Enhanced degradation of pesticides has been studied extensively25,57 and is closely
related to natural attenuation. For example, carbamates,25,57 chlrophenoxyacetates,25
dinitrocresol, atrazines,25 and some organophosphates serve as growth substrates for
bacteria and would be good candidates for natural attenuation. A variety of other
pesticides are hydrolyzed by extracellular enzymes derived from soil bacteria but
provide no advantage to the organisms that produce the enzymes. Similarly, some
of the organohalogen insecticides can be reductively dehalogenated but provide no
advantage to specific organisms. Their biodegradation rates are proportional to the
biomass and activity in the soil. Other organohalogens, such as lindane, can serve
as growth substrates for specific bacteria,25,58,59 but such bacteria seem not to be
widely distributed (Figure 3.16).
Microbial Transformation of Inorganic Contaminants: Many research reports
have documented that microorganisms can transform inorganic contaminants.1 However, unlike organic compounds, which microbes can destroy completely to CO2,
H2O, and other innocuous products, most inorganic contaminants can be changed
only to forms with different solubilities and mobilities. Microbial reactions can lead
to precipitation, volatilization, sorption, or solubilization of inorganic compounds.
These outcomes can be the direct result of enzymes produced by the microbes, or
they can be the indirect result of microbiological production of materials that alter
the biogeochemical environment.
One nearly universal means by which microorganisms lower concentrations of
inorganic contaminants in water is adsorption to the microorganisms themselves.
Adsorption can be caused by electrostatic attraction between the metals and the
microbes or by highly specific scavenging systems that accumulate metals to high
concentration within the cells.1,60 Although sorption to microbial biomass probably
cannot be harvested from the subsurface, which would be required to prevent later
release of contaminants, it is not likely to be a major factor in natural attenuation.
Metals: Microbial effects on metals vary substantially depending on the metal
involved and the geochemistry of the particular site. The behavior of many toxic
metals depends on the microbially mediated cycling of naturally occurring elements,
106
Cl
Cl
Cl
Cl
Cl
Cl
Cl
Cl
Cl
Cl
- 3,4,5,6,- tetrachloro
cyclohexane
Lindane
Cl
Cl
Cl
Cl
Metabolites
Cl
Figure 3.16
Pathways of lindane degradation.
especially iron and manganese. The possible fates of chromium and mercury illustrate the variable effects of microbially mediated reactions on metals.
Chromium: As with many metals, the effects of microbial transformation on
chromium vary with its chemical form (technically, its oxidation state). In groundwater, the predominant form of chromium is the oxidized form, Cr(VI), present as
chromate (CrO42 ) and dichromate (Cr2O72 ) ions. Cr(VI) (known as hexavalent
chromium) is toxic and mobile. Reduced chromium, Cr(III), is less toxic and less
mobile because it precipitates as Cr(OH)3 at groundwater pH values of 4.5 to 10.5.
A variety of aerobic and anaerobic microorganisms enzymatically reduce Cr(VI) to
Cr(III), but the physiological reason for this ability has not been adequately investigated. Among the hypotheses explaining these reduction reactions are detoxification (to move Cr away from the cells), cometabolism (fortuitous enzymatic
107
reactions), and the use of Cr(VI) as a respirator electron acceptor. Microbes also
may cause indirect reduction of Cr(VI) by producing sulfide, Fe(II), and reduced
organic compounds because Cr(VI) reduction occurs spontaneously in the presence
of these substances. Regardless of the mechanism involved, natural attenuation that
relies on chromium reduction requires environmental conditions that strongly favor
the reduced form of chromium.
Mercury: Mercury is sometimes present in soils and sediments at contaminated
sites in the form of mercuric ion, Hg(II), elemental mercury, Hg(0), and the biomagnification-prone organic mercury compounds monomethyl- and dimethylmercury
(both of which can accumulate at hazardous levels in the food chain). All microbial
transformations of mercury are detoxification reactions that microbes use to mobilize
mercury away from themselves.1 Most reactions are enzymatic, carried out by
aerobes and anaerobes, and involve uptake of Hg(II) followed by reduction of Hg(II)
to volatile forms (elemental Hg(0) and methyl- and dimethylmercury) or the formation of highly insoluble precipitates with sulfide. In general, natural attenuation based
on microbial mercury reduction and volatilization seems implausible because the
volatile forms remain mobile, although immobilization as Hg(II) sulfides may be
possible if the electron donors needed to sustain the microbial production of enzymes
and the sulfate needed for precipitation are present together.
Nonmetals: Arsenic is a relatively common toxic groundwater contaminant, due
both to its use in industry and agriculture and to its natural weathering from rocks.
Arsenic can exist in five different valence states: As(-III), As(0), As(II), As(III), and
As(V), where the roman numerals indicate the charge on the arsenic atom. Depending on its valence state and the environment in which it exists, arsenic can be present
as sulfide minerals (e.g., As2S3), elemental As, arsenite (AsO2 ), arsenate (AsO43 ),
or various organic forms that include methylated arsenates and trimethyl arsine. The
two most common forms of arsenic in natural systems are arsentate As(V) and
arsenite As(III). As(V) is less soluble and less toxic than the more soluble As(III)
form. The more oxidized arsenate would be expected as the dominant form in aerobic
surface waters, and arsenite may be the dominant form in reduced groundwater
systems. As(V) (arsenate), like phosphate, exists mainly in its deprotonated forms
at natural pH levels, and so is readily adsorbed onto the positively charged surfaces
of minerals such as Fe(III) oxides. The more toxic aresenite exists primarily as a
neutral dissolved species at pHs typical of natural systems, and its transport is
therefore not as much retarded by sorption onto oxide surfaces. Half times for
oxidation of an arsenite in the presence of Mn(IV) oxides in laboratory experiments
have been measured as 1020 min, compared to 17 h in natural systems and 8760
h for solution of arsenite and dissolved oxygen without Mn oxides. Arsenic speciation in natural systems is not consistent with thermodynamic equilibrium and the
kinetics of redox conversions of arsenic are relevant to its fate and transport.
Microorganisms can transform arsenic for one of several physiological reasons.
Under anaerobic conditions, microbes can use As(V) as a terminal electron acceptor.
Under aerobic conditions, oxidation of reduced As (e.g., arsenite) generates energy
for microbes. Under anaerobic and aerobic conditions, microbes transform arsenic
by methylation, oxidation, or reduction mechanisms that mobilize it away from
108
microbial cells. However, microbial transformation of arsenic is not promising

because this element can exist in many mobile forms.
Selenium, another nonmetal, is used in a number of commercial and industrial
processes (including photocopying, steel manufacturing, glass making, and semiconductor manufacturing) and is sometimes present at contaminated sites. Selenium
contamination has also resulted from irrigation practices that led to the accumulation
of selenium dissolved from soils. Although selenium is an important micronutrient
for plants, animals, humans, and some microorganisms (largely because of its role
in some key amino acids) when present at very low concentrations, it is toxic at
higher concentrations. In natural environments, selenium has four inorganic species:
Se(VI) (selenate, SeO42 ), Se(IV) (selenite, SeO32 ), Se(0) (elemental selenium), and
Se(-II) (selenide) and exists primarily as the two soluble species, Se(VI) and
Se(IV).1,61 Like arsenic, selenium also has many volatile organic forms. Reduced
inorganic selenium compounds can be oxidized under aerobic conditions, although
the oxidation does not support microbial growth. Oxidized selenium (selenate) can
serve as a final electron acceptor for anaerobic microorganisms, resulting in production of selenide and/or elemental Se. Methylation of the various selenium compounds
is a detoxification mechanism that mobilizes Se away from microbial cells, but
methylselenium is mobile and highly toxic to mammals. Anaerobic microbial reduction of selenate and selenite to insoluble elemental selenium can immobilize and
remove Se from aqueous solution. Nonetheless, given the complex chemical and
biological processes that influence the fate of selenium and its many mobile forms,
microbial reactions are not a promising means for controlling Se contamination.
The speciation of Se in natural systems is dependent on the redox potential, pH,
microbial interactions, solubility, complexing ability of soluble and solid ligands,
and reaction kinetics. Se(VI) (selenate), the predominant water soluble Se species,
mainly occurs in well aerated alkaline soils of higher redox potential, while Se(IV)
selenite occurs mostly in natural systems of moderate or reduced redox potential.
Although both ions are highly water soluble, the higher adsorption properties of
Se(IV) make it less mobile in the subsurface than (Se(VI). Overall the redox status
appears to be the most predominant controlling factor over Se speciation.61
Oxyanions: Oxyanions are water-soluble, negatively charged chemicals in which
a central atom is surrounded by oxygen. Nitrate (NO3 ) is one such oxyanion. It can
come from natural sources or human sources including nitrogen fertilizers. Although
NO3 can occur naturally, it is a serious health concern at high concentrations because
it can cause the respiratory stress disease methemoglobinemia in infants and because
it can produce cancer-forming nitrosamines.
The major microbial process that destroys nitrate is reduction to nitrogen gas
(N2) via a process called denitrification. Microbes can use nitrate as a terminal
electron acceptor when oxygen is not available. The denitrification process has been
ongoing for millions of years and is widespread among microorganisms; it occurs
reliably in every anaerobic habitat with abundant carbon and electron sources.
Natural attenuation by denitrification is possible, as long as the supply rate of an
electron donor is sufficient to sustain the reaction. Many organic compounds, as
well as H2 and H2S, can serve as the electron donor.1
109
The oxyanions chlorate (C1O3 ) and perchlorate (C1O4 ) or their precursors

(chlorine dioxide, hypochlorite, and chlorite) are produced by a variety of paper
manufacturing, fertilizer, water disinfection, aerospace, and defense industries.
Although not naturally occurring, these highly oxidized forms of chlorine are energetically favorable electron acceptors for microorganisms. Knowledge of chlorate
and perchlorate biodegradation reactions is quite limited compared to understanding
of denitrification.61 However, laboratory studies using bacterial cultures and environmental samples (soil, freshwater sediments, and sewage) have shown that microorganisms can reduce perchlorate and chlorate when supplied with common electron
donors (such as carbohydrates, carboxylic acids, amino acids, H2, or H2S). Reducing
perchlorate and chlorate generates nontoxic chloride iron.1,61 Microbial transformation of perchlorate or chlorate is plausible if the supply rate of electron donors is
adequate.62
3.5
MONITORING AND SAMPLING FOR NATURAL ATTENUATION
At long last, natural attenuation has come into its own. Over the past five years,
great strides have been made in conceptualizing natural attenuation and developing
protocols, field methodologies, guidance documents, and strategies for implementation. However, the most important aspect of a monitored natural attenuation (MNA)
evaluation at a site is the need to collect biogeochemical and groundwater quality
data of the highest quality to predict the natural attenuation capacity of the system.
As typically practiced, natural attenuation studies place heavy emphasis on quantifying aqueous-phase electron acceptors, contaminants, and byproducts by sampling
groundwater in monitoring wells. In response to this need, a number of companies
offer multiparameter, in situ and down-hole groundwater quality field monitoring
devices that can facilitate the collection of the biogeochemical information.
It can be easily concluded that groundwater samples from zones in which contaminants are being naturally biodegraded are often in dramatic nonequilibrium with
ambient conditions. Furthermore, contact of these samples with the atmosphere can
cause significant shifts in aqueous biogeochemistry. The key to minimizing or
avoiding shifts in the biogeochemistry of reduced samples, in particular, is minimizing contact with atmospheric air. Associated sampling considerations to avoid
include the following:
Purging wells at a high rate may lower the water level in the monitoring well.
During recharge, there is significant contact between the groundwater and the
atmospheric air as the groundwater trickles into the well.
Use of a bailer for sample collection results in exposure of the sample to the
atmospheric air as the sample is poured into the sample bottle.
Sample holding times, typical with many commercial laboratories, offer the opportunity for changes in the biogeochemistry of the sample.
Other than samples for volatile organic compounds (VOCs) analysis, groundwater
samples are often collected in such a way that there is headspace in the sample
bottle. Agitation of the sample bottle during handling and shipping may result in
mixing and thus altering of biogeochemistry.
110
Since many of the commonly employed groundwater sample collection techniques in the past presented varying degrees of contact between the sample and the
atmosphere, an inherent concern always exists regarding the reliability and representativeness of results obtained through these sampling methods for the biogeochemical parameters of interest. During the past few years, a low-flow, minimal
aeration method has evolved which produces the most representative samples for
parameters particularly sensitive to artificial aeration and resulting changes in biogeochemistry. This method involves slow purge rates, a down-hole pump, a flow
cell for probe measurements, and a sample-bottle filling procedure that minimizes
sample aeration (Figures 3.17 and 3.18). Various studies have reported that the lowflow, minimal aeration method using the Grundfos pump produces the most representative results for most parameters. Minor biases in the results of methane, dissolved iron (Fe2+), and sulfide are possible.
Many devices have been developed to collect data in situ (down-hole); consequently, data errors related to sampling artifacts associated with above-ground data
collection and sequential parameter measurements can be avoided. Furthermore,
because many of these units can be coupled to automatic data recorders that provide
for immediate data collection and storage in the field and subsequent data transfer
to personal computers in the laboratory, errors related to data transcriptions can also
be eliminated.
Meter
3-Way
Valve
Probe
Flow Cell Probe
Measurement Device
Fill to Overflowing
With Discharge
End of Tube
Fully Submerged
Valve for Additional

Regulation of Pump
Discharge Rate
Flexible Tube
Beaker
(for Probe
Measurement)
or Sample Bottle
Water Table
Monitoring Well
(2" or Greater)
Slow Purge Rate

to Minimize Water
Table Drawdown
Submersible
Pump
Figure 3.17
Schematic of minimal aeration, low-flow groundwater sampling technique.
111
Atmosphere
O2 = 21%
CO2 = 0.03%
CH4 = 0%
O2
(Eh )
Anaerobic, Reducing
Groundwater
0.5
DO
Fe2+ = 10 - 50 mg/L
CH4 = 2 - 20 mg/L
Alkalinity = 500 mg/L
Figures 3.18
CO2
CH4
Fe2+
Fe(OH)3
Precipitate
Geochemical consequences due to atmospheric interferences during sampling.
Field portable meters capable of measuring (DO) concentrations are available

from a variety of manufacturers. These instruments can record DO levels in fresh
water or saltwater and most are equipped to make temperature and salinity corrections. Oxidation/reduction potential (ORP, Eh, or REDOX) can be difficult to measure even with the best available instrumentation. The sensing device (most often a
platinum electrode in a circuit with a standard reference electrode) may be unstable
in fresh waters with low ionic strength. The time required to obtain a stable reading
may be quite long in some cases. Although it is possible to measure REDOX in the
field, considerable operator skill and experience are necessary to obtain accurate
results.
Two types of field measurements for DO and REDOX are possible with the
current generation of water quality instrumentation: on-site and in situ. On-site refers
to measurements in which a water sample is removed from the aquifer or body of
water and a sensor immediately placed in it for measurement. Great care is taken
to isolate the sample from the atmosphere. In situ or down-hole sensors refer to
measurements made by lowering the probe directly into the well or surface water
at the desired depth. After a suitable equilibration time, continuous monitoring of
water quality can be performed.
Two types of on-site measurements are available: discrete sampling and flowthrough sampling. Discrete samples are collected in the appropriate sample container
(e.g., 300-mL biological-oxygen-demand (BOD) bottles or other suitable glassstoppered bottles capable of preventing entrainment of atmospheric oxygen). The
DO or REDOX sensor is then placed in the sample for measurement. Flow-through
cells incorporate the sensor in a cell in line with a pump. DO and/or REDOX and
other primary water quality parameters are continuously monitored as the water
flows through the cell. The flow-through technique provides immediate results and
minimizes problems resulting from the collection and transport of samples to an onsite laboratory or measurement station.
112
Two types of in situ measurements are available: short-term continuous monitoring and long-term continuous monitoring. Once calibrated, positioned at the
desired depth, and equilibrated to the sample conditions, most probes can send
continuous readings to surface instrumentation. Meters may display or log these
results for a short period of time. A probe designed for long-term monitoring
incorporates features to allow it to be anchored in place and operated unattended
for long periods of time. Long-term monitoring can be useful in evaluating groundwater quality before and during corrective action.
The membrane electrode has been used to monitor DO levels for a long time
during site characterizations. Dual DO/REDOX measurements can be complementary. If REDOX measurements indicate a negative or reducing environment, the
corresponding DO reading should be low (e.g., <1 mg/L). In situ DO/REDOX
measurements can also be used to evaluate stratification in an aquifer.
Despite their data-collection virtues, however, it is important to realize that such
units, especially when they are leased, can collect inaccurate data if certain precautions and procedures are not followed prior to and during their use in the field.
Therefore, the following sections provide considerations and recommendations
regarding the use of such multiparameter, groundwater quality field equipment
designed to maximize the accuracy of biogeochemical data collected. It is very
important that the field technician has considerable experience with general field
monitoring equipment and procedures to avoid human bias and that he or she has
been afforded the opportunity to become familiar with the multiparameter monitoring system to be used.
Equipment consideration: Many firms that lease multiparameter monitoring units
will calibrate the sensing electrodes in the laboratory prior to shipment to the end
user. As a consequence, the remediation engineer is typically told that field calibrations of the sensors in the unit are unnecessary. However, there are two considerations
with respect to the as-received accuracy and utility of the monitoring system. First,
the previous user may have subjected the equipment to severe groundwater environments, improper handling, and inadequate cleanup. If those conditions are not
completely corrected by the vendor prior to shipping, erroneous readings can be
collected. Second, the monitoring system may have been subjected to harsh treatment
during shipping such that the calibrated function of one or more of the parameters
has been seriously altered or perhaps completely eliminated. As a consequence, it
is a good practice to follow the instructions specified to ensure proper system
function and to maximize the probability that the key electrode sensors are indeed
providing accurate field measurements.
Initial system checkout: Upon receipt of the monitoring equipment, it should be
carefully unpacked and inspected for signs of damage or fouling. Inspect both the
meter housing for cracks or blemishes and the electrode sensing unit to verify it has
been properly cleaned. Expose the electrodes in the sonde according to the manufacturers directions and verify that each electrode is intact and has been properly
packaged for shipment. Also inspect the cable between the meter and the sonde for
damage or contamination. If any evidence of equipment damage is identified, immediately contact the vendor and evaluate the need for a replacement unit.
113
Otherwise, attach the cable to the meter, place the sonde in a beaker of distilled
water or tap water, and turn on the system. Within moments, the unit typically
performs an internal system checkout and the readouts for the different parameters
should become activated. If necessary, scroll through the different parameter readouts
to verify proper function and reasonable readings. If any spurious readings are
observed, one or more of the electrode sensing units may be experiencing problems.
Check to make sure the suspect electrode is firmly attached to the sonde. If spurious
readings are still observed, contact the vendor for technical advice and evaluate the
need to replace the unit.
Response time is the most important quality control check to be made in the
field for DO/REDOX systems. It is used to determine the condition of the electrodes,
especially those in water with high contaminant concentrations, dissolved inorganic
salts, sediments, and other insoluble material. Fouling of the sensing electrodes is
the most likely cause of errors in measurement of DO/REDOX.
3.5.1
Dissolved Oxygen (DO)
Electrode inspection and membrane replacement: The user should inspect

the membrane covering the DO electrode in the sonde for any bubbles that may
have formed beneath the membrane during shipment. Although an unlikely development with the current generation of DO electrodes, if any bubbles are present
beneath the membrane, spurious DO readings are likely to result. Consequently, if
any bubbles are observed, the membrane must be replaced using the materials and
instructions provided in the field kit supplied with the multiparameter unit. Once a
membrane has been properly replaced, the electrode should be immersed in distilled
water for a minimum of five minutes prior to field use to allow the new membrane
to equilibrate. After the membrane has been checked, verify the proper function of
the DO sensing system by turning on the meter and placing the sonde in a beaker
of aerated, room temperature (20C) tap water and observing the DO readout on
the meter. After about two minutes, the DO reading at sea level should be about 9
mg/L. Refer to the table provided in Appendix B to determine the appropriate DO
reading for the altitude of interest and the current barometric pressure.
Probes designed to detect DO consist of reference and sensing electrodes
immersed in supporting electrolyte and separated from the sample solution by a
selective membrane (Figure 3.19). The oxygen sensor consists of the membrane and
a closely fitted electrode. The sensing electrode is considered the cathode where
molecular oxygen is reduced, and the reference electrode is considered the anode.
Only species that can permeate the membrane and are reduced at the sensing
electrode will produce a signal, resulting in the highly selective and sensitive nature
of the DO sensor. The cell current is linearly proportional to the DO concentration
and can be converted to concentration by simple calibration procedures.
Several types of DO sensor designs are available; the most commonly used
electrode is the polarographic (commonly called the standard) electrode. This probe
utilizes an applied potential to reduce molecular oxygen and requires circulation of
the water being analyzed. If the water is not moving at about one foot per second,
an error in DO concentration will result. The error is caused by the buildup of a
Figure 3.19
Permeable Membrane
Permeable Membrane
Principle of measurement of dissolved oxygen.
Cathode (Gold)
Cathode (Silver)
Polarographic Electrode
KCI Electrolyte
Alkaline Electrolyte
114
DO Cell of Galvanic Type
Anode (Lead)
e - (Applied Voltage)
Anode (Lead)
e - (Spontaneous Reaction)
115
concentration gradient in the vicinity of the DO membrane as oxygen is consumed

by the sensor. Circulation of the water replenishes the sample near the sensor.
The galvanic cell (Figure 3.19) is less commonly used for detecting DO. The
voltage detected by this type of probe is produced by the spontaneous reduction of
molecular oxygen at the cathode (analogous to a fuel cell). Because less oxygen is
consumed from the sample, this cell is less sensitive to low water flow. For both types
of sensors, molecular oxygen is reduced by a noble metal cathode fitted closely to the
permeable membrane. Chemical changes that occur in the electrolyte, and on the
surface of the electrode as a result of the chemical reactions in the cell, will eventually
necessitate cleaning the electrode surfaces and changing the electrolyte. There is a
third type of DO sensor which reportedly consumes no oxygen from the sample.
Field Calibrations: On the day of the site visit, obtain the current site specific
barometric pressure and altitude. Upon arrival at the site, the monitoring unit should
be activated and allowed to warm up for at least five minutes before any field
calibrations are attempted. For the highest level of accuracy in DO measurements,
the multiprobe system should be calibrated at the ambient groundwater temperature.
This can be accomplished as follows:
Lower the sonde down a monitoring well or a measuring cell that is uncontaminated and upgradient from the other monitoring wells of interest. Avoid aerating
the groundwater surface during sonde passage into the groundwater. Monitor the
temperature function on the meter and determine when the sonde has attained thermal
equilibrium with the groundwater. This may take over 90 seconds. Remove the sonde
and immediately calibrate the DO electrode using the standard procedure provided
in the operation manual. Because the sonde will tend to maintain the ambient
groundwater temperature during calibration, DO calibration will have been essentially accomplished at the ambient groundwater temperature. Remember to adjust
the calibration procedure to account for the current barometric pressure and the sites
altitude.
For DO calibrations at groundwater sites where low DO conditions are anticipated, the meter and sensing unit should be calibrated at two end points. The first
end point, the higher-end calibrated value, is obtained by following the procedures
provided in the operation manual. The method provides the high-end value because
it calibrates the instrument under oxygen-saturated conditions.
To obtain the low-end calibration value, three different methods are recommended:
For the first method, add one tablespoon of sodium sulfite (Na2SO3) crystals to a
beaker containing 300 ml of tap water. After three minutes, lower the sonde in
the beaker (making sure that the DO electrode is immersed in the solution) and
observe the DO reading. It should descend to 0 mg/L within three minutes. If not,
adjust the meter to read 0 mg/L. After calibration, rinse the electrode with distilled
water.
For the second method, add a cube or packet of bakers yeast to a beaker containing
300 ml of tap water and allow the yeast to dissolve completely. Lower the DO
electrode into the solution and wait three minutes. Again, if the DO reading does
116
not descend to zero after three minutes, adjust the meter to read 0 mg/L. After
calibration, rinse the electrode as before.
For the third method, bring a small bottle of pressurized nitrogen gas to the field.
Attach a small flexible hose to the outlet of the pressure regulator on the nitrogen
bottle and slightly open the regulator. This will allow a slow flow of nitrogen gas
to exit the tubing. Orient the tubing to within two centimeters of the oxygen
electrode to deliver the nitrogen gas directly to the surface of the oxygen electrode
membrane. After three minutes, the DO reading on the meter should decline to 0
mg/L. If it does not, adjust the meter to read 0 mg/L.
Regardless of which method is used to obtain the low-end calibration value, the
calibration should be conducted immediately after the high-end value has been
obtained at the ambient groundwater temperature. If no adjustment to the meter was
required to obtain the low-end calibration value, the DO function of the meter is
now calibrated. If a meter adjustment was required for the low-end reading, immediately repeat the high-end calibration step under ambient groundwater temperature
conditions. The DO function of the meter should now be properly calibrated.
Field Measurements: The sonde should be slowly lowered into the groundwater
of the well until the DO and other parameter sensing devices are immersed in the
groundwater. Again, avoid aerating the groundwater during sonde passage into the
groundwater. The sondes electrodes should be placed at either: 1) the midpoint of
the well screen or, 2) in cases where the water column in the well is shorter than
the length of the well screen, the midpoint of the available water column in the well.
The appropriate depth should be determined by knowing the depths of the upper
and lower ends of the well screen and by obtaining the depth to groundwater in the
well on the day of sampling. The DO measurement should be recorded when the
reading has stabilized, generally within two minutes.
During the collection of field measurements in multiple groundwater monitoring
wells, the DO membrane should be checked after each well monitoring event for
bubbles or organic fouling due to the presence of nonaqueous phase liquids (NAPLs)
or microbial slimes in the groundwater in the monitoring well. If bubbles are
encountered or the membrane is severely fouled with an organic film or microbial
slime, the membrane should be replaced prior to further use.
If only light organic fouling is observed, however, the membrane may be cleaned
by immersing the sonde in a dilute detergent solution and swishing the electrode
around in the solution. For electrodes lightly fouled with microbial slimes, the
electrodes can be disinfected using a 10% solution of denatured alcohol in distilled
water. Once it has been verified that the membrane has been cleaned, it should be
rinsed with distilled water.
Regardless of the presence or absence of organic films, however, for most
groundwater monitoring circumstances, it is good practice to decontaminate the
sonde and any cabling exposed to groundwater. Decontaminate using appropriate,
standard decontamination procedures prior to the using the equipment in each subsequent wells.
3.5.2
117
OxidationReduction (REDOX) Potential (ORP)
The oxidation-reduction potential of groundwater is a measure of electron activity and an indicator of the relative tendency of a biogeochemical system to accept
or transfer electrons. In a very oxidizing environment the activity of electrons is low
and in a very reducing environment the activity of electrons is high. The electron
activity is characterized by using the lowercase p notation (just as in pH).
pe = log [e]
(3.19)
The pe of a surface water at pH 7, in equilibrium with atmospheric oxygen, is

calculated to be 13.6; it decreases to approximately 4 in an environment where Fe3+
reduction takes place and drops to approximately 4 where sulfate reduction and
methanogenic conditions exist. pe can be calculated from the measured concentrations of reactants and products in a REDOX half-reaction (Figure 3.20). A scale
equivalent to pe is the Eh scale, which is expressed in volts and is based on the
determination of electron activity using electrochemical methods. At temperatures
typical of the natural environments:
Eh =
pe
16.7
(3.20)
where Eh is in volts.
Eh is often confused with the closely related REDOX potential or ORP measurement. ORP or REDOX is measured by placing a REDOX electrode into the water
sample; the REDOX electrode is a piece of metallic platinum, which acquires a
more negative potential with respect to its reference electrode under reducing conditions where electron activities are higher (Figure 3.21). ORP is the voltage measured between this REDOX electrode and the reference electrode placed in the same
environment. If the activities of the oxidizing species are greater than those of the
reducing species, a voltage greater than the reference electrode voltage will result.
Although REDOX is temperature dependent, temperature corrections are rarely
performed because of the lack of theoretical knowledge involving the exact nature
of the active species in the sample.
ORP provides a useful, approximate characterization of REDOX conditions in the
aquatic invironment, although it lacks precise theoretical definition. Although ORP
and Eh are both measured in volts (millivolts) and do show some rough correlation,
they are defined quite differently and should not be treated as synonymous.
Electrode inspection: The surface of the oxidation-reduction potential (ORP)
electrode should be inspected and it should be verified that the surface is clean of
any organic or inorganic films. If it appears to be fouled, it can be gently cleaned
using a slightly abrasive cloth dipped in a mild detergent solution as described
previously. After cleaning, it should be rinsed with distilled water.
-300
-5
O2
NO -3
MnO 2
Fe(OH)3
2SO4
Methanogenesis
300
Sulfate Reduction
10
Iron Reduction
600
Approximate range due in part

to variability in reaction/product
concentrations
Manganese Reduction
15
Denitrification
900
Aerobic Respiration
Eh(mV)
118
CO2
Oxidant in Use
Figure 3.20
The REDOX sequence of different electron acceptor reactions catalyzed by

microorganisms.
Laboratory reference checks: ORP sensing systems tend to be quite robust

with respect to maintaining calibration and are typically calibrated by the vendor
prior to shipment to the user. The ORP electrode tends to respond to a linear
fashion over a large range of ORP conditions at groundwater sites. However, where
strongly negative ORP readings are possible, it may be advisable to verify the
proper operation of the ORP function by conducting high-end and low-end ORP
reference checks. In those cases, the proper operation of ORP electrode systems
can be evaluated upon receipt of the monitoring unit using the following two-point
reference check method:
1. For high-end reference value, obtain the ZoBell solution from the vendor or
prepare 125 ml of the solution using the method supplied in many chemical texts
such as Standard Methods. Regardless of whether you purchase or prepare the
solution, make sure you obtain a copy of the ORP temperature table from the
vendor. Immerse the sondes ORP electrode in the solution and observe the ORP
reading on the meter. At 25C, the ORP reading should be +237mV.
Figure 3.21
119
Principle of measurement REDOX.
2. At low-end reference value evaluation can be obtained by using the sodium sulfite
solution prepared for the low-end DO calibration method described previously.
Once the sonde has been immersed in the sodium sulfite solution, the ORP value
should be negative.
If the value observed at the high-end check is considerably different from the
expected value or if the value obtained during the low-end evaluation is positive,
the ORP function may be damaged and the vendor should be contacted for further
guidance or perhaps for meter and/or sonde replacement.
Field measurement: Once the sonde has been lowered to the appropriate depth
in the monitoring well, the ORP measurement can be recorded after it has stabilized,
typically after 90 seconds.
3.5.3
pH
The acidity of a given sample is determined by the concentration of hydrogen

ions present. This concentration is expressed by the pH. The value of pH is usually
expressed by the equation:
pH = log [H+]
(3.21)
120
Although this equation is written in terms of concentration, in fact the quantities

in the brackets should be activity, which may be thought of as corrected concentrations that take into account nonideal effects in aqueous systems. These nonideal
effects arise from electrostatic forces between ions dissolved in the water, and they
increase as the total concentration of dissolved ions, measured as ionic strength
increases.
Electrode Inspection: The pH electrode should be inspected and it should be
verified that any organic or inorganic films are absent. If the electrode appears to
be fouled, the sensing region of the electrode can be gently cleaned using a nonabrasive cloth dipped in a mild detergent solution as described previously. After
cleaning, the electrode should be rinsed with distilled water.
Laboratory Calibrations: There are several standards available for calibrating
a pH electrode. A three-point calibration should be performed using standards
anticipated to bracket the range of pH levels expected to be observed in the field.
For example, for most groundwater situations, calibrations using standard solutions
of pH = 4, 7, and 10 would be appropriate.
Calibrate the pH function using the pH = 7 standard first. At sites where alkaline
conditions are anticipated, calibrate the pH electrode with the pH = 10 standard last.
At sites where acidic conditions are anticipated, calibrate the electrode with the pH
= 4 standard last. Once the calibrations have been completed, rinse the pH electrode
with distilled water. The proper operation and calibration of the pH function has
now been verified.
Field Measurements: pH measurements can be recorded once the pH reading
has been stabilized, typically within 60 seconds.
3.5.4
Filtered vs. Unfiltered Samples for Metals
One of the most hotly contested protocols in the last few years is whether to
fieldfilter samples that are to be analyzed for dissolved metals. While partisans
commonly make the case either for always filtering or always not filtering, two
essential factors lead inevitably to the conclusion that filtering is technically appropriate in most cases and not in others:
Metal concentration data may be used for many purposes, and the data use dictates
whether filtering is appropriate. For example, if direct ingestion from a drinkingwater source is involved, data from an unfiltered sample is appropriate. Alternatively, for assessment of contaminant removal during a remediation project, filtered
samples may be appropriate.
Different hydrogeologic conditions may cause groundwater samples to be turbid,
no matter what well installation, development, purging, or sampling methods are
used. As indicated above, turbid water may give metal concentrations that are not
indicative of the concentrations actually moving in the aquifer and would be biased
high relative to actual dissolved metals transport.
121
3.5.4.1 Field Filtration and the Nature of Groundwater Particulates

Monitoring wells are purged and samples are brought to the surface by pumps
of many types or by bailer. The types of sampling devices and their advantages
and disadvantages are discussed in numerous research papers and regulatory
guidance manuals. For a given well sampling event, one device may be used for
purging stagnant water from the well, while another may be used to take the
sample.
Filtration is most often conducted on samples to be analyzed for metals content.
The distinction is commonly made between a sample to be analyzed for total metals
content (an unfiltered sample) and a sample to be analyzed for dissolved metals
content (a filtered sample). As discussed later, the presence of very small particles
called colloids adds substantial complexity to the discussion of total vs. dissolved
metals content. Many of these colloidal particles typically will not settle out due to
gravitational forces.
Many types of filters are available with regard to both the type of filter apparatus
and the pore size of the filter. Filtration can occur in the open: a water sample is
poured into a filter funnel and the sample is pulled by vacuum through a membrane.
Alternatively, the filtration can occur in a closed system where the sample is pushed
by the sampling pump through its discharge tube and finally through an in-line
filter unit. In either the open or closed system, the filtrate, once through the filter,
is directed into the sample bottle for preservation (usually with nitric acid for metals)
and shipment for analysis.
A wide range of filter pore sizes is available. Since the late 1970s, the most
standard nominal pore diameter used in the environmental business has been 0.45
micrometers (m). Other common filters that have been used in environmental
research and for special applications have pore diameters ranging from 5 m at the
high end to 0.1 and 0.03 m at the low end.
Historically, the groundwater system was viewed as having two parts: the immobile rock/soil phase and the mobile water phase. However, in the recent past, emphasis has been placed on another partially mobile phase colloids in evaluating
contaminant transport. Colloids are very small organic or inorganic particles that
can range from less than 0.1 to 10 m in diameter. The truly dissolved phase has
molecules or polymers that are substantially smaller than 0.1 m. Colloid composition, charge, and aquifer conditions vary considerably through space and time, but
research has shown that particles up to about 2 m in diameter can move with
groundwater.63 Particles at the higher end of the colloid size range may be trapped
by small pore spaces in the soil matrix or settle out due to gravity.
Colloidal particles may be present naturally in groundwater or may be released
from soil or rock surfaces during well installation or sampling or may be deposited
at the bottom of the well due to precipitation of the dissolved metals in the well
volume itself. Even the action of a bailer in a well can substantially increase the
concentration of colloids in a groundwater sample. If the objective of an investigation is to assess the movement of metals in the subsurface, field filtration will
122
remove some intermediate-to-large size colloids that are not mobile under natural
conditions, but have been mobilized near a well due to well installation or sampling
disturbance.
Of special importance is that the standard environmental filter has a pore size
(0.45 m) that is in the middle of the size range where colloids can be expected to
move in the subsurface. This filter does not provide a clean cutoff between dissolved
and colloidal species that are mobile and colloids and larger particles that are not.
As a matter of fact, no single filter pore size could provide the correct cutoff between
mobile and immobile species because aquifer, well, and sampling conditions and
circumstances vary widely. Short of making an intensive research effort for each
project site, until recently there has been no way to accurately distinguish mobile
from immobile particulates. As discussed later, recent research and experience with
low-flow sampling has provided a means, under some circumstances, of retrieving
samples with only dissolved, naturally occurring, and mobile colloids.64,65
Before the installation of numerous monitoring wells at contaminated sites during
the past 20 years, the thinking about groundwater samples was shaped largely by
our experiences with production wells. These wells were installed in true aquifers
that generally, in the case of unconsolidated formations, were composed of relatively
coarse-grained, well-sorted materials with high hydraulic conductivities. These wells
could be readily developed to yield water with low turbidity, so filtration was not
usually needed to obtain a water sample considered representative of formation
water. In addition, filtration to remove any particles was not desirable because water
from such a well was expected to be directly consumed.
Filtration can be considered undesirable because the extra handling in the field
can alter the samples chemistry. Aside from the intended removal of particulates
larger than the pore size of the filter, dissolved or colloidal chemicals in the sample
can adsorb onto the filter membrane or apparatus and the filter pore size may be
altered by particle clogging. Alternatively, ions associated with the filtration system
can leach into the sample, thereby giving false positive results. Finally, the exposure
of a sample to air during filtration can cause metals such as iron to oxidize and
precipitate. These iron precipitates may be stopped by the filter, thereby lowering
the iron concentration in the sample filtrate. The precipitation may also entrain other
metals, resulting again in lowered concentrations in the sample.
3.5.4.2 Reasons for Field Filtration
Many monitored sites are located over aquifers with low hydraulic conductivities.
By definition, an aquifer is a formation that contains sufficient saturated permeable
material to yield sufficient quantities of water to wells and springs. Although the
concepts low hydraulic conductivity and aquifer seem mutually exclusive, as a
regulatory matter, the uppermost aquifer is frequently the most contaminated and
requires intense monitoring. Low hydraulic conductivity formations screened by
monitoring wells may be uniformly fine grained, such as in a silty clay unit. Alternatively, a lower permeable unit to be monitored may be characterized by a wide
array of grain sizes; a common example of such poorly sorted material is glacial
123
till. In either case, fine-grained materials of clay or colloid size (particle diameter
of less than 2 m) will be present.
Monitored formations with low hydraulic conductivities present numerous challenges with respect to an excess of colloids being present in a groundwater sample.
First, such fine-grained formations intrinsically contain numerous small particles.
Second, because of the difficulty of making water flow through the formation,
removal of colloidal particles in the zone around the well through well development
is difficult. The colloid load present in the sample can still be larger than what is in
the formation, even after a substantial well development effort has been made and
the well has been sampled numerous times. In contrast, production wells are developed continuously as large volumes of water are pumped for long periods of time.
Finally, in low permeability materials, water levels are substantially drawn down to
the point that a well may have little or no remaining water in it, even at very low
pumping rates. The drawdown causes a high groundwater gradient near the well,
with the attendant increase in groundwater flow rate in individual pore spaces. The
action of purging and sampling may easily mobilize particles that would not normally
be moving with the groundwater. It should be noted that the expected shearing of
colloidal particles from large soil particle surfaces is proportional to the square of
the groundwater pore velocity.
In many geologic units, large amounts of iron oxyhydroxides are present. If the
REDOX conditions are oxidizing, these oxyhydroxides are in the low solubility
ferric form and are present as coatings on the surfaces of large, immobile aquifer
solids like sand and grains. At low or near neutral pH values, these ferric oxyhydroxide coatings are positively charged and can therefore attract and pull colloidal
clay particles from the groundwater solution. However, if substantial amounts of
natural or contaminant organic matter are present, the REDOX conditions can be
reducing, and the ferric oxyhydroxides convert to the more soluble ferrous form,
which enters the groundwater phase. This combination of soluble ferrous ions and
associated colloidal clay increases groundwater turbidity.
Much of the regulatory literature creates the expectation that, regardless of
geology, if sufficient care is taken, a well can almost always be designed, installed,
and developed so that it produces water with low colloid content, and therefore, low
turbidity. There is also the expectation that well purging will be conducted so that
the water sample will have low turbidity. The most common criterion for acceptable
well construction and development is a well that yields samples with turbidity of
less than five nephelometric turbidity units (NTUs). However, some geologic matrices will yield turbid water to a monitoring well, no matter how proficient the well
installation and development. As discussed more fully in the section on low-flow,
the only recourse in such formations is either to purge and sample a well at a rate
that does not exceed the natural recharge to the well or to use a bailer, which has
its disadvantages.
As a practical matter in tight formations, however, purging and sampling rates
cannot be lowered to the level of natural groundwater flow. Substantial drawdown
and the attendant disturbance to the formation will occur even at the lowest pumping
rate achievable with current technology. Therefore, if low-flow rate sampling is not
124
possible, the next best procedure is to sample at a higher flow rate followed by
sample filtration.
Hydrogeologic and biogeochemical conditions can vary through time at a monitoring location. In addition, sampling method and operator technique can change
during the history of a monitoring program. As a result, the turbidity and metal
concentrations in a series of samples can vary above and beyond the real changes
of concentration in the aquifer. At wells where it is difficult to control the turbidity
and colloid concentration in samples, filtration will help to level out the variations.
Frequently, the ability to track changes in concentration through time is an important
objective of any remediation project. More consistent data will increase the power
of statistical analyses such as trend evaluations.
3.5.5
Low-Flow Sampling as a Paradigm for Filtration
The desire to disturb the aquifer as little as possible has led to research and the
rapid acceptance of minimum aeration, low-flow sampling of wells. Research in the
late 1980s and 1990s has shown that, in many geologic formations, groundwater
moves horizontally through the screened portion of the well and interacts little with
the water standing in the well above the screened zone.64 If the sample is pumped
from the well at a rate that is less than or equal to the natural flow rate through the
screen, no stagnant water from above the screen zone will be present in the sample.
In contrast to traditional well purging techniques with pumping rates of 4 liters per
minute or more, low-flow purging and sampling occurs typically in the range of 0.1
to 1 L/min. Current pump technology allows pumping rates down to about 0.1 L/min;
for wells that yield less than this amount, the low-flow methodology is not as
applicable.
The insertion of a bailer or sampling pump into a well causes substantial disturbance to the water in and around the well. Bailing is particularly troublesome in
this regard; comparison studies show that bailed samples have much higher turbidity
and order of magnitude or more higher-metals concentrations in samples collected
via low-flow pumping rates. As a result, it is essential that low-flow equipment is
used during sampling of MNA parameters.
Low-flow sampling with dedicated pumping equipment has proven to be an
important advance in groundwater sampling. Research and practice indicate that
low-flow samples have lower turbidity and are more representative of formation
water than samples obtained at higher flow rates with bailers or pumps. The lack of
particulates has been demonstrated by showing little change in analyte concentration
when low-flow samples are filtered with membranes ranging in pore size from 0.03
to 5 m in one study65 and 0.1 to 10m in another.64
In conclusion, filtered samples, even those taken with a bailer, have similar
analyte concentrations to unfiltered samples taken by the low-flow methodology,
which is state of the art with respect to collecting samples considered representative
of aquifer conditions.
3.5.6
125
A Comparison Study
During the mid-to late 1990s, filtered and unfiltered pairs of samples were
collected at two study sites by ARCADIS Geraghty & Miller, Inc. The wells and
temporary well points were mostly installed in the shallow, unconsolidated zone,
characterized chiefly by fill (cinders and a variety of other natural and artificial
materials), till, and meadow mat (high natural organic matter). Lithologic logs for
many locations describe the presence of fine-grained materials. REDOX measurements were taken, and because of the presence of dissolved organic matter (both
natural and contaminants), conditions were reducing at a large number of the wells
in portions of both sites. The presence of fine-grained materials and low REDOX
values enhanced the formation of colloids in groundwater.
As part of this study, ARCADIS Geraghty & Miller, Inc. reviewed the 1266 pairs
(i.e., each location multiplied by the number of analytes) of filtered and unfiltered
groundwater sample results. The ratios of filtered (dissolved) to unfiltered (total)
concentrations varied widely from the dissolved concentrations being less than 1%
of the total concentration to cases where the dissolved concentrations were greater
than the total concentration.
Of special note is that dissolved concentrations of only certain metals were
frequently low (10% or less) compared to total concentrations. Aluminum, iron,
copper, chromium, lead, vanadium, and zinc fell into this category. This study
showed that filtered, bailer or high-flow samples give results most similar to the
unfiltered low-flow samples, which are presumably most representative of undisturbed formation water.
A detailed evaluation of the analytical data and geologic conditions revealed that
samples with lower values of dissolved concentrations had the following characteristics:
Higher organic matter concentrations

Low REDOX potentials and reducing conditions
Fine-grained particles in the lithology
Very low yield to the point where they can be pumped or bailed dry
As discussed in detail, filtration has both good and bad aspects. The improved
accuracy and consistency derived from the removal of the large, normally immobile
particles liberated during well installation and sampling outweighs the loss of some
of the smaller particles yielding better overall results.
An important argument for filtration is that the sample results from location to
location and sampling event to sampling event will be more consistent with filtering.
Turbidity and colloid load will vary between samples; by reducing the importance
of this variable through filtration, spatial and temporal relationships will emerge
more quickly. It is these relationships that help to determine the location of a source
area, the effectiveness of a remedial action, or the behavior of dissolved constituents
over time.
Perhaps the most powerful argument for filtration arises from the results of lowflow sampling. When wells are pumped at no more than the rate of natural recharge
126
to the well, analyte concentrations in samples are considered to be the most representative of formation water quality. In cases where low-flow pumping is not practical, the closest results are achieved by filtering samples obtained by bailer or highflow pumps. Unfiltered samples obtained by these methods would be expected to
have a substantially high bias.
In selected cases where there are data collection objectives different from general
site characterization and remediation planning, there may be reason to collect unfiltered samples as well as filtered samples. Furthermore, dedicated, low-flow sampling
equipment may be considered at specific locations if frequent sampling is indicated,
well yield is adequate, and there is no expectation that data from these wells will
need to be compared to data from wells without such equipment.
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47. Bedard, D. L. et al., Stimulation of microbial para-dechlorination of polychlorinated
biphenyls that have persisted in Housatonic River sediment for decades, Environ. Sci.
Technol., 30, 687694, 1996.
48. Flanagan, W. P. and R. J. May, Metabolite detection as evidence for naturally occurring aerobic PCB biodegradation in Hudson River sediments, Environ. Sci. Technol.,
27, 22072212, 1993.
49. Spain, J. C., Biodegradation of nitroaromatic compounds, Ann. Rev. Microbiol., 49,
523555, 1995.
50. Spain, J. C., Ed., Biodegradation of Nitraromatic Compounds, Plenum Publishing
Corp., New York, 1995.
51. Bradley, P. M. et al., Potential for intrinsic bioremediation of a DNT-contaminated
aquifer, Ground Water, 35, 1217, 1997.
52. Funk, S. B. et al., Full scale anaerobic bioremediation of trinitrotoluene (TNT)
contaminated soil, Appl. Biochem. Biotechnol., 5152, 625633, 1995.
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129
53. Binks, P. R. et al., Degradation of hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) by

Stenotrophomonas, Int. Conf. Remed. Chlorinated and Recalcitrant Compds.,
Monterey, CA, May 2225, 2000.
54. French, C. E. et al., Aerobic degradation of 2,4,6-trinitrotoluene by Enterobacter
cloacae PB2 and by pentaerythritol tetranitrate reductase, J. Appl. Environ. Microbiol., 64, 28642868, 1998.
55. White, G. F. and J. R. Snape, Microbial cleavage of nitrate esters: defusing the
environment, J. Gen. Microbiol., 139, 19471957, 1993.
56. White, G. F. et al., Biodegradation of glycerol trinitrate and pentaerythritol tetranitrate
by Agrobacterium radiobacter, J. Appl. Environ. Microbiol., 62, 637642, 1996.
57. Topp, E. et al., Isolation and characterization of an N-methylcarbamate insecticide
degrading methylotrophic bacterium, J. Appl. Environ. Microbiol., 59, 33393349,
1993.
58. Siddartha, K. S. et al., Degradation of alpha-, beta-, and gamma- hexachlorocyclohexane by a soil bacterium under anaerobic conditions, J. Appl. Environ. Microbiol.,
56, 36203622, 1990.
59. Cookson, J. T., Bioremediation Engineering: Design and Application, McGraw-Hill,
New York, 1994.
60. Chen, S. and D. B. Wilson, Genetic engineering of bacteria and their potential for
Hg2+ bioremediation, Biodegradation, 8, 97103, 1997.
61. Dungan, R. S. and W. T. Frankenberger, Microbial transformations of selenium and
the bioremediation of seleniferous environments, Bioremed. J., 3, 171188, 1999.
62. Logan, B. E., A review of chlorate and perchlorate respiring microorganisms,
Bioremed. J., 2, 6980, 1998.
63. Puls, R. W. and R. M. Powell, Transport of inorganic colloids through natural aquifer
material: Implicaitons for contaminant transport, Environ. Sci. Technol., 26, 614621,
1992.
64. Puls, R. W. and M. J. Barcelona, Groundwater Sampling for Metals Analyses,
EPA/540/4-89/001, VSEPA, 1989.
65. Puls, R. W. and R. M. Powell, Acquisition of representative groundwater quality
samples for metals, Groundwater Monitor. Rev., 167176, Summer, 1992.
CREDIT
Materials from pages 100 through 104 contain substantial excerpts from Spain,
J., Synthetic chemicals with potential for natural attenuation, Bioremediation Journal, 1(1): 19, 1997.
CHAPTER
In Situ Reactive Zones

CONTENTS
4.1
4.2
Introduction ..................................................................................................132
Engineered Anaerobic Systems ...................................................................135
4.2.1 Enhanced Reductive Dechlorination (ERD) Systems .....................135
4.2.1.1 Early Evidence..................................................................135
4.2.1.1.1 Biostimulation vs. Bioaugmentation...............136
4.2.1.2 Mechanisms of Reductive Dechlorination .....................138
4.2.1.3 Microbiology of Reductive Dechlorination ...................142
4.2.1.3.1 Cometabolic Dechlorination .........................142
4.2.1.3.2 Dechlorination by Halorespiring
Microorganisms ..........................................144
4.2.1.4 Electron Donors ..........................................................147
4.2.1.4.1 Production of H2 by Fermentation ................149
4.2.1.4.2 Competition for H2 ......................................152
4.2.1.5 Mixture of Compounds on Kinetics.................................155
4.2.1.6 Temperature Effects ....................................................158
4.2.1.7 Anaerobic Oxidation ...................................................158
4.2.1.8 Electron Acceptors and Nutrients .................................158
4.2.1.9 Field Implementation of IRZ for Enhanced Reductive
Dechlorination ............................................................160
4.2.1.10 Lessons Learned .........................................................163
4.2.1.11 Derivation of a Completely Mixed System for
Groundwater Solute Transport of Chlorinated Ethenes ..170
4.2.1.12 IRZ Performance Data......................................................177
4.2.2 In Situ Metals Precipitation .............................................................183
4.2.2.1 Principles of Heavy Metals Precipitation.........................187
4.2.2.2 Aquifer Parameters and Transport Mechanisms ..............195
4.2.2.3 Contaminant Removal Mechanisms.................................196
131
132
4.2.3 In Situ Denitrification.......................................................................197

4.2.4 Perchlorate Reduction ......................................................................199
4.3 Engineered Aerobic Systems .......................................................................200
4.3.1 Direct Aerobic Oxidation.................................................................200
4.3.1.1 Aerobic Cometabolic Oxidation.......................................202
4.3.1.2 MTBE Degradation ..........................................................204
4.4 In Situ Chemical Oxidation Systems...........................................................205
4.4.1 Advantages .......................................................................................206
4.4.2 Concerns...........................................................................................207
4.4.3 Oxidation Chemistry ........................................................................208
4.4.3.1 Hydrogen Peroxide ...........................................................211
4.4.3.2 Potassium Permanganate ..................................................213
4.4.3.3 Ozone ................................................................................216
4.4.4 Application .......................................................................................218
4.4.4.1 Oxidation of 1,4-Dioxane by Ozone................................222
4.4.4.2 Biodegradation Enhanced by Chemical
Oxidation Pretreatment.....................................................223
4.5 Nano-Scale Fe (0) Colloid Injection within an IRZ ...................................223
4.5.1 Production of Nano-Scale Iron Particles .........................................228
4.5.2 Injection of Nano-Scale Particles in Permeable Sediments............231
4.5.3 Organic Contaminants Treatable by Fe (0) .....................................231
References ...................................................................................................233
Oxidation-reduction process plays a major role in the mobility, transport, and

fate of inorganic and organic contaminants in natural waters. Hence, the manipulation of REDOX conditions to create an in situ reactive zone (IRZ) to meet
the cleanup objectives was a predictable evolution .
4.1
INTRODUCTION
The concept of in situ reactive zones is based on the creation of a subsurface

zone, where migrating contaminants are intercepted and permanently immobilized
or degraded into harmless end products. Figures 4.1a and b pictorially describe the
concept of in situ reactive zones (IRZ). The successful design of these reactive zones
requires the ability to engineer two sets of reactions: 1) between the injected reagents
and the migrating contaminants; and 2) between the injected reagents and the
subsurface environment to manipulate the bio-geo-chemistry to optimize the required
reactions, in order to effect remediation. These interactions will be different at each
contaminated site and, in fact, may vary within a given site. Thus, the major challenge
is to design an engineered system for the systematic control of these reactions under
the naturally variable or heterogeneous conditions found in the field.
The effectiveness of the reactive zone is determined largely by the relationship
between the kinetics of the target reactions and the rate at which the mass flux of
contaminants passes through it with the moving groundwater. Creation of a spatially
IN SITU REACTIVE ZONES
133
Source Area IRZ Grid
Contaminant
Plume
Individual
Reactive Zones
Created by
Individual Injection
Points Providing a
Collective In Situ
Reactive Zone
(IRZ) Curtain
Plan View
Figure 4.1a
Pictorial depiction of an in situ reactive zone (IRZ) formation.
Reagent
Contaminant
Zone

Figure 4.1b
Cross sectional view of the creation of an IRZ around an individual injection well
at a selected location.
fixed reactive zone in an aquifer requires not only the proper selection of the reagents,
but also the proper mixing of the injected reagents uniformly within the reactive
zone. Furthermore, such reagents must cause few side reactions and be relatively
nontoxic in both its original and treated forms.
When dealing with dissolved inorganic contaminants such as heavy metals, the
process sequence in a pump and treat system required to remove the dissolved heavy
metals present in the groundwater becomes very complex, operation- and maintenance-intensive, and costly. In addition, the disposal of the metallic sludge, in most
cases as a hazardous waste, is also very cost prohibitive. Therefore, in situ treatment
methods capable of achieving the same mass removal reactions for dissolved contaminants in an in situ environment are evolving and gradually gaining prominence
in the remediation industry.
The advantages of an in situ reactive zone to address the remediation of groundwater contamination are as follows:
An in situ technology enables implementation of most ground treatment processes
and eliminates the expensive infrastructure required for a pump and treat system
with no disposal of water or wastes
134
Inexpensive installation because primary capital expenditure for this technology

is the installation of injection wells at appropriate locations
Inexpensive operation that allows inexpensive reagents to be injected at fairly low
concentrations and, hence, should result in insignificant cost; only sampling
required is for groundwater quality monitoring and performance monitoring
parameters are usually done in the field; remediation of large volumes of contaminated water without any pumping or disposal needs
Can be used to remediate deep sites because cluster injection wells or in-well
mixing systems can be installed to address deeper sites
Unobtrusive because once the system is installed, site development and operations
can continue with minimal obstructions
In situ degradation of contaminants because organic contaminants and a few
inorganics such as NH4+ , NO3 , and CIO4 can be degraded by implementing the
appropriate reactions
Immobilization of contaminants because once the dissolved heavy metals are
precipitated out, the capacity of the soils and sediments is utilized to adsorb, filter
out, and retain inorganic contaminants
Manipulation of the reduction-oxidation (REDOX) potential of an aquifer is a

viable approach for in situ remediation of REDOX-sensitive groundwater contaminants. In addition, various microbially induced or chemically induced reactions also
can be achieved in an in situ environment. As noted earlier, creation of spatially
fixed reactive zones to achieve these reactions is very cost effective in comparison
to treating the entire plume as a reaction zone.
Since the first IRZ for the precipitation and remediation of hexavalent chromium
(Cr6+), was installed in 1993, this technology has advanced by leaps and bounds.1
Currently the application of this technology can be classified into three categories
based on the creation of specific bio-geo-chemical and REDOX environments: 1)
engineered anaerobic systems, 2) engineered aerobic systems, and 3) in situ chemical
oxidation.
The engineered anaerobic systems can be further divided into enhanced reductive
dechlorination (ERD) systems, in situ denitrification, in situ perchlorate transformation, and in situ heavy metals precipitation. The ERD application has been expanded
to many contaminants since the first trichloroethene (TCE) application site. The IRZ
technology has been successfully applied to remediate the following chlorinated
compounds:
Chlorinated ethenes: tetrochloroethane (PCE), trichloroethane (TCE), dichloroethene (Cis 1,2 DCE, and 1,1 DCE), vinylchloride
Chlorinated ethanes: 1,1,2,2 tetrachloroethane (1,1,2,2 PCA), 1,1,1 trichloroethane, (1,1,1 TCA), 1,1,2 trichloroethane (1,1,2 TCA), 1,1 and 1,2 dichloroethane
(DCA), chloroethane (CA)
Chlorinated phenols: pentachlorophenol (PCP), and tetrachlorophenol
Chlorinated pesticides
Perchlorate
In addition, the IRZ technology has been successfully applied to precipitate the
following dissolved metals at contaminated sites: Cr6+, Pb2+, Cd2+, Ni2+, Zn2+, Hg2+.
4.2
4.2.1
135
ENGINEERED ANAEROBIC SYSTEMS
Enhanced Reductive Dechlorination (ERD) Systems
4.2.1.1 Early Evidence

The first microbially mediated reductive dechlorination of PCE and TCE was
observed in the early 1980s, and this study2,3 reported the degradation of PCE to
nonchlorinated end products in an acetate-fed, continuous-flow methanogenic glass
bead column. It appeared that the first step in the degradation pathway was dechlorination to TCE. Further anaerobic oxidation of TCE to carbon dioxide and hydrochloric
acid was suggested. In 19844, further evidence of dechlorination of PCE beyond TCE
came in an experiment where sediments from an aquifer recharge basin were incubated
with PCE and methanol as the electron donor. Significant concentrations of TCE, cis1,2 DCE and VC were observed after three weeks, whereas in sterile controls no
dechlorination had occurred. Another study in the 1980s demonstrated that dechlorination of PCE to VC in a methanogenic column was achievable.5 Similar studies using
13C-TCE, showed that TCE was dechlorinated exclusively to cis-DCE in soil.6
In 1989, the first evidence of complete dechlorination of PCE to ethene under
methanogenic conditions with methanol as electron donor was demonstrated.7
Another study found PCE reduction via ethene to ethane with lactate as electron
donor in a flow-through column filled with a mixture of polluted sediment and
anaerobic granular sludge.8 Meanwhile, numerous publications showed that microorganisms capable of reductively dechlorinating chlorinated ethenes are abundant
in polluted anaerobic environments. (An overview of the biological reductive dechlorination pathway of chlorinated solvents is shown in Figure 4.2.) PCE and TCE are
dechlorinated mainly to cis-DCE, although sometimes trans-DCE and 1,1-DCE have
also been found as products.9,10 However, the formation of the 1,1-DCE is believed
to be a result of abiotic dechlorination in the presence of sulfide.10
Evidence from the earlier studies indicated that the dechlorination of PCE to
cis-DCE was found to be a relatively fast process, whereas, subsequent rates of
dechlorination of cis-DCE to VC and ethene were significantly slower or even
absent.7,11 Dechlorination of 1,1-DCE and trans-DCE was less studied.
In some of the earlier reports and studies the dechlorination of chlorinated
ethenes was often found to be incomplete, both in the laboratory and in field
experiments, resulting in an accumulation of cis-DCE and VC. It was not fully
understood at that time why dechlorination beyond these compounds was problematic, other than raising valid questions regarding the required microbial consortia
for complete dechlorination. During that time (late 1980s and early 1990s) microorganisms capable of dechlorinating DCE and VC had not been isolated yet, although
several enrichment cultures existed. Little was known about the substrate requirements of these bacteria. Later studies reported that PCE dechlorination in a contaminated soil down to ethene was only achieved by adding a complex mixture of organic
electron donors. Significant research was focused, during the early to mid 1990s,
on the microbial ecology that could perform complete dechlorination of PCE to
136
PCE
CT
TCE
cis-1,2 DCE*
1,1- DCE
VC
Ethene
1,1,1-TCE
CF
1,1- DCA
DCM
CA
CM
Acetic Acid
Ethane
CO2, H2O,
CI-
Biotic Reactions
Figure 4.2
Abiotic Reactions
* Primary Reaction
Biological and abiotic degradation pathways of the common chlorinated compounds encountered at contaminated sites (adapted from McCarty and Semprini,
1994; after Vogel et al., 1987, and Wiedermeier et al., 1999).
ethene and the biogeochemical conditions under which this biotransformation could
be achieved.
The choice of a suitable electron donor for the stimulation of in situ dechlorination is still a matter of discussion and may be dependent on local conditions; this
will be discussed in detail in a later section. When hydrogen is assumed to be the
major electron donor for dechlorination, its amendment can only be achieved by
using substrates yielding hydrogen after anaerobic degradation.12 Often, short-chain
organic acids are produced as intermediate products, which may lead to acidification
of the groundwater and soil. Additionally, electron donors that support dechlorination
are generally readily degraded by nondechlorinating microorganisms, leading to
competition for the substrate and excessive bacterial growth in soil pores near the
injection well. As a result, significantly more electron donor mass will be needed
than theoretically necessary to reduce all chlorinated ethenes present to ethene.
4.2.1.1.1 Biostimulation vs. Bioaugmentation
The first level of the treatment hierarchy for chlorinated ethenes is intrinsic
bioremediation, or natural biodegradation, whereby indigenous microflora destroy
the contaminant(s) of concern without any stimulation or enhancements. The second
choice in this hierarchy, biostimulation or enhanced biodegradation, involves stimulating the indigenous microbial populations and thus enhancing microbial activity
137
so that they destroy the target compounds at a rate that meets the cleanup objectives
at the site. At almost every contaminated site a natural population of degradative
microorganisms exists within the contaminated zone; however, specific nutrients,
growth substrates inducers, electron donors, and electron acceptors may be required
to create optimal microbial activity.12 Thus, through the introduction of required
additional reagents, the native degradative microbial population can be stimulated
to grow, multiply, and destroy the target contaminants. Most environments contain
microorganisms able to grow on and destroy a variety of chlorinated compounds;
at some sites, the persistence of these compounds, is not a consequence of the
absence of organisms but rather of the absence of the full set of conditions necessary
for the indigenous species to function rapidly.12 In the past there was a significant
debate among remediation experts whether the microorganisms responsible for
cometabolic degradation and dehalorespiration are ubiquitous. Current belief is that
these organisms are nearly ubiquitous.
When intrinsic bioremediation or biostimulation is not feasible at a given site
due to the absence of an appropriate microbial population, bioaugmentation may be
utilized. Bioaugmentation involves injection of selected exogenous microorganisms
with the desired metabolic capabilities directly into the contaminated zones along
with any required nutrients to effect the rapid biodegradation of target compounds.
Two distinct bioaugmentation approaches have been developed for remediating
chlorinated ethenes. In the first approach, degradative organisms are added to complement or replace the native microbial population. The added microorganisms can
be selected for their ability to survive for extended periods or to occupy a specific
niche within the contaminated environment. If needed, stimulants or selective cosubstrates can be added to improve survival or enhance the activity of the added
organism. Thus, the goal of this approach is to achieve prolonged survival and growth
of the added organisms and degradation of the target contaminants.
In the second bioaugmentation approach, large numbers of degradative bacteria
are added to a contaminated environment as biocatalysts which will degrade a
significant amount of the target contaminant before becoming inactive or perishing.12
Additional microbes can be added as needed to complete the remediation process.
Attempts can be made to increase the production of the degradative enzymes or to
maximize catalytic efficiency or stability, but long-term survival, growth, and establishment of an active microbial population are not the primary goals of this treatment
approach.
In the past, bioaugmentation has been implemented frequently and successfully
only in bioreactors. The conditions in these bioreactors are controlled and quite
different from those in nature, and prior to start-up, no microorganisms are present
anyway. Hence, the addition of enriched cultures is essential. Furthermore, bioreactors are engineered and controlled systems where conditions can be readily altered
or optimized for a particular process and can be designed to promote the multiplication and activity of the inoculated species in contrast to contaminated field sites.
The record of success of in situ bioaugmentation systems for chlorinated compounds has been rather spotty. On the one hand, the initiation or enhancement of
degradation has been reported (far more commonly in samples of the contaminated
environments in simulated laboratory experiments) following the addition of
138
enriched bacterial cultures that can metabolize and grow on chlorinated ethenes. On
the other hand, a number of failures in the field have been reported.
Such reports of failure of bioaugmentation came as no surprise to microbial
ecologists. Without question, a species with a substrate uniquely available to it has
a distinct advantage, yet that advantage may not be sufficient to compensate for
many other traits also necessary for survival, no less multiplication, in a natural
ecosystem. Possessing the requisite enzymes to metabolize a novel compound is a
necessary attribute for the organism, but it is not sufficient for the organism to
succeed. Populations of introduced microorganisms are subject to a variety of abiotic
and biotic stresses, and these must be overcome for these organisms to be able to
express beneficial traits.
The reasons for the frequent failures of bioaugmentation are many:12 limiting
nutrients and growth factors in the uncontrolled natural environment, suppression
by predators and parasites, inability of the introduced bacteria to penetrate significant
space, metabolism of other nontarget organic compounds present, concentration of
the target chlorinated compound too low to support multiplication, and other inhibitory biogeochemical conditions such as pH, temperature, salinity, and toxins.
In summary, the problems usually encountered in scaling up the bioaugmentation
successes achieved in laboratory experiments can be summarized as follows:12
Contaminant rates established in controlled laboratory studies may differ substantially from those in pilot-scale, full-scale, or even other laboratory studies.
Positive biotransformation results from small systems often are not reproduced in
different systems.
Instantaneous biotransformation rates vary widely and in an apparently stochastic
manner, even in well-operated, steady-state systems.
4.2.1.2 Mechanisms of Reductive Dechlorination

Naturally occurring biological processes can degrade organic contaminants in
situ or during transport in the subsurface under aerobic and/or anaerobic conditions.
Microorganisms catalyze degradation reactions to obtain energy for growth, reproduction, and cell maintenance. Useable energy is recovered through a series of
REDOX reactions where the microorganisms act as electron transport mediators
(Figure 4.3). Biologically mediated electron transfer couples the oxidation of an
electron donor (organic compound) with the reduction of an electron acceptor (inorganic or organic) and results in the production of useable energy for microbial
consortia.12,13,14 The bulk electron donor acts as a fuel source for the reactions and
the reactions proceed as long as there is a source of bioavailable electrons. Fuel
sources can be the target chlorinated compounds, native organic carbon, co-contaminants such as fuel hydrocarbons, or organic compounds such as carbohydrates. In
aerobic environments, the chlorinated compounds act as electron donors and under
anaerobic conditions they act as electron acceptors.
There are two primary mechanisms involved in the biodegradation of chlorinated
organic contaminants (Table 4.1). First, biodegradation may be growth-linked and
provide carbon and energy to support growth when the compound is used as primary
(mediator)ox
(bulk)ox
+ ne-
+ ne-
(Contaminant)ox
- ne-
+ ne-
(mediator)red
(bulk)red
Figure 4.3
139
(Contaminant)red
Description of microorganisms acting as electron transport mediators (after

Schwarzenbach et al., 1993).
substrate and directly utilized by the mediating organisms via the processes included
in Category 1. Some chlorinated solvents are used as electron donors and some are
used as electron acceptors when serving as primary growth substrates. When used
as an electron donor (under aerobic and anaerobic conditions) the contaminant is
oxidized. Conversely, when used as an electron acceptor, the contaminant is reduced
via the reductive dechlorination process called halorespiration.17
Table 4.1 Summary of the Categories of Degradation Pathways for Chlorinated Organic
Compounds (Adapted from Wiedemeier et al., 1999)14
Category 1
(used as primary substrate)
Chlorinated
Compound
Tetrachloroethylene
(PCE)
Trichloroethylene
(TCE)
Dichloroethene
(DCE)
Vinyl Chloride (VC)
Trichchloroethane
(1,1,1 TCA)
Dichloroethane
(1,2 DCA)
Carbontetrachloride
(CT)
Methylenechloride
(MC)
Category 2
(used as cometabolic substrate)
Anaerobic
Direct
Direct
Aerobic
Cometabolism
HaloAerobic Anaerobic Cometabolism
(reductive
respiration Oxidation Oxidation (co-oxidation) dechlorination)
X
X
X
X
X
X
X
X
X
In addition to their use as a primary growth substrate, chlorinated solvents can

also be degraded via cometabolic pathways. During cometabolism, microorganisms
gain carbon and energy for growth from metabolism of a primary substrate, and
chlorinated solvents are degraded fortuitously by enzymes present in the metabolic
140
pathways. Cometabolism is a process where the organism receives no direct benefit

from the degradation of the organic compound.13,16 There are two types of cometabolic reactions: co-oxidation and reductive dechlorination, described as Category 2
in Table 4.1. Cometabolic reactions tend to be incomplete and can possibly lead to
an accumulation of more toxic daughter products. To date, vinyl chloride (VC) and
dichloroethene (cis/trans) are the only chlorinated solvents that can be degraded by
all aerobic and anaerobic pathways.15
The predominant mechanism for the biodegradation of chlorinated solvents in
anaerobic environments is reductive dechlorination, whether the organic compound
is a primary electron acceptor (halorespiration) or is cometabolized. Before 1994,
reductive dechlorination was thought to be strictly a cometabolic process because
the organisms that cause these reactions are ubiquitous at most contaminated
sites.14,15 However, research has shown that combetabolic reductive dechlorination
is sufficiently slow and frequently incomplete.15,18 During reductive dechlorination,
the chlorinated solvents act as an electron acceptor and a chlorine atom is replaced
with a hydrogen atom (Figure 4.4).
Cometabolic reduction of the chlorinated solvents is catalyzed by the reductive
dehalogenase and reductase enzymes produced by microorganisms.14,20 Cometabolic
degradation occurs under iron reducing, manganese reducing, sulfate reducing, and
methanogenic environments.21 The enzymes of these reducing microorganisms are
induced to reduce abiotic forms of Fe (III) to Fe (II), Mn (IV) to Mn (II), sulphate
to sulfide or hydrogen sulfide, and carbon dioxide to methane. Electrons are transferred to dissolved contaminants coincidentally during the reducing processes. These
degradation reactions are often incomplete, resulting in an accumulation of toxic
daughter products.
Just as aerobic biodegradation systems utilize oxygen as a terminal electron
acceptor to stimulate microbial activity, oxidative anaerobic systems require other
terminal electron acceptors, such as nitrate or ferric iron (Fe III), to stimulate
biodegradation. Anaerobic oxidation occurs when anaerobic bacteria use the chlorinated contaminant as the electron donor and, in most instances, allow the microorganism to derive useful amounts of energy from the reaction. It has been shown
that vinyl chloride can be oxidized to carbon dioxide, water, and chloride ion via
Fe (III) reduction.22 Significant anaerobic mineralization of DCE, VC, and methylene
chloride also have been reported in the literature.
While in oxidative anaerobic systems the contaminant is used as an electron
donor, in reductive systems highly oxidized contaminants (such as PCE) are used
as electron acceptors. The process begins by supplying excess reduced substrate
(electron donor) to a microbial consortium, i.e., a cooperative community of microbial species (Figures 4.3 and 4.5). The presence of the substrate expedites the
exhaustion of any naturally occurring electron acceptors. As the natural electron
acceptors are depleted, microorganisms capable of discharging electrons to other
available electron acceptors, such as oxidized contaminants, gain a selective advantage. The intricacies of these microbial communities are complex, but recent research
has provided some insight into methods for enhancing populations of contaminantdegrading microorganisms.
141
Electron
Flow
Perchloroethene
CI
e-
CI
C
H2
CI
CI
Trichloroethene
CI
CI
C
CI
C
CI
CI
CI
C
H
+
H ion
(Predominant Biological
Reaction)
cis-1,2,-Dichloroethene
CI
(Limited Biological
Reaction)
1,1-Dichloroethene
+CI
(Limited Biological
Reaction)
trans-1,2,-Dichloroethene
H
C
H
CI
CI
C
H
Vinyl Chloride
H
CI
C
Ethene
h
H
C
C
H
Ethane
H
C
H
H
Figure 4.4
H
H
C
H
Hydrogenolysis reactions of PCE during reductive dechlorination with H2 acting

as the electron donor and the chlorinated compounds acting as electron acceptors (adapted from Vogel et al., 1987, and Wiedermeier et al., 1999).
The reductive dechlorination of PCE to ethene proceeds through a series of

hydrogenolysis reactions (Figure 4.4). Each reaction becomes progressively more
difficult to carry out; subsequently, the DCEs, particularly cis-DCE, and vinyl chloride (VC), tend to accumulate in anaerobic environments under natural conditions
due to the absence of sufficiently reducing conditions.
142
Reducing Conditions
Electron
Acceptor
Processes
ORP
Hydrogen
Generation
Electron Donors
Dissolved
Organic
Compounds
BTEX
Environmental Conditions
Temperature pH
Fermentable
Substrates
Anaerobic
Conditions
Reductive
Dechlorination
Figure 4.5
Pictorial description of the conditions which control reductive dechlorination.
The oxidation-REDOX potential (ORP) affects the thermodynamics of reductive

dechlorination. Microorganisms will facilitate only those oxidation-reduction
reactions that have a net yield of energy. For reductive dechlorination to be thermodynamically favorable the REDOX potential must be sufficiently low, thereby
excluding the presence of oxygen and nitrate as terminal electron acceptors. Furthermore, the presence of nitrate may have an inhibitory effect on PCE dechlorination.23 The REDOX potential range for reductive dechlorination is shown in Figure
4.6. It is important to note that the values of Eh ranges shown in Figure 4.6 and the
values of ORP measured in the field by remediation engineers are not the same.
Both parameters have some correlation and do not represent the same conditions.
Figure 4.5 summarizes the mechanisms and the required environmental condition
for the degradation of chlorinated solvents.
4.2.1.3 Microbiology of Reductive Dechlorination
4.2.1.3.1 Cometabolic Dechlorination
A cometabolic process is defined here as a process in which the compound of
interest (e.g., PCE) is converted by a biological enzyme system or cofactor in which
the compound does not serve as a source of carbon or energy.
Pure Microbial Cultures: Reductive dechlorination is the only biodegradative
conversion known for PCE. This reaction can occur cometabolically or in a metabolic
energy-producing reaction. In both cases, the cofactors of the enzymes involved are
metal-containing porphyrins. Examples25 of acetogenic and methanogenic bacteria that
dechlorinate PCE cometabolically are listed in Table 4.2. In general, acetogenic bacteria
dechlorinate PCE at higher rates than methanogenic bacteria. Metal-containing cofactors have been found to catalyze the in vitro degradation of chlorinated ethenes.24,25
In general, reductive dechlorination rates decrease with a declining amount of
chlorine atoms in the molecule. In vivo experiments with methanogenic and acetogenic bacteria indicate that dechlorination rates are low (0.5 to 235 nmol PCE
143
1,000mV
REDOX Potential (Eh)

in millivolts (mV) at
pH=7 and T=25C
Aerobic
500mV
NO3- Reduction
Mn4+ Reduction
Anaerobic
0mV
Fe3+ Reduction
Possible
Range of
Reductive
Dechlorination
SO42- Reduction
Methanogenic
Optimum
Range for
Reductive
Dechlorination
-500mV
Figure 4.6
Optimal range for reductive dechlorination.
Table 4.2 Examples of Acetogenic and

Methanogenic Bacteria that
Dechlorinate PCE
Cometabolic Dechlorination
Cosubstrate
Methanosarcina sp.
Methanosarcina mazei
Sporomusa ovata
Acetobacterium woodii
Methanol
Methanol
Methanol
Fructose
(mg protein)1 day1), compared with those of halorespiring bacteria25,26 (Table 4.3).
In vivo usually only one halogen atom is removed. An exception is the reductive
dehalogenation of dibromoethene by Methanobacterium and Methanococcus that
yields acetylene as a product.27 However, in many studies the possible formation of
nonchlorinated products during dechlorination reactions was not included in the
carbon balance. Complete dechlorination of PCE to ethene by pure cultures of
acetogenic or methanogenic bacteria has not been observed. This is in contrast to
144
Table 4.3 Examples of Halorespiring Bacteria

Halorespiration
Dehalobacter restrictus
Dehalospirillum multivorans
Desulfitobacterium sp. strain PCE1
Desulfitobacterium sp. strain TCE1
Strain MS-1
Electron Donor
H2
Pyruvate
Lactate
Lactate
Yeast extract
findings with mixed anaerobic cultures in which more extensive dechlorination has
been observed.7,8,27-29 The latter may be due to the interactions between different
microorganisms. Sometimes, however, it is difficult to distinguish between cometabolic and specific dechlorination in these mixed cultures, and often it is not even
clear which microorganisms are responsible for the dechlorination.
The most often observed degradation pathway of PCE is via reductive dechlorination to cis-DCE.10,25,30-32 Several dechlorination rates for chlorinated ethenes have
been reported in the literature, but it is difficult to compare the data because often
the numbers of bacteria involved were not known. Nevertheless, it can be stated that
dechlorination rates in mixed cultures are generally higher than those found for
single acetogenic or methanogenic strains.
There are a few reports on the degradation of PCE by granular methanogenic sludge
from upflow anaerobic sludge blanket reactors. This sludge is enriched with acetogenic
and methanogenic bacteria and contains high concentrations of cofactors. Such bacterial
consortia, therefore, are suitable as a source of cometabolic dechlorinating activity. In
one of these reactors, fed with a mixture of sucrose, lactic acid, propionic acid, and
methanol as primary substrates, granular sludge showed a fast adaptation to high PCE
concentrations. Influent concentrations of 360 to 420 M PCE were completely dechlorinated to ethene.26,33 Average removal rates of 7.6 mol (g VSS)1 day1 were achieved,
with a maximum removal rate of 28.3 mol (g VSS)1 day1. A bacterial consortium in
a similar reactor operated in batch mode converted PCE to TCE, cis- and trans-DCE
and traces of 1,1-DCE with ethanol as the primary substrate.
4.2.1.3.2 Dechlorination by Halorespiring Microorganisms
Halorespiration is a type of anaerobic respiration in which a chlorinated compound is used as a terminal electron acceptor. In this reductive dechlorination
process, which enables the conservation of energy via electron transport phosphorylation, one or more chlorine atoms are removed and replaced by hydrogen. Examples of halorespiring bacteria species are shown in Table 4.3.
Halorespiration, also referred to as dehalorespiration, occurs when the organic
compound acts as an electron acceptor (primary growth substrate) during reductive
dechlorination. During halorespiration, the chlorinated organic compounds are used
directly by microorganisms (termed halorespirators), such as an electron acceptor
while dissolved hydrogen serves as an electron donor:15,34
H2 + C Cl C H + H+ + Cl
(4.1)
145
where C Cl represents the chlorine bond to the carbon in the chlorinated ethene
molecule. Halorespiration occurs as a two-step process which results in the interspecies hydrogen transfer by two distinct strains of bacteria. In the first step, bacteria
ferment organic compounds to produce hydrogen. During primary or secondary
fermentation, the organic compounds are transformed to compounds such as acetate,
water, carbon dioxide, and dissolved hydrogen. Fermentation substrates are either
biodegradable, nonchlorinated contaminants (i.e., BTEX benzene, toluene, ethyl
benzene, and xylenes or sugar) or naturally occurring organic carbon. In the
second step, the nonfermenting microbial consortia utilize the hydrogen produced
by fermentation for halorespiration.35,36 Denitrifiers, iron reducers, sulfate reducers,
methanogens, and halorespirators can all utilize hydrogen as an electron donor.14
Figure 4.7 shows which reducing environment is favored depending on the hydrogen
concentration. Although compounds produced during fermentation and hydrogen
have been demonstrated to drive halorespiration,32 hydrogen appears to be the most
important electron donor for this process.36.37 Halorespiration has been found to be
limited if available nutrients are not present. Direct injection of H2 is able to serve
as an electron donor for reductive dechlorination of PCE to VC and eventually to
ethene in cultures provided with the proper nutritional supplements.34,38
Because reductive dechlorination of chlorinated ethenes is a reductive process,
microorganisms may exist that can use chlorinated compounds as a terminal electron
acceptor and possibly conserve the concomitant energy gain into ATP. This hypothesis, developed in the early 1990s, proved to be true.25,26 The first evidence that
bacteria exist that can couple reductive dechlorination of PCE to growth (halorespiration) under strict anaerobic conditions was presented in the early 1990s.25,39 A
highly purified enrichment culture able to grow by the reduction of PCE to cis-DCE
using hydrogen as the electron donor was described. The dechlorinating organism,
later designated Dehalobacter restrictus, uses only hydrogen as the electron donor
and can couple growth to the reduction of PCE or TCE to cis-DCE. A recent study25,40
described a new isolate, strain TEA, which is closely related to Dehalobacter
restrictus. Another strict anaerobic bacterium, Dehalospirillum multivorans, capable
of coupling dehalogenation of PCE to growth, was identified and described
recently.25,41 This bacterium is less restricted concerning both electron donors and
acceptors.
Several dechlorinating strains belonging to the genus Desulfitobacterium were
isolated from different sources. The strictly anaerobic D. dehalogenans, able to grow
by the reductive dechlorination of chlorinated phenolic compounds was isolated
recently. Another Desulfitobacterium, strain PCE1, was isolated from polluted soil
and is reported to couple the reduction of both chlorinated phenols and chlorinated
ethenes to growth.43 This strain dechlorinates PCE only to TCE, whereas other known
halorespiring microorganisms dechlorinate PCE further. The same authors also
described a Desulfitobacterium sp. strain TCE1, which is able to use several electron
donors for the reduction of PCE to cis-DCE.43,44 Another researcher has described
a Desulfitobacterium sp. (strain PCE-S) that converts PCE to cis-DCE.45 All isolated
Desulfitobacterium strains are able to use a number of different electron donors and
acceptors for growth. The nature and origin of the dechlorinating enzymes in these
organisms are still unknown.
146
15
Hydrogen Concentration (nM)
Possible Reactions
10
0
Denitrifiers
Figure 4.7
Fe(III) Halorespirators Sulfate

Methanogens
Reducers
Reducers
Range of hydrogen concentrations for the different anaerobic metabolic pathways

(after Wiedermeier et al., 1999).
A recent study described two facultative aerobic bacteria, strain MS-1 and the
closely related Enterobacter agglomerans biogroup 5, which can reductively dehalogenate PCE to cis-DCE under anaerobic conditions.46 It is not clear yet whether
strain MS-1 and E. agglomerans biogroup 5 are actually halorespiring organisms.
Recently, an anaerobic bacterium, Desulfuromonas chloroethenica (strain
TT4B), has been isolated which can not only reductively dechlorinate PCE to cisDCE with acetate as an electron donor, but also can reduce Fe (III) and polysulfide.
These are unique features for PCE-dehalogenating organisms.47
All the above-mentioned organisms are only able to couple growth to the partial
reduction of PCE or TCE. An exception is Dehalococcoides ethenogenes strain 195
that couples growth to rapid dehalogenation of PCE to VC, followed by a substantially
slower reduction to ethene.37 Growth of this bacterium is restricted to the presence of
hydrogen, which is the only electron donor supporting the dechlorination reactions.
Dechlorination was only sustained by using hydrogen, acetate, vitamin B12, anaerobic
digester sludge supernatant, and cell extracts from mixed cultures in the medium.
147
Chloroethene Reductive Dehalogenases: The biochemistry of PCE dehalorespiration has been studied with enzymes that were purified from a reductively dechlorinating pure culture or enrichment, which is able to couple dechlorination to energy
conservation (halorespiration). PCE respiration has been studied most extensively
in Dehalobacter restrictus42,49 and Dehalospirillum multivorans.26,41,45 In general, a
PCE respiration chain should contain an electron-donating enzyme, electron carriers,
and a reductive dehalogenase as terminal reductase. Studies with D. multivorans
and Desulfitobacterium strain PCE-S indicate that a proton gradient or a membrane
potential may also be essential for chloroethene respiration because several ionophores have been found to inhibit dechlorination in whole cell suspensions.45,50 The
nature of the electron-donating enzyme depends on the electron donor. In D. restrictus, which uses hydrogen as electron donor for PCE respiration, hydrogenase activity
has been localized on the membrane, facing the outside.49 D. multivorans and
Desulfitobacterium strain PCE-S are able to use several electron donors for dechlorination, and different electron-donating activities have been found.45,50 The electrons
thus generated are transported to the dehalogenase via electron carriers such as
quinones and cytochromes. It was demonstrated that menaquinone is involved as
electron carrier for PCE respiration in D. restrictus,49 but not in D. multivorans.45,50
Cytochrome b is present in both organisms, but its involvement in PCE respiration
has not been established.
In contrast to the well studied PCE and TCE dechlorination, little is known about
the mechanism of DCE and VC dechlorination. It was found that the enzymes
catalyzing VC dechlorination in an enrichment culture are membrane bound and, in
contrast to the known PCE reductase, cobalamin independent.51 It remains unclear
whether this enrichment is able to use VC as terminal electron acceptor. Recently,
an enzyme has been obtained from an enrichment containing D. ethenogenes that
catalyzes the dechlorination of TCE to cis-DCE, VC, and ethane. This cobalamincontaining TCE-reductive dehalogenase is membrane bound and dechlorinates its
substrates at similar rates, as have been reported for the PCE dehalogenases. More
research is needed to know what determines the difference in substrate specificity
of the cobalt-containing reductive dehalogenases.
4.2.1.4 Electron Donors
The selection of an appropriate electron donor may be the most important design
parameter for developing a healthy population of dechlorinating microorganisms
during implementation of an IRZ for enhanced reductive dechlorination. Recent
studies have indicated a prominent role for molecular hydrogen (H2) in the reductive
dechlorination of chloroethenes.34,39,48 Most known dechlorinators can use H2 as an
electron donor; some can use only H2. Because more complex electron donors are
broken down into metabolites and residual pools of H2 by other members of the
microbial community, they may also be used to support reductive dechlorination.
From the small but growing pool of knowledge about dechlorinating organisms,
it thus appears that H2 may serve an important role in reductive dechlorination of
PCE in many environments. The author recently has observed the quick or direct
transformation of PCE or TCE to ethene under very reducing conditions leading to
148
Complex Organics
PCE
Ethene
4 H+ + 4CI-
H2
Dechlorinators
CO2
Methanogens
Acetic Acid
Figure 4.8
Conceptual diagram of microbial activity to derive energy for growth and multiplication.
fs electrons
Carbon Substrate
Cell Synthesis Reactions
fs electrons
Target
Electron Donor
Substrate
H electrons
First Intermediate
Electron Donor
Substrate
fe electrons
Electron Acceptor Substrate

Energy Generation Reactions
fe electrons
H electrons
fs electrons
Figure 4.9
Second Intermediate
Electron Donor
Substrate
fe electrons
Distribution of electrons to generation and cell synthesis during the breakdown

of organic electron donors.
149
speculations of the probable effect of high H2 concentrations or reductive dechlorination. In natural systems, including contaminated aquifers, most H2 becomes available to hydrogenotrophic microorganisms through the fermentation of more complex
substrates by other members of the microbial consortium. The dechlorinators must
then compete with other organisms, such as methanogens and sulfate-reducing
bacteria, for the evolved H2 (Figure 4.8). Figure 4.9 also describes the distribution
of electrons during the microbial breakdown of organic electron donor substrates.
During studies in which ethanol or lactate was used to stimulate dechlorination in
mixed anaerobic enrichment culture, both active dechlorination and methanogenesis
at high H2 levels was observed; however, when H2 levels fell, dechlorination continued, albeit slowly, while methanogenesis ceased entirely. It was speculated that
the addition of electron donors fermented only under low H2 partial pressures might
give selective advantage to dechlorinators over methanogens.
One school of thought in the past was that the rate and quantity of H2 made
available to a degrading consortium must be carefully engineered to limit competition for hydrogen from other microbial groups, such as methanogens and sulfatereducers. Competition for H2 by methanogens is a common cause of dechlorination
failure in laboratory studies. As the methanogen population increases, the portion
of reducing equivalents used for dechlorination quickly drops and methane production increases.17,18,36 Speculation was that the use of slowly degrading nonmethanogenic substrates would help prevent this. Recent thinking on this issue is evolving
to be different and is discussed later.
Many different compounds may serve as electron donors for the reductive dechlorination of chlorinated solvents (Table 4.4). Several researchers suggest that the
microbial reductive dechlorination of chlorinated ethenes depends on the presence
of molecular hydrogen as the actual electron donor, either directly available or
produced from other substrates by fermentation.32,34,55,56 Although this statement
applies to many studies, in several cases it does not hold. Acetate, from which usually
no hydrogen is produced during anaerobic metabolism, has been shown to support
reductive dechlorination of chlorinated ethenes both in microcosms and environmental samples5,7,26,58 and in pure culture.47
Until recently, most research activities concerning the anaerobic degradation of
chlorinated compounds focused on methanogenic systems. Such systems typically
involve the introduction of a fermentable organic compound, such as acetate, lactate,
hexoses (present in molasses) or even a co-contaminant such as toluene or phenol,
which is fermented to produce hydrogen, among other things. It is now clear that
these systems probably contained at least two distinct strains of bacteria. One strain
fermented the organic carbon to produce hydrogen, and another utilized the hydrogen
as an electron donor for dehalorespiration.15 Only in the last two or three years have
researchers finally recognized the role of hydrogen as the electron donor in the
reductive dechlorination process.
4.2.1.4.1 Production of H2 by Fermentation
The production of H2 by different microorganisms is intimately linked with their
respective energy metabolisms. The production of H2 is one of the specific
150
Table 4.4 Electron Donors That Have Been Used to Enhance

Reductive Dechlorination and Relative Costs per lb of
PCE5153
Electron Donor
Bulk Price
$/lb
$/lb of
PCE
Soluble (Fast Release) Donors

Methanol
Milk
Ethanol
Molasses
Sugar (Corn Syrup)
Sodium Lactate
0.05
0.05
0.20 0.25
0.20 0.35
0.25 0.30
2.20
0.64
0.18
NA
0.16
0.40
NA
Slow Release Donors

Whey
Edible Oils
Flour (Starch)
Cellulose
Chitin
Methyl Cellulose
HRC (Regenesis Commercial Material)
0.05
0.20 0.50
0.30
0.40 0.80
2.25 3.00
4.00 5.00
12.00
0.04
NA
0.85
NA
NA
NA
NA
NA Not Analyzed.
mechanisms to dispose excess electrons through the activity of hydrogenase present

in H2 producing microorganisms.59 All hydrogen producing microorganisms can be
categorized into four groups:60
Hetertrophic facultative anaerobes that contain cytochromes and lyse formate to
produce H2
Desulfovibrio desulfuricans, which is the only strict anaerobe in this group with
a cytochrome system
Photosynthetic bacteria with light-dependent evolution of H2 from reduced NADH
Strict anaerobic heterotrophs that do not contain a cytochrome system (clostridia,
micrococci, methanobacteria, etc.)
Production of H2 by obligate anaerobic microorganisms 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.60
Under natural conditions, fermentation is the process that generates the hydrogen
used in reductive dechlorination. In the absence of externally available electron
acceptors, many organisms perform internally balanced (different portions of the
same substrate are oxidized and reduced) oxidation-reduction reactions of organic
compounds with the release of energy; this process is called fermentation. Since
only partial oxidation of the carbon atoms of the organic compound occurs, fermentation yields substantially less energy per unit of substrate compared to oxidation
reactions. (Oxidation reactions are those in which external electron acceptors participate in the reaction). For instance, the fermentation of glucose to ethanol and
CO2 has a theoretical energy yield of 57 k cal/mole, enough to produce about
151
6 ATP. However, only 2 ATPs are produced, which implies that the organism operates
at considerably less than maximum efficiency.59
In any fermentation reaction, there must be a balance between oxidation and
reduction. In a number of these reactions, electron balance is maintained by the
production of molecular hydrogen, H2. In H2 production, protons (H+) of the medium,
derived from water, serve as electron acceptor. 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 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 controlling the biogeochemical
environment of anaerobic aquifers. Bacterial fermentation can be divided into two
categories:14,58
Primary fermentation is the fermentation of primary substrates such as sugars, amino
acids, and lipids to yield acetate, formate, CO2, and H2, but also yields ethanol,
lactate, succinate, propionate, and butyrate. While primary fermentation often yields
H2, production of H2 is not required for these reactions to occur.
Secondary fermentation or coupled fermentation is the fermentation of primary
fermentation products such as ethanol, lactate, succinate, propionate, and butyrate
to yield 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 balance the oxidation of the carbon substrates. These secondary fermentation reactions are energetically favorable only if hydrogen concentrations are very
low (102 to 104 atm or 8000 to 80 nM dissolved hydrogen, depending on the
fermentation substrate). Thus these fermentation reactions occur only when the
produced 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 interspecies hydrogen transfer.
It should be noted that the terminal products of anaerobic decomposition, CH4, and
CO2, respectively, are the most reduced and the most oxidized carbon compounds.
There are a number of compounds besides the ones listed in Table 4.4 that can
be fermented to produce hydrogen (Figure 4.10). While anaerobic degradation of
BTEX compounds has been confirmed for a long time, there is still some controversy
as to whether aromatic compounds (without any oxygen in the molecule) such as
the BTEX compounds can be completely mineralized to CO2 without alternate
electron acceptors coupled solely by fermentation with methanogenesis.
Based on a number of field observations of the presence of methane, it is well
known that fermentation occurs at almost all sites where BTEX compounds are present
in groundwater.14,53 Since methane production requires fermentation products as methanogenic substrates, the presence of methane is clear evidence that fermentation is
occurring. Metabolism of BTEX compounds to produce hydrogen probably requires
the involvement of several strains of bacteria. One possible mechanism is a series of
reactions, in which other electron acceptors are used by nonfermenters to break down
the aromatics to simpler compounds that can be used by the fermenters.
152
Figure 4.10
Steps in the process of biodegradation of PCE by reductive dechlorination. As

shown, biodegradable organic matter is required as an electron donor to initiate
the process. Different types of microbes are involved at each stage. The bottom
step shows that PCE must compete for electrons with sulfate, iron, and carbon
dioxide, meaning that a large amount of organic electron donors may be needed
to supply enough electrons. Note: CDCE = cis-dichloroethene. Source: after
McCarty, 1997.
4.2.1.4.2 Competition for H2

In environments where hydrogen is the most important electron donor for dechlorination of chlorinated solvents, competition for the uptake of hydrogen between
different types of microorganisms, such as methanogenic, homoacetogenic, sulfidogenic, and dechlorinating bacteria, becomes important. In several studies it has been
shown that dechlorinating organisms have a higher affinity for molecular hydrogen
than methanogens.27,35,55 This indicates that the dechlorinating organisms are able to
survive at lower hydrogen levels, but will possibly be outcompeted by other microorganisms when elevated hydrogen levels are present. These studies suggest that a more
effective dechlorination may be achieved by using an electron donor that generates
low hydrogen concentrations during its fermentation, such as propionate or butyrate.
The speculation is that this would then create more favorable conditions for dechlorinating bacteria than for hydrogen-consuming methanogens.27,35
Reductive dechlorination of PCE requires the addition of two electrons for each
chlorine removed; for three of the seven recently identified dechlorinating organisms,
H2 is one of the substrates (and in some cases, the only one) that can serve as the
153
direct electron donor. Dehalobacter restrictus is another direct dechlorinator that

uses only H2 as an electron donor, but dechlorinates PCE only to cis-1,2-dichloroethene (cisDCE).46,47 Dehalospirillum multivorans also dechlorinates PCE to cisDCE using H2, but has a much more widely varied biochemical repertoire: it is
additionally able to use various organic substrates such as pyruvate, lactate, ethanol,
formate, and glycerol as electron donors.7,37,44 Other PCE-dechlorinating organisms
have been isolated that do not use H2.34,61 It was later determined that the halfvelocity constant with respect to H2 for this dechlorinator was one-tenth that of the
methanogenic organisms in the culture. The threshold H2 level for dechlorination
was also correspondingly lower than values typically reported for methanogens.
Though confirmed thus far with only this one dechlorinator, there are thermodynamic
reasons (i.e., the relatively high free energy available from dechlorination) to suspect
that the threshold for H2 use by dechlorinators may generally be lower than that for
hydrogenotrophic methanogens.15,27 This suggests a strategy for selective enhancement of dechlorination managing H2 delivery so as to impart a competitive
advantage to dechlorinators.
Numerous microcosm and site studies have shown successful stimulation of
dechlorination with substrates such as methanol, ethanol, lactate, butyrate, and
benzoate.3,32,36,62,57 However, understanding the fate of the electron donors and that
of the H2 evolved from their degradation, as well as the extent to which their reducing
equivalents are channeled to desirable dechlorination or competing H2 sinks, has
important implications for determining how best to effectively stimulate latent
dechlorinating activity for in situ enhanced reductive dechlorination in an IRZ.
Leading to a new school of thought, recent studies have suggested that the type
of substrates and the rate of fermentation may not have an impact on reductive
dechlorination. One study showed the ability of four fermentable substrates to sustain
PCE dechlorination long-term (i.e., approximately four months).35 The choice of
organic substrates was based upon their rates of fermentation and the H2 partial
pressures that could be developed and maintained. Despite the difference in the
resulting H2 partial pressures (ranging approximately 1 105 to 3 103 atm), no
long-term effect on dechlorination was observed. This result may indicate either that
low H2 partial pressures were not required to maintain a competitive dechlorinating
community or that several isolated PCE respiring bacteria do not utilize H2 as an
electron donor.43,46 H2 was not the source of PCE-reducing equivalents in all systems
tested. Other laboratory and field studies have also suggested that the steady state
concentration of hydrogen is controlled by the type of bacteria utilizing the hydrogen
and is almost completely independent of the rate of hydrogen production.
As discussed earlier, when hydrogen is produced by fermentative organisms, H2
is rapidly consumed by other bacteria. This utilization of H2 by nonfermenters is
known as interspecies hydrogen transfer and is essential for fermentation reactions
to proceed.59 Note, for example, that a glucose fermenter is unable to utilize glucose
by itself so that both the glucose fermenter and the methanogen benefit from this
symbiotic relationship.
Although H2 is a waste product of fermentation, it is a highly reduced molecule,
which in turn makes it an excellent, high-energy electron donor. In this symbiotic
relationship, the hydrogen utilizing bacteria gain a high energy electron donor, while,
154
for the fermenters, the removal of hydrogen allows continuous fermentation to be

favorable energetically.
In addition to methanogens, a wide variety of bacteria can utilize hydrogen as
an electron donor: denitrifiers, Fe (III) reducers, sulfate reducers and halorespirators.
As discussed earlier, for dechlorination to take place, halorespirators must successfully compete against all these hydrogen utilizers.
It was suggested that the competition is mainly controlled by the Monod halfsaturation constant Ks (H2) (the concentration at which a specific bacterial strain can
utilize hydrogen at half the maximum utilization rate).14,27,56 The measured value of
Ks (H2) for halorespirators was 100 nM and for methanogens 1000 nM.14 This led
to the suggestion that halorespirators would compete successfully for H2 only at low
concentrations.
However, a more detailed analysis of halorespiration kinetics and competition
for hydrogen based on the Monod kinetic model was performed recently.14,27 Using
this model, the ability of hydrogen-utilizing bacteria to compete for hydrogen can
easily be predicted from substrate concentration and two properties of the bacteria,
max (maximum specific growth rate), and Ks. Table 4.5 lists these parameters for
the various hydrogen-utilizing bacteria.
Table 4.5 Maximum Specific Growth Rate
(max) and Half Saturation
Coefficient (Ks) for Various H2Utilizing Bacteria (Modified from
Wiedermeier et al., 1999)
Bacterial Strain
max (hr1)
Ks (mg/L)
Halorespirator
Denitrifier
Sulfate Reducer
Methanogen
0.019950
0.058080
0.003936
0.003792
0.0002
0.0019
Table 4.5 illustrates that, from the max term, halorespirators will outcompete
methanogens and sulfate reducers at any hydrogen concentration (since at high
substrate concentration growth rate max and at low substrate concentration
(max.S)/Ks). However, denitrifiers will probably outcompete halorespirators under
most conditions as their maximum specific growth rate is approximately three times
faster than halorespirators. Based on these detailed analyses and the synthesis of
wide ranging data from field observations, the following probable sequence takes
place at most sites undergoing halorespiration reactions:14,27
Aerobic bacteria consume nonchlorinated organic substrates until the oxygen is
depleted; to implement enhanced reductive dechlorination, oxygen depletion is
forced intentionally in an IRZ.
Similarly, denitrifying bacteria will consume nonchlorinated organic substrates
until the nitrate is exhausted; nitrate depletion will be forced for enhanced reductive dechlorination.
Iron reducing bacteria consume nonchlorinated organic substrates until the available Fe (III) is expended.
155
Fermentation processes consume nonchlorinated organic substrates and generate

hydrogen; dechlorinating bacteria consume hydrogen for dechlorination, while
sulfate-reducing bacteria consume nonchlorinated organic substrates and methanogens consume hydrogen to generate methane.
End of Remediation
Hydrogen Concentration
Recently researchers have found that steady state H2 concentrations in the field
are controlled by the type of bacteria utilizing the hydrogen.14 For example, under
nitrate reducing concentrations, steady state H2 concentrations were less than 0.05
nM, under Fe (III) reducing conditions they were less than 0.2 to 0.8 nM, under
sulfate reducing conditions they were 1 to 4 nM, and under methanogenic conditions
they were 5 to 14 nM (Figure 4.7). Thus it is clear that an increased rate of hydrogen
production will result in increased halorespiration without affecting the competition
between various bacteria for the available hydrogen (Figure 4.11). Attempting to
stimulate halorespiration with poor fermentation substrates, as has been suggested
in the past, may unnecessarily limit the amount of dechlorination taking place.
O2
Depletion
Figure 4.11
NO3 Depletion Fe (iii) Depletion
SO42- Depletion
Methanogenic Conditions
Effect of oxidative poise on H2 concentrations during field scale implementation

of enhanced reductive dechlorination systems, if methanogenic conditions can
be achieved and maintained (adapted from Weidermeier et al., 1999).
It is clear from this this discussion that, during field scale enhanced reductive
dechlorination at contaminated sites, the oxidative poise contributed by dissolved
oxygen, nitrate, Fe (III), Mn (IV) and sulfate has to be depleted as quickly as possible
to achieve efficient steady state reductive dechlorination reactions.53 Thus it is prudent to use the cheapest fermentable substrate available (see Table 4.4) to overcome
the oxidative poise (Figure 4.12).
4.2.1.5 Mixture of Compounds on Kinetics
Because few studies have systematically investigated the effect of multiple contaminants, and not all biochemical mediators of chlorinated aliphatic transformation
156
Fermentation
Substrate
Demand for
Production of H2
SO42Fe3+, Mn4+
NO3-
O2
Figure 4.12
Pictorial depiction of oxidative poise to be overcome during implementation of

an IRZ for engineered anaerobic systems.
in methanogenic cultures are known, it is difficult to predict how any two chlorinated
aliphatics may influence each others transformation. Several possible interactions
can be hypothesized wherein chlorinated aliphatic biotransformation rates may
increase, decrease, or remain unaffected. Increased rates may be observed through
induction of transformation pathways or growth on one chlorinated aliphatic, such
as dichloromethane (DCM), which then supports transformation of other aliphatics
present. Decreased rates may result from competitive inhibition, competition for
reducing equivalents, or synergistic toxicity effects. There may be no observable
effect if transformation processes are independent, or concentrations of chlorinated
aliphatics are low.
Mixtures of chlorinated aliphatics often result from reductive dechlorination of
a single parent compound; discerning the effect of mixtures on the transformation
of individual compounds is difficult. The most frequently cited example is the
sequential reductive dechlorination of polychlorinated ethenes (e.g., perchloroethene, trichloroethene) to ethene. Rates of reductive dechlorination in this series tend
to decrease as the number of chlorine substituents decrease, so compounds such as
vinyl chloride and dichloroethene often accumulate.64 Since all chlorinated ethenes
are transformed by the same mechanism, it is conceivable that competitive interactions also influence the distribution of products, although it has not been systematically investigated.
The sequential reductive dechlorination of 3,5-dichlorobenzoate to 3-chlorobenzoate to benzoate has been reported.63 In this case, reduction of the 3-chlorobenzoate
did not proceed until the 3,5-dichlorobenzoate was completely transformed. This
could not be explained by competing reaction rates, but was successfully described
157
with a competitive inhibition model. Similar behavior for the reduction of 4-amino3,5-dichlorobenzoate to 4-amino-3-chlorobenzoate also was observed.
It is important to note that competition may be significant during degradation of
chlorinated methanes and ethanes as they can be transformed by reductive dechlorination and other mechanisms.65,66 Methylene chloride (DCM) can be oxidized to
CO2 or converted to acetate while serving as a growth substrate.7 Chloroform (CF)
and carton tetrachloride (CT) can be hydrolyzed.66 1,1,1 Trichloroethane (TCA) can
be hydrolyzed or undergo dechlorination.19 Hydrolysis processes for these compounds are of particular interest since the products are reactive in some cases
decomposing to harmless end products or reacting with cell material whereas
hydrolysis of CF and TCA yields strong nucleophiles (phosgene and acid halide),
which may be toxic to the cell. Subsequent hydrolysis of these intermediates yields
CO2 and acetate; both are subject to complete metabolism in anaerobic culture.
The interaction of dechlorination amongst CM, CF, and TCA in methanogenic
acetate-enrichment cultures was investigated in another study.67 Complex interactions occurred when mixtures of these chlorinated aliphatics were present: TCA
transformation rates were reduced by the presence of DCM or CF, DCM transformation was enhanced by CF and TCA, and CF transformation rates increased or
decreased depending on the mixture. Acetate utilization varied depending on the
mixture fed, complicating the interpretation of results. Where acetate utilization was
inhibited, biomass concentrations decreased and steady-state conditions were not
achieved during the study.
In all cases where CF and TCA were fed together, the rate of their transformations
was lower than when they were fed individually. The decrease in the rate of transformation increases with the concentration of either compound, CF being more
inhibitory than TCA on mg/L basis. Results were described by a competitive inhibition model, which was more predictive for the effect of TCA on CF transformation
than the effect of CF on TCA transformation.67
Competitive interactions between substrates can introduce significant limitations
to bioremediation processes. Studies investigating the cometabolic transformation
of chlorinated ethenes by methanotrophs,68,69 nitrifiers,70 and phenol-induced
aerobes71 have identified many problems at full scale that result from similar interactions. The decrease of biodegradation rates that results from competitive inhibition
may limit the applicability of bioremediation processes. This is particularly true with
CF and TCA, whose growth and biotransformation rates decrease rapidly as their
concentrations increase.
The effect of multiple substrates on the kinetics of biotransformation reactions
has not been extensively studied. The results reported in the literature demonstrate
that a range of effects may be observed even with a mixture of compounds that are
structurally similar. No unifying model can be constructed on the basis of the
available information. These studies also demonstrate the difficulty of assessing the
interactions that occur when the compounds of interest may have dissimilar degradation pathways.
Unraveling the complex interactions of compounds such as those often encountered in contaminated groundwaters will require further research. It is clear from
these studies that certain combinations of compounds will lead to decreased rates
158
of biotransformation. This is certainly true for the combination of CF and TCA. For
engineers hoping to implement anaerobic bioremediation, this is important information in the decision making and design processes. If these interactions are not
considered, any existing model will significantly underestimate the time required
for remediation. Additional studies should attempt to enhance our fundamental
understanding of these interactions, and identify other mixtures commonly found
that significantly affect biodegradation rates. Such knowledge will minimize the
application of bioremediation to sites where its efficacy would be limited.
4.2.1.6 Temperature Effects
Many studies have reported anaerobic reductive dechlorination of chlorinated
solvents to occur within a mesophilic temperature range (20 to 37C). However,
several authors have shown dechlorination of these compounds at more ambient
groundwater temperatures between 10 and 20C,8,26,55 indicating the applicability of
reductive dechlorination in many groundwater environments.
Microbial dechlorination has also been demonstrated under thermophilic conditions.26 An enrichment culture, obtained from polluted harbor sediment, rapidly dechlorinated PCE to cis-DCE at an optimum temperature of 65C. Fumarate appeared to
be the best electron donor. A large number of samples from high-temperature anaerobic
environments has been investigated for the presence of dechlorinating microorganisms
as well, but no dechlorinating activity has been found.
4.2.1.7 Anaerobic Oxidation
Microorganisms can anaerobically mineralize VC and DCE in the presence of
a complex, bioavailable electron acceptor such as Fe (III) EDTA.72,73 Studies have
focused on the possibility of oxidation of VC and DCE when they are used as a
primary growth substrate under anaerobic environments.72,73,74 These results show
VC and DCE mineralization under methanogenic and iron reducing conditions in
anaerobic streambed sediments without the accumulation of ethene or ethane and
buildup of carbon dioxide.14 Decreases of VC and DCE concentrations corresponded
quantitatively to the production of carbon dioxide.
4.2.1.8 Electron Acceptors and Nutrients
Nutrients: In addition to proper electron donor selection, nutrient availability
may be a critical factor in maintaining a healthy dechlorinating consortium. In one
instance, attempts to isolate a microbial species responsible for dechlorination led
to the discovery that nutritional factors probably had been supplied by other consortium members. Highly enriched dechlorinating cultures required the addition of
vitamin B12 and sludge supernatant to sustain dechlorination.38 Speculation exists
that acetogens may supply the unknown nutritional factors required by the dechlorinating organism(s).34 Fortunately, in situ applications support a variety of microbial
species. This microbial diversity, combined with the addition of nutritional supplements, should support a healthy dechlorinating microbial community.
159
Alternative Electron Acceptors: Microbial dechlorination of chlorinated aliphatic hydrocarbons has been found to occur at low REDOX potentials, mainly
under methanogenic conditions, although dechlorination under sulfate-reducing conditions has also been reported.26
A recent study found that, in reactions involving polychlorinated methanes and
organic reductants exhibiting mercapto groups, an alternative initial reaction step
may be a halophilic dissociative two-electron transfer.75 The proposed reaction
mechanisms(s) involving R-S-H or R-S-S-R groups in the complete dechlorination
of polychlorinated methanes may be helpful in the (re)interpretation of microbially
mediated dechlorination reactions of such compounds.
Indirect microbial reductive dechlorination of PCE has also been observed under
iron-reducing conditions due to magnetite formation by iron-reducing bacteria. Magnetite can chemically reduce PCE to lower chlorinated ethenes.76 Besides reduction
of chlorinated solvents under iron-reducing conditions, oxidation of cis-DCE and
VC has been reported to occur under conditions where Fe (III) is the final electron
acceptor.73 The same authors also reported the oxidation of DCE and VC in methanogenic, organic compound-rich bed sediment, indicating that the oxidation of these
compounds is coupled to the reduction of humic acid compounds.74
As discussed in the previous section, the successful application of enhanced
reductive dechlorination depends upon the depletion of electron-accepting chemical
species. The most environmentally relevant species include O2, NO3 , Mn (IV), Fe
(III), and SO42 . When evaluating a site for enhanced reductive dechlorination applicability, one must investigate the relative abundance of these compounds in both the
groundwater and the aquifer solids. Although aqueous-phase acceptors such as O2
and NO3 take primary consideration, it is imperative that aquifer solids be characterized because they can serve as a reservoir of relatively insoluble electron-accepting
species such as Fe (OH)3 or CaSO4. Once the electron-accepting species have been
quantified, the amount of electron donor required to deplete them can be estimated
by evaluating the stoichiometric relationship between the selected electron donor
and each electron acceptor present on site (Figure 4.12). Higher levels of electron
acceptor increase the oxidative poise and thus require more electron donor, therefore
raising treatment costs. A series of generic reactions is given in Table 4.6 to illustrate
some of the possible reactants and products.
Table 4.6 Possible Reactants and Products of Specific Terminal
Electron-Accepting Processes
Predicted Reaction
Electron
Electron
Electron
Electron
Electron
donor
donor
donor
donor
donor
+
+
+
+
+
O2 CO2 + H2O
NO3 CO2 + H2O + N2
Mn4+ Mn2+ + CO2 + H2O
Fe3+ Fe2+ + CO2 + H2O
SO42 H2S + CO2 + H2O
Process
Aerobic respiration
Denitrification
Manganese reduction
Iron reduction
Sulfate reduction
Once an electron donor has been selected and electron acceptors have been
characterized, the stoichiometric relationship between them can be determined. An
equation for each electron acceptor present at the site must be balanced using the
160
selected electron donor. Once balanced, the molar ratio of donor to acceptor can be
determined from these equations.
These molar ratios represent an ideal case where the entire electron donor dosage
is used to reduce the electron acceptor present in the treatment zone. When calculating
the actual electron donor dosage, a safety factor must be incorporated to account for
uncharacterized electron sinks and the advective transport of electron acceptors into
the treatment zone. Site-specific conditions such as groundwater flow rate, surrounding
electron acceptor concentrations, depth to the water table, rainfall frequency, and level
of site characterization will influence the selection of the safety factor.
Because treatment alternatives and budgetary constraints are different for each site,
no rule of thumb exists for screening sites based on electron acceptor concentrations.
The required mass of electron donor should be estimated so its cost can be calculated.
Afterwards, a site-specific, cost-benefit analysis must be undertaken to determine if
the site is a good candidate for enhanced reductive dechlorination (ERD) application.
4.2.1.9 Field Implementation of IRZ for Enhanced Reductive
Dechlorination
The authors success and significant experience in creating an IRZ for enhanced
reductive dechlorination is based purely on biostimulation of the indigenous capacity
of microorganisms present at a contaminated site for dechlorination rather than
bioaugmentation. This experience is based on successful implementation of this
technology at more than 100 sites. Creation of such an IRZ involves the addition of
an electron donor and supplemental nutrients to the contaminated groundwater zone
in order to provide the optimum biogeochemical environment conducive for reductive dechlorination.1
The authors wide experience in this technology is mostly based on the soluble
electron donor, such as molasses that must be added semicontinuously or in batch
injections1 in order to sustain the microbial activity for the fermentation reactions.
Recently, cheese whey has been used as a slow release substrate in less permeable
geologic environments. Preference of molasses and cheese whey is based purely on
economics as illustrated in Figure 4.12 and Table 4.4.1
The geologic and hydrogeologic setting in which an IRZ system is installed
governs its successful application. IRZ systems rely on the delivery of dissolved
reagents, such as dilute molasses, throughout a contaminant plume; administering
delivery of these amendments through both the vertical and horizontal extent of
contaminant plumes sounds deceptively easy, but requires careful engineering and
a knowledge of the geologic parameters affecting groundwater flow and transport.
Different configurations, in plan view and cross sections, used for IRZ system
designs are shown in Figures 4.13a and b, and 4.14a and b. Creative engineering
considerations have to be taken into account to accommodate the requirements of a
smaller plume vs. a larger plume and a shallower plume vs. a deeper plume. The
ultimate objective of the IRZ system design engineer should be to deliver the electron
donor as fast as possible and to create a uniformly mixed reactive zone in the
subsurface, as well as to maintain the optimum biogeochemical conditions for
enhanced reductive dechlorination to occur.
161
Groundwater
Flow Direction
Injection Points
Figure 4.13a
Staggered plume-wide injection grid for an IRZ system for remediation of a small
plume.
Groundwater
Flow Direction
Source Zone Grid

Containment Curtains
Figure 4.13b
Source area staggered grid and containment curtains at mid-plume and downgradient locations for a large-size plume.
The total treatment time for an IRZ will encompass the time it takes to overcome
the oxidative poise (deplete available electron acceptors), acclimatize and stimulate
a healthy population of dechlorinating microorganisms, and allow the dechlorination
reactions to proceed to conclusion. Site-specific conditions will obviously influence
the total time required for treatment; for instance, anaerobic and particularly methanogenic sites exhibiting a significant level of natural dechlorination will require
considerably less time than sites with aerobic groundwater and no evidence of
dechlorination. Other factors incluencing the time required to treat a site include
aquifers with low hydraulic conductivities, which will require more time for delivery
of substrate throughout the subsurface, and the presence of DNAPL, which would
require considerably longer treatment times due to the rate limitation imposed by
dissolution of the contaminant.
The time required for oxidative poise depletion depends on the electron donor
supply and utilization rate, on initial electron acceptor concentrations, and the rate
at which they are replenished by groundwater flow and recharge events. The large
number of variables affecting electron acceptor depletion makes it difficult to predict
the time lag; field data indicate that this lag could be anywhere from ten days to
about three months.
When considering the time required to implement an enhanced reductive dechlorination IRZ system, one should include a minimum of six months to perform a
162
Dilute Molasses
Reactive
Zones
Figure 4.14a
Injection well clusters for depths between 40 feet and 100 feet of saturated zone
containment.
field pilot test to obtain the design parameters to design and scale up a full scale
system. This six month testing time frame assumes one to two months for creation
of a reducing environment after the depletion of the oxidative poise and three to
four months of evaluating treatment data. The actual time required for a pilot test
may exceed six months and will depend on hydrogeologic conditions and whether
the site was already reduced with partial declorination initially.
The assessment of a particular site for IRZ application should include the
development of a contaminant profile, a hydrogeological profile, and a biogeochemical profile.
An inventory of contaminants, their concentrations, and distribution throughout
the plume will be the first step in assessing the feasibility of an IRZ. The presence,
relative concentration, and distribution of daughter products is particularly important
when assessing sites for enhanced dechlorination potential. Co-contaminant impacts
may be either beneficial or detrimental, so it is important to assess before the onset
of a pilot study.
The success of an IRZ application primarily depends upon the effective delivery
and distribution of the electron donor and nutrients throughout the contaminated
subsurface. Hence, the ability to control the movement of the injected reagents is
imperative at sites with a hydraulic conductivity less than or equal to 105 cm/sec.
These sites require the addition of a slow releasing electron donor. Faster geologic
Dilute Molasses
163
100'
Submersible
Pump
200'
Submersible Pump
Figure 4.14b
In well mixing systems with submersible pumps for creating deeper IRZ systems.
settings require the addition of a soluble and fast releasing electron donor such as
molasses. Figure 4.15 illustrates the need to inject a soluble electron donor at higher
concentrations to achieve a reasonable size reactive zone from each injection point
to achieve the scale up of the full scale system cost effectively.
Biogeochemistry influences the potential for stimulating and maintaining microbially catalyzed reductive dechlorination. These microorganisms require highly
reducing conditions reflected by low REDOX potential measurements and the production of hydrogen sulfide and methane gas. Additional biogeochemical parameters
such as pH, alkalinity, temperature, and dissolved organic carbon can also affect the
health and stability of dechlorinating microorganisms.
4.2.1.10
Lessons Learned
Typically a pilot test or smaller-scale field test follows the initial screening
process. The two primary issues to be addressed during the field testing phase are
the provision of properly placed observation wells and allowing for sufficient time
to demonstrate the success of ERD. The amount of time it takes to see positive
164
A - Distance of the Reactive Zone for the Slow Release Electron Donor
B - Distance of the Reactive Zone for the Soluble Electron Donor
Concentration at Injection Point
Soluble and Fast Degrading

Electron Donor
Such as Molasses
Slow Releasing and

Slower Degrading Electron Donor
Such as Soybean Oil
Minimum Concentration
Required for Adequate
Production of H2
A
Distance From Injection Point

Figure 4.15
Effects of a soluble electron donor and a slow release electron donor in an IRZ
where the hydraulic conductivity is greater than 105 cm/sec.
results of the IRZ implementation is related to many factors, including groundwater

velocity, the time required for introduced reagents to overcome the ambient REDOX
conditions in groundwater, and the locations of observation wells in relation to the
injection area. It is prudent to evaluate geochemistry and achievable degradation
rates from data collected from wells located at least several months of travel time
apart. Consequently, the minimum duration of a typical pilot study is six months
with the flexibility to extend the testing based on data collection and site-specific
costs. Field tests that are shorter in duration, or are applied in too small an area,
often do not provide information that is applicable to a successful or economical
large-scale implementation. This minimum period of time should be sufficient to
overcome the initial aquifer REDOX conditions and allow for the degradation of
constituents to a degree that will be observed in the pilot test. Some observation
wells should also be placed within one to two months groundwater travel time from
the injection area. This timing/placement should allow for early observations of the
IRZ development, and allow for modification of the reagent injection program
(strength and frequency) early enough in the planned test duration.
Reagent Delivery: The successful application of an IRZ to remediate chlorinated
solvents in groundwater first and foremost relies on the timely and consistent delivery
of the organic carbon reagent to the treatment zone.
The authors experience is primarily based on injecting a dissolvable sucrose
solution (molasses) as a reducing reagent. This serves as a cost effective reagent
(0.20 $0.30/pound) that can aggressively alter the REDOX state of groundwater
(oxidative poise) in a short time period. Other reagents, or electron donor substrates,
such as edible oils and semisolid forms of lactate (such as Regenesis HRC) will
rely more on dissolution and diffusion for delivery. On a unit cost basis, these donors
165
are more expensive. However, the application of a slow diffusing reagent may be
more efficient in a highly reducing, slower groundwater velocity environment. The
proper reagents should be selected based on the site hydrogeology and desired
treatment time frame. Cheese whey has been used by the author as the slow release
substrate in less permeable, slow moving groundwater environments.1
Based on the implementation of IRZs for the application of ERD to date, reagent
delivery becomes most complicated in low permeability geologic environments (105
centimeters per second (cm/sec) or less hydraulic conductivity) or those with low
groundwater flow velocities (less than 50 ft/yr). These settings can limit the area of
influence of individual reagent injection points due to the absence of sufficient
reagent dispersion. Poor donor delivery can also result in other potential complications. These complications can include:
Uneven application of reagent and resulting treatment; not achieving treatment
goals
Lack of sufficient or timely demonstration of the technology during pilot phase
Requirement of too many injection points for a full-scale application
In low permeability and/or low groundwater velocity environments, the reagent

can also accumulate in the vicinity of the injection point. Careful monitoring of the
pH, ORP, and total organic carbon (TOC) levels in the groundwater near the injection
well is necessary to avoid deleterious side effects. These effects are related to
fermentation and byproduct formation and are discussed later in this section.
Natural Surfactant Effect: The injection of an abundant source of easily
degradable organic carbon during the application of ERD typically results in a rapid
and large increase in the population of microorganisms in the treatment zone. As in
any microbiological system, this large population increase will also result in an
increase in production of natural biosurfactants and bioemulsifiers by the microorganisms. Natural biosurfactants result in desorption of the chlorinated contaminants
adsorbed to the aquifer media.
To assimilate less soluble substrates, such as chlorinated solvents, microorganisms require a large contact area between themselves and the contaminant. They
achieve this by emulsifying the adsorbed contaminants into an aqueous phase. Most
microbes frequently synthesize and excrete chemicals that promote such emulsification. These excreted chemicals fall into two main groups: biosurfactants and
bioemulsifiers (Table 4.7).
Table 4.7 Microbial Surfactants
Structural Type
Producing Microorganism
Carbohydrates lipids
Trehalose lipids
Amino acids lipids
Lipopeptides
Fatty acids neutral lipids
Nocardia, Mycobacterium, Coryne

bacterium, Arthrobacter
Bacillus, Streptomyces,
Corynebacterium, Mycobacterium
Pseudomonas, Acinetobacter,
Mycococcus, Micrococcus, Candida
Pseudomonas, Thiobacillus,
Gluconobacter
Ornithine lipids
166
Biosurfactants reduce the interfacial tension between water and the chlorinated
contaminant so that the chlorinated contaminant (or less water soluble compounds
such as PAHs) is easily micro-emulsified into the water phase. These micro-emulsion
droplets are known to be smaller than microbial cells. Some bacterial glycolipids
are extremely effective surfactants. In addition to enhancing the mobilization of
the contaminants by microemulsions, biosurfactants can also increase apparent solubilities by the partitioning the contaminants into surfactant micelles.
This desorption, or natural surfactant effect, is observed in many biological
treatment processes as an increase in the constituent levels in the treatment zone
and, in some cases, downgradient of the treatment zone. In some cases, the constituent concentrations in the treatment zone may remain unchanged, due to increased
solubilization of the contaminants, for a short period even when biodegradation endproduct data support the conclusion that sufficient mass is being degraded by the
ERD processes.
The production of surfactants that facilitate the partitioning of contaminants from
the DNAPL to the dissolved phase (thus resulting in enhanced biodegradation) has
received considerable attention recently.12,13 The success of this approach depends
on enhancing and maintaining biodegradation rates faster than the rate of mass
transfer from NAPL to the dissolved phase.
100
Koc = 265 (PCE)
Percent Sorbed
80
Koc = 94 (TCE)
60
40
K oc = 36 (cis-1,2-DCE)
20
0.000
0.002
0.004
0.006
0.008
0.010
Organic Carbon Fraction (foc )
Figure 4.16a
Effect of Koc on Masssorbed/Masstotal.
The magnitude and composition of soil organic carbon content combined with
the distinct differences in partitioning among the chlorinated alkenes have the potential to develop additional mechanisms that cause temporary increases in constituent
concentrations during enhanced reductive dechlorination applications (Figure
4.16a).76 A high TOC gradient present between the groundwater and the aquifer soil
matrix, resulting from the injection of molasses, will also result in desorption of
hydrophobic contaminants for the following reasons:76
167
Successive dechlorination of alkene compounds is accompanied by successive

decreases in organic carbon-water partition coefficients, Koc (the solubility of
aliphatic compounds rapidly increases with decreasing molecular weight). If the
degradation rate for daughter compounds is equal to or lower than the rate of
parent compound degradation, temporary increases in aqueous-phase concentrations will be observed.
Electron donors such as molasses, typically applied to enhance reductive dechlorination, comprise soluble and colloidal carbon compounds, creating an aqueousphase organic carbon pool that was essentially nonexistent prior to the creation
of the IRZ. Creation of an aqueous-phase carbon pool is expected to result in a
partial migration of chlorinated alkenes to aqueous-phase carbon sorption, resulting in increased apparent concentrations. Since the aqueous-phase carbon is
mobile, chlorinated alkenes may also be transported from their point of origination.
As the soluble organic carbon is consumed by the microbial community, a portion
of the chlorinated alkenes may remain in dissolved phase for a while until eventual
degradation within the IRZ.
Intuitively, the increased desorption of target constituents within the IRZ allows
for greater access to the typically untreatable adsorbed and separate phase contaminant mass present at source areas and DNAPL locations. However, this microbial
surfactant effect must be anticipated and pilot or full-scale treatment should incorporate provisions to evaluate and account for it. For example, the potential for initial
increases of stable parent constituent trends can be of concern to both responsible
parties and regulatory bodies as the data would tend to indicate the technology is
not working and, in some cases, could be considered as actually making conditions
worse. Therefore, during the full scale or pilot test planning stages the possibility
of this desorption effect must be evaluated in detail and anticipated in advance. Also,
the possibility for an increase of dissolved chlorinated solvent concentrations to
occur in areas downgradient of the treatment zone must be addressed. Typically, an
outside-in approach is applied, whereby a steady state IRZ is established in a
downgradient portion of the plume before applying ERD to the source area. Desorbed
constituents would then move into an area already undergoing treatment and capable
of treating the increased level of mass flux.
Fermentation and By-Product Formation: During application of ERD a highly
reducing biogeochemical environment is generally created throughout the treatment
zone. This zone will also contain a large excess of organic carbon in the vicinity of
the injection points, particularly if the geology is less permeable. During the implementation of an IRZ, at (105 cm/sec or less), these conditions can result in the
formation of organic acids and alcohols in the groundwater as part of the degradation
process. If the formed acids and alcohols are not consumed quickly the zone around
the injection zone will mimic a fermenter where additional by-products can be
formed.
The formation of undesirable byproducts (including acetone and thiol compounds and 2-butanone) has been observed at sites where injection was initiated
without careful monitoring of altered groundwater conditions near the injection
wells. The occurrences of these byproducts are generally limited in extent and often
sporadic in nature. It is expected that these oxidized by-products will also be utilized
168
by microbes within the IRZ. Therefore, the lessons learned regarding these potential
occurrences are as follows:
Careful and regular monitoring of groundwater within the treatment zone should
be provided in order to ensure that pH levels are not depressed below pH = 4.04.5,
and TOC levels are not excessive (site specific, but generally within 2 to 3000
mg/L).
The remediation plan for application of ERD should be flexible enough to allow
for modification of both frequency of delivery and mass of organic carbon delivered to prevent the build-up of organic carbon and creation of conditions amenable
to formation of these byproducts. Modifications in reagent delivery should be tied
to the pH, ORP, and TOC monitoring in the treatment zone.
Overcoming Oxidizing Conditions/High Groundwater Velocity: As discussed, the implementation of an IRZ for the application of ERD relies on the
creation of a highly reducing biogeochemical environment through provision of
excess organic carbon to the groundwater. Achieving these conditions can be problematic in groundwater flow systems in which the ambient conditions are very
oxidizing (due to shallow groundwater with abundant recharge) or the groundwater
velocity is very high (>1,000 ft/yr). In both situations, the amount of reagent needed
to overcome the oxidative poise of the naturally oxidizing conditions will be cost
prohibitive. In addition, the scale-up cost for the full-scale system will be uneconomical due to extremely narrow (cigar-shaped) zones of influence from each injection point.
In high groundwater velocity settings the limited transverse dispersion in groundwater can limit the extent of the reactive zone created by an individual injection
point. This is of particular importance in settings where drilling costs may be high
(i.e., deep settings or complex geology). In such cases, these site-specific considerations need to be weighed against other treatment alternatives.
Biofilm Developments: When injecting an electron donor such as molasses (and
electron acceptors) into an aquifer via injection wells, biofilm development around
the injection wells should be anticipated. Biofilms are large aggregations of bacteria
and other microorganisms bound together in a sticky mass of tangled polysaccharide
fibers that connect cells together and tie them to a surface. Aerobic and anaerobic
bacteria not only can thrive side by side within biofilms when biogeochemical
conditions permit, but also actually seem to collaborate to make themselves more
powerful. The polysaccharide coating acts like armor, giving the microorganisms
protection beyond their usual defense mechanisms.
While the typical average diameter of a bacterium in established biofilms is
about 0.51 m, 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 inorganic molecules trapped by these short-range forces,
they form slime that anchors them to solid surfaces. This slime becomes a home for
additional bacterial growth. If the biofilm becomes too thick to permit adequate
oxygen penetration, under aerobic conditions any additional biofilm growth may
actually decrease biofilm adherence due to shearing. The thickness of the biofilm
169
under anaerobic conditions is significantly smaller due to the above-mentioned

shearing effects and the fact that the rate of biomass growth is substantially lower
under anaerobic conditions.
Under unaerobic conditions, typical of an IRZ, reduction in porosity within the
saturated zone due to biofilm growth will not be significant enough to impact the
hydrogeologic conditions for reagent transport. However, well clogging around the
injection wells is an issue to be taken into consideration. Electron donor solutions,
such as dilute molasses, are injected at reasonably high concentrations of TOC before
it gets diluted by mixing with the groundwater within the IRZ. As a result of the
higher concentrations of TOC present around the injection wells, the amount of
biomass and biofilm growth will be significant.
Since the electron donor solutions are injected in a batch mode at most of the
IRZ applications, resistance to injection due to clogging may be an operational issue
only during the injection events. In all the sites in the authors experience, there
were only two sites where injection under pressure was difficult due to significant
head buildup. Manual cleaning of the well screens will be required under those
conditions.
Application in Areas of Low Constituent Concentration: The application of
ERD to portions of an aquifer where the constituent concentrations are low (i.e.,
less than 100 g/L) can pose additional challenges. A low concentration plume will
impart less microbial conditioning and, therefore, will be more difficult to stimulate
the microbial community. In these environments, a longer lag time for microbial
growth and conditioning should be expected. It is also difficult to observe direct
evidence of degradation through the monitoring program in a low concentration
plume.
Application in Areas of High Constituent Concentration/DNAPL: Given the
inherent problems with the use of conventional remediation techniques in areas
where the constituent concentrations are very high and/or where free phase contaminant (DNAPL) may be present, ERD has been an attractive potential alternative.
The benefit of applying ERD in high concentration regimes (>50 to 200 mg/L of
chlorinated VOCs) is related to the microbial surfactant effect that usually accompanies this technique.
The surfactant molecule is typically composed of a strongly hydrophilic (water
loving) group (or moiety) and a strongly hydrophobic (water fearing) group; in fact,
the entire surfactant monomer is often referred to as amphiphillic because of its dual
nature. The hydrophobic portion of the surfactant monomer is typically a long
hydrocarbon chain, referred to as the tail of the molecule. The hydrophilic head
group often includes anions or cations. The hydrophilic group of most surfactants
provides a high solubility in water; however, the hydrophobic group prefers to reside
in a hydrophobic phase such as a DNAPL. These compelling effects result in the
accumulation of surfactant monomers at DNAPL-water interfaces (Figure 4.16b).
Physical mobilization of the residual or adsorbed DNAPL by the surfactants is
undesirable and will not happen during the IRZ application due to low levels of
surfactant production (compared to a surfactant flood). Enhanced solubilization of
the DNAPL will take place and has to be controlled by the enhanced rate of
biodegradation.
170
Water Phase
DNAPL Phase
Figure 4.16b
Surfactant monomer accumulation at the DNAPLwater interface.
When the groundwater equilibrium is altered, the transfer of more constituent

mass from the free or adsorbed phase into the dissolved phase should be expected.
An increase in the levels of dissolved constituents in groundwater results in a more
treatable portion of the total contaminant mass. This effect can be used by itself or
in conjunction with other ongoing technologies (such as pump and treat) to reduce
treatment life span and costs. Care needs to be taken that increased dissolution and
desorption does not result in the vertical or horizontal migration of elevated dissolved
concentrations from the treatment zone.
The possibility of enhancing downgradient migration is more pronounced when
applying ERD in a potential DNAPL environment. Therefore, prior to ERD application in these settings a clear plan to address these possibilities must be developed.
This could include application of the technology in an outside-in approach in which
the downgradient areas are treated initially to develop a steady state containment
IRZ and encroach to the source area gradually.
However, if properly accounted for, the possibility of concentration increases,
and the impacts to overcome, an ERD can be successfully applied in these settings.
The application of ERD will increase the levels of mass reduction within the IRZ
and once the initial disruption in phase equilibrium is overcome the IRZ technology
will provide greater control of constituent migration from the source area.
4.2.1.11
Derivation of a Completely Mixed System for Groundwater

Solute Transport of Chlorinated Ethenes78
Assumptions and Definitions: The measured concentrations in a well (C1)

represent conditions in a unit volume of groundwater, the volume of which is defined
by the saturated aquifer thickness times the effective porosity, e, as follows:
171
V = haq 1 1 e
(4.2)
This volume of water moves through the soil at a velocity computed by using Darcys
Law (gw), while dissolved constituents migrate at a reduced velocity proportional
to the retardation factor:
con = gw Rf
(4.3)
Similarly, the measured concentrations (s1) in the volume characterize the dissolved
mass, while the total mass of the constituent can be as follows:
s10 = s0 Rf1
(4.4)
The dissolved constituent in the groundwater is assumed to decay through first order
process that can be represented in terms of half-life as follows:
1 =
ln 2
t1
(4.5)
As a constituent degrades, a daughter product is formed at a rate proportional to a

yield factor equal to the ratio of the molecular weights of the daughter compounds
to the parent compounds:
12 =
MW2
MW1
(4.6)
Solution for a single constituent:

The differential equation representing describing the concentration within this
volume written as the change in mass is equal to the mass in minus the mass out
minus the rate of decay; or mathematically as:
V
ds
= W(t ) Qs Vs
dt
where:
V =
Q =
s =
W=
=
Volume [L3]
Flow through the system [L3/T]
Concentration [M/L3]
Mass loading term [M/T]
First order reaction coefficient [1/T]
(4.7)
172
Equation 4.7 can be written more concisely as follows:

V
ds
+ Qs + Vs = W(t )
dt
ds
+ s(Q + V) = W(t ), or
dt
ds
+ s = W(t )
dt
(4.8)
where:
= Q + V
Equation 4.8 is a nonhomogeneous ordinary differential equation. The general solution to this classification of equations can be expressed as the sum of the complementary or general solution when W(t) equals zero, and a particular solution when
W(t) has a specific form.
s = sc + sp
Consider first, the solution to Equation 4.8 for a single constituent, with initial
conditions s = s0, at t = 0. Dividing Equation 4.8 by V, the equation describing the
complementary function is written as:
ds
+ s=0
dt V
Separation of variables,
ds
= dt
s
V
ds
ln s =
t + C0
V
s = V dt
(4.9)
C0 = Integration Constant
If W(t) = 0, sp = 0 and the above equation is also the specific solution. The integration
constants in Equation 4.9 can be solved by exponentiation and applying the initial
conditions.
173
s = exp t + C 0
V

s = C 0 exp t
V
At t = 0, s0 = C0, the initial concentration in the control volume. Therefore, the
equation describing the change in concentration (mass) in the control volume is as
follows:

s = s 0 exp t
V
(4.10)
Equation 4.10 can be applied to simple steady-state groundwater transport problems

(no dispersion) by recognizing analogous processes. Consider a well in a contaminant plume, and measured concentrations have been stable through multiple groundwater sampling rounds, implying an equilibrium has been reached between the
continued release of the constituent from residual source materials, and the significant transport process (advection, adsorption, and degradation). The question to be
answered is how far and at what level these constituents will migrate. The control
volume, V, is equivalent to the volume of active groundwater beneath the water table,
i.e., V equals the saturated aquifer thickness, T, times the effective porosity, e. Time,
t, is equal to the constituent transport time, i.e., t equals distance (x) divided by the
groundwater velocity (gw) times the retardation factor. The unit flow through the
control volume, Q, is equivalent to groundwater recharge (or percolation), N. The
initial dissolved concentration can also be expressed as ratio of the total mass to the
retardation factor (s10 /Rf1).
x

s1 (t ) = s 0 exp t = s 0 exp 1
R f1
gw
T
or
s1 (t ) =
s10
x
exp 1 R f1
R f1
gw
where
1 =
N + 1T
T
(4.11)
174
Evaluation of Daughter Products

Now consider the presence of a second constituent, which could exist in the
environment due to a release or be a degradation product, for example, TCE. The
fate of constituent 2 can be represented mathematically as the sum of 2 separate
expressions.
TCE(t) = f(t) + g(t)
where f(t) describes the fate of the portion of the mass that was released to the
environment, and g(t) describes the fate of the TCE generated from the degradation
of PCE. By inspection, f(t) can be written from Equation 4.11 as:
f (t ) =
s 20
x
exp 2 R f2
R f2
gw
Similiarly, g(t), the mass of TCE generated by the degradation of PCE, can also be
written from Equation 4.11 as:
( t ) =
12
x
s10 s10 exp 1 R f
1
R f1
gw
or
( t ) =
s1012
x
1 exp 1 R f
1
R f1
gw
The above expression describes the change in the total mass over time of the TCE
generated through the degradation of PCE. Therefore, the equation describing the
change in the dissolved concentration (consistent with Equation 4.11 and f(t) above,
and implicitly assuming that only the dissolved PCE degrades) is as follows:
(t ) =
s1012
x
1 exp 1 R f
1
R f1 R f2
gw
(4.12)
The mass of TCE generated from the degradaion of PCE also degrades consistent
with f(t). Therefore g(t) is written as follows:
g(t ) =
s1012
x
x
1 exp 1 R f
exp 2 R f2
1
R f1 R f2
gw
gw
(4.13)
175
The total change in concentration of TCE over time is therefore expressed as:
s 2 (t ) =
s 20
x s1012
x
x
1 exp 1 R f
exp 2 R f
exp 2 R f2
+
1
2
R f2
gw R f1 R f2
gw
gw
(4.14)
Now, consider cis-1,2 DCE, the degradation byproduct of TCE. There are three
possible fate and transport pathways for cis-1,2 DCE:
a) existing cis-1,2 DCE
b) cis-1,2 DCE formed by degradation of an existing source of TCE (existing)
c) cis-1,2 DCE formed by degradation of TCE which originated from the degradation
of PCE
a ) ( t ) =
s 30
x
exp 3 R f3
R f3
gw
b) (t ) =
s 20 23
x
x
1 exp 2 R f
exp 3 R f
2
3
R f2 R f3
gw
gw
c) The generated total cis-1,2 DCE from the decay of dissolved TCE from dissolved
PCE is
s1012 23
x
x
1 exp 1 R f
1 exp 2 R f
1
2
R f1 R f2
gw
gw
The equivalent dissolved cis-1,2 DCE is:
s1012 23
x
x
1 exp 1 R f
1 exp 2 R f
1
2
R f1 R f2 R f3
gw
gw
which changes in concentration with time:
(t ) =
s1012 23
x
x
x
1 exp 1 R f
1 exp 2 R f
exp 3 R f
1
2
3
R f1 R f2 R f3
gw
gw
gw
176
The equation describing the maximum down gradient concentrations of cis-1,2 DCE
is
DCE = s3(t) = (t) + (t) + (t)
or in expanded form,
s3 (t ) =
s 30
x s 20 23
x
x
1 exp 2 R f
exp 3 R f
exp 3 R f3
+
2
3
R f3
gw R f2 R f3
gw
gw
s10 2312
x
x
x
1 exp 1 R f
exp 3 R f
exp
R
1
2 f2
3
1
R f1 R f2 R f3
gw
gw
gw
x
* exp 3 R f3
gw
(4.15)
From inspection, the maximum concentrations of vinyl chloride, s4(t), are expressed
as:
s 4 (t ) =
s 40
x s 30 34
x
x
1 exp 3 R f
exp 4 R f
exp 4 R f4
+
3
4
R f4
gw R f3 R f4
gw
gw
s 20 23 34
x
x
x
1 exp 2 R f
1 exp 3 R f
exp 4 R f
3
4
2
R f2 R f3 R f4
gw
gw
gw
s1012 23 34
x
x
1 exp 1 R f
1 exp 2 R f
1
2
R f1 R f2 R f3 R f4
gw
gw
x
x
exp 4 R f
*1 exp 3 R f3
4
gw
gw
(4.16)
Again, from inspection, the equation for the transformation of vinyl chloride to
ethane can be written. Figure 4.17 describes the transformation of PCE to the final
desired end product ethene; the shapes of the individual curves will depend on the
degradation rates, retardation factor and other biogeochemical parameters.
Aqueous-phase concentration
177
Total VOC
PCE
TCE
DCE
Vinyl Chloride
Time
Figure 4.17
4.2.1.12
Aqueous-phase concentrations of chlorinated alkene compounds resulting from

the successive dechlorination of PCE.
IRZ Performance Data
The author and his colleagues have implemented about 100 IRZ applications,
beginning in 1993.1 During the technology evolution a lot of lessons were learned
and have been described earlier. The performance data presented in the next few
figures describe only the transformation or degradation of the contaminants during
IRZ applications. It should be noted that the information is not presented as sitespecific case studies, due to shortage of space.
Site in California
This site was a former metal plating facility and was contaminated with TCE
and Cr (VI). Very few daughter products were present prior to injection of molasses.
A grid-ike IRZ injection system was installed throughout the entire plume (two acres
in size) and injection of molasses began during the first quarter of 1996. Figure 4.18
presents the degradation and remediation of TCE and the formed daughter products
in terms of average concentrations throughout the entire plume. Figure 4.19a
describes the highest concentration of TCE found at the site and its decline during
the implementation of the IRZ. The increased concentration of TCE at this well (17
ppm) is believed to be a result of the microbial surfactant effect. The REDOX
potential within the plume was maintained at less than 250 mV via batch injections
of molasses. The TOC concentrations were always maintained above 200 ppm.
Figures 4.19b and 4.19c describe the reduction of Cr (VI) concentrations at the
same site.
Site in Northeastern U.S.
At a site in northeastern U.S., PCE and its daughter products were found in a
fractured bedrock environment. The plume was very long and a pump and treat
system was already in place at the site. Pilot studies for IRZ implementation were
performed and the primary objective was to implement a containment IRZ curtain
Sept.
1995
Dec.
1995
Mar.
1996
Sept.
1996
Dec.
1996
cis-1,2-DCE
Jun.
1996
TCE
Initial
Injection
Apr.
1997
June
1997
Performance data on enhanced reductive chlorination at a site in California.
0
Apr.
1995
500
1000
1500
2000
2500
3000
3500
4000
4500
Oct.
1997
Dec.
1997
ERD Application - Observation Well COC Concentrations
Mar.
1998
VC
June
1998
Oct.
1998
Feb.
1999
178
Figure 4.18
Concentration
5000
179
20
Concentration
15
TCE
10
Vinyl Chloride
DCE
April '97
June '97
Sept. '97
Dec. '97
Mar. '98
June '98
Sept. '98
Dec. '98
Date
Figure 4.19a
The reduction of TCE from about 17 ppm at the California site during an IRZ
implementation.
Injection of
molasses begins
180
Hexavalent Chromium (mg/L)
160
140
120
100
80
60
40
20
Dec. '96
April '97
June '97
Oct. '97
Dec. '97
Date
Figure 4.19b
Hexavalent chromium reduction at abandoned manufacturing facility in

California.
to bifurcate the plume. Figure 4.20 describes the performance of the IRZ at a
monitoring well with the decline of PCE and the formation and degradation of the
daughter products. This figure also shows the formation of ethene as the final end
product. Figure 4.21a and b is important to note because of the transformation of
cis-1,2 DCE to the final end product ethene, and also the observed mass balance of
the conversion.
Figure 4.22 describes the installation locations of the containment IRZ curtain,
and the bifurcation of the plume in a short time frame (nine months). At this point,
180
Remediation Injection
Events
70,000
Concentration (mg/L)
60,000
50,000
40,000
30,000
Total Chromium
Hexavalent Chromium
20,00
Jan. '99
Jan. '99
Jan. '99
Jan. '99
Oct. '98
July '98
Apr. '98
Jan. '98
Oct. '97
July '97
Apr. '97
Jan. '97
Nov. '96
Aug. '96
May '96
Feb. '96
10,00
Date
Figure 4.19c
Aerobic reduction of concentrations at all the wells.
ERD applications are taking place within the source area at this site after the
establishment of the downgradient IRZ curtain.
Site in Wisconsin
This was a former dry cleaning location within a strip mall in Wisconsin. Figure
4.23 describes the performance of the implemented IRZ at a monitoring well located
within the plume. All monitoring wells within the plume exhibited similar performance. Due to development activities at this site, some of the monitoring wells had
to be replaced at identical locations after these activities were finished. That is the
reason the pre-injection concentrations are shown as estimated instead of actual
concentrations. In all probability, the concentrations shown as estimated are the
actual pre-injection concentrations at those locations.
It is important to note the decline of PCE and the formation and degradation of
the daughter products. Ethylene concentrations were increasing until all the chlorinated compounds were degraded.
Site in Ohio
Another IRZ for ERD is being implemented at an industrial facility in Ohio.
The performance of the IRZ is described by a monitoring well located about 50 feet
from the injection locations (Figure 4.24). The disproportionate increase in DCE
concentrations shortly after injection is believed to be due to a combination of the
microbial surfactant effects and the enhanced degradation rates of the desorbed
contaminants.
Site in North Carolina
At this site a pilot study was initiated to address contamination at very high
concentrations of TCE (more than 100 ppm). The performance of the ongoing
Figure 4.20
Concentration changes in a performance monitoring well within an IRZ for ERD, 70 feet downgradient from the injection well. Note: There
is a gradual increase of the final transformation product ethene and a reasonably steady level until all the chlorinated ethenes have been
transformed.

181
182
Figure 4.21
Concentration changes in mg/L and M at a monitoring well 50 feet from the

injection zone.
pilot study is shown in Figure 4.25. This is the first site where the author has
implemented an IRZ when the initial chlorinated contaminant concentrations were
more than 100 ppm.
Site in Pennsylvania
An ongoing pump and treat system had reached asymplotic concentrations at
this site after 13 years of operation and the desire was to accelerate the time required
for closure. Once the IRZ was established, the site was closed after reaching cleanup
levels in less than 12 months. (Figure 4.26).
Figure 4.22
4.2.2
183
The effect of containment IRZs on a long plume of PCE (contamination shown

are total VOCs).
In Situ Metals Precipitation
The presence of metals in the subsurface environment can be in many forms:

elemental, ionic, and/or organometallic. Distribution of the commonly encountered
metals in the subsurface can be categorized as follows:
Elemental form
Mercury
Lead
Gold, silver and the other noble metals
Metal alloys: brass (copper and zinc); bronze (copper, tin, and zinc); nickelcadmium
Ionic form
Arsenic: As (III) arsenite, AsO32 ; As (V) arsenate, AsO43
Chromium: trivalent Cr (III); hexavalent Cr (VI), Cr2O72 and CrO42
Iron: Ferrous Fe (III); Ferric Fe (III)
Copper, lead, zinc, cadmium: Cu+1, Cu2+, Pb2+, Zn2+, Cd2+
Mercury: Hg+1, Hg+2
Organometallic form
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)21 ; Fe (CN)64
The common range of concentrations of naturally encountered metals in the

subsurface environment is shown in Table 4.8.
In order to understand the fate of heavy metals in the soil-water system, it is
important to understand the general characteristics of soil and the chemistry of heavy
metals in an aqueous solution. In the aquatic environment, heavy metals may be
classified into at least two different categories: 1) in true solution as free or complexed ions, and 2) in particulates from adsorption onto other particles, or incorporation into biomass of living organisms and inorganic precipitates such as hydroxides, carbonates, sulfides, and sulfates.
Apr.
1997
Nov.
1997
PCE
Estimated Pre-Remediation
Groundwater Conditions
TCE
June
1998
Dec.
1998
July
1999
cis -1,2-DCE
Initial
Injection
VC
Jan.
2000
Ethylene
Concentration declines in a monitoring well within an IRZ for enhanced reductive dechlorination at a site in Wisconsin.
0
Oct.
1996
500
1000
1500
2000
2500
3000
0
Aug.
2000
50
100
150
200
250
300
350
400
450
Figure 4.23
Concentration
Groundwater Contamination Concentrations vs. Time
184
Ethylene
Figure 4.24
185
Performance data from a monitoring well 50 feet downgradient of the injection

zone. Substantial increase in mass was observed due to the microbial surfactant
effects. Note the increasing concentration of the daughter products with time and
the excellent correlation of mass balance on a milli molar basis. The last data
point shows that the transformation is complete to ethene.
160000
140000
Concentration (ug/L)
TCE
120000
cis-1,2-DCE
100000
80000
60000
PCE
40000
Vinyl Chloride
20000
Aug. '99
Oct. '99
Dec. '99
Jan. '00
Mar. '00
May '00
June '00
Aug. '00
Oct. '00
Date
Figure 4.25
Concentrations of VOCs in the pilot observation well vs. time, in situ reactive
zone pilot test.
186
In-Situ Remediation
Using Molasses
Injection
Pump and Treat

Remediation
1000
Concentration (ug/L)
Chromium
TCE
100
10
May '90
Mar. '94
Aug. '95
Mar. '96
Mar. June Sept.

'97 '97 '97
Date
Figure 4.26
TCE and chromium concentrations vs. time.
Table 4.8 Common Concentration

Range of Metals in Soils
(mg/Kg)77
Element
Range
Average
Antimony (Sb)
Arsenic (As)
Barium (Ba)
Beryllium (Be)
Cadmium (Cd)
Chromium (Cr)
Cobalt (Co)
Copper (Cu)
Lead (Pb)
Mercury (Hg)
Nickel (Ni)
Selenium (Se)
Silver (Ag)
Tin (Sn)
Vanadium (V)
Zinc (Zn)
210
150
1003,000
0.140
0.010.7
11,000
140
2100
2200
0.020.3
5500
0.12
0.015
2200
20500
10300
--5
430
6
0.06
100
8
3
10
0.03
40
0.3
0.05
1
100
50
Dec.
'97
187
Many metals are found as very insoluble sulfide (Zn, Ag, Hg, Cu, Cd, Pb, Ni,
Co) carbonate and hydroxide (Cr, Fe) forms. Biogeochemical impacts on the groundwater concentrations of species such as sulfides (from sulfate reduction) and carbonates (via CO2 formation) enable many dissolved metallic ions to be precipitated
and immobilized.
In a soil-water system, the fate of heavy metals is directly related to their states
of identity and the existing biogeochemical conditions. The free and complexed
metal ions may be removed from solution by adsorption and precipitation mechanisms, while the particulate heavy metals may be transformed by their own dissolution and filtration mechanism of soils. In principle, the concentration of heavy
metals in an aqueous system is controlled by the congruent and incongruent solubility
of various oxides, carbonates, sulfates, and sulfides.
Metal precipitates in soil systems represent a selective accumulation of at least
two or more constituent ions into an organized solid matrix 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 which separates from a continuous medium. The fact that solid phases form
in soil-water systems 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 formation 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.80 Under classical
nucleation theory, three steps are generally considered necessary for those microscale
processes to result in the formation of crystals that will persist and survive over
relatively long periods of time: nuclei formation, crystallite formation, and crystal
(precipitate) formation.80
Complexation reactions are also important in determining the saturation state of
groundwater. A complex is an ion that forms by combining simpler cations, anions,
and sometimes 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 S2, CO32 , SO42 , PO43 , NO3, Cl. The ligand might
also be an organic molecule such as amino acid.
4.2.2.1 Principles of Heavy Metals Precipitation
The mechanisms that can be used to reduce the concentrations of heavy metals
dissolved in groundwater are transformation and immobilization. These mechanisms
can be induced by both abiotic and biotic pathways. Abiotic pathways include
oxidation, reduction, sorption, and precipitation. Examples of biotically mediated
processes include: reduction, oxidation, precipitation, biosorption, bioaccumulation,
organo-metal complexation and phytoremediation. In this chapter, immobilization
mechanisms induced only by precipitation will be discussed.
Dissolved heavy metals can be precipitated out of solution through various
precipitation reactions shown below. A divalent metallic cation is used as an example
in these reactions.
188
Hydroxide precipitation: Me++ + 2OH Me (OH)2

Sulfide precipitation:
Me++ + S2 MeS
Carbonate precipitation: Me++ + CO3 MeCO3
(4.17)
(4.18)
(4.19)
Theoretical behavior of solubility of these precipitation mechanisms is shown

in Figure 4.27.
log [Me++]
Carbonate Precipitate
Hydroxide
Precipitate
Sulfide
Precipitate
pH
Figure 4.27
Theoretical pathways of solubility of metals.
Hydroxide and sulfide precipitation of heavy metals have been used successfully
in conventional industrial waste water systems. Lime (Ca(OH)2) or other alkaline
solutions such as potash (KOH) are used as reagents for hydroxide precipitation.
Sodium sulfide (Na2S) is normally used as the reagent to form extremely insoluble
metallic sulfide precipitates. Injection of these chemical reagents into the contaminated aquifers to create a reactive zone will precipitate the heavy metals out of
solution. However, injection of a reactive, pH altering chemical reagent into the
groundwater may be objectionable from a regulatory point of view. Obtaining the
required permits to implement chemical precipitation may be difficult. Furthermore,
the metallic cations precipitated out as hydroxide could be resolubilized slightly as
a result of any significant shift in groundwater pH.
189
Under reducing conditions, heavy metal cations can be removed from solution
as sulfide precipitates if sufficient sulfur is available. In systems containing a sufficient supply of sulfur, neutral to mildly alkaline pH and low REDOX conditions are
most favorable for the precipitation of many heavy metals. Chromium is insoluble
under reducing conditions, as Cr (III) hydroxide, but only at neutral to mildly acidic
and alkaline pH values.
Precipitation as sulfides is considered the dominant mechanism limiting the
solubility of many heavy metals. Sulfide precipitation is particularly strong for
chalcophilic metals exhibiting so-called B-character, such as Cu (I), Ag, Hg,
Cd, Pb, and Zn; it also is an important mechanism for transition elements such as
Cu (II), Ni (I), Co (II), Fe (II) and Mn (II).81 Two situations can be distinguished in
natural systems during sulfide precipitation conditions: the existence of a certain
sulfide precipitation capacity (SPC), or (when exceeding the SPC) the accumulation
of free sulfide (as H2S or HS) in the aqueous phase. At excess sulfide concentrations,
solubility of some metals can be increased by the formation of thio complexes.
However, the stability of these complexes is still questionable. Possible pathways
of metal precipitate interactions are shown in Figure 4.28. Figure 4.29 describes the
fields of dominance of the different sulfur species in groundwater.
Mineral Surface
Figure 4.28
Organic Surface
Inorganic
Complex
Free
Ion
Organic
Complex
Precipitate
Occlusion
Living Biomass
Heavy metal interactions in an aquifer matrix.
The sulfide ions necessary to mediate sulfide precipitation can be directly injected
into a reactive zone in the form of sodium sulfide (Na2S). However, the sulfide ion
(S2) is one of the most reduced ion and its stability within the reactive zone is short
lived. It will be converted to sulfate (SO4 ) very quickly in the presence of oxidizing
190
1.40
1.20
Water Oxidized
1.00
0.80
HSO4-
Eh, in Volts
0.60
0.40
SO2-
S0
0.20
0.00
H2Saq
-0.20
-0.40
HS-
-0.60
Water Reduced
S2
-0.80
-1.00
0
10
12
14
pH
Figure 4.29
Fields of dominance of sulfur species at equilibrium at 25C and 1 atmosphere

(adapted from Hem, 1985).
conditions within the contaminated plume. Addition of a very easily biodegradable

organic substrate, such as carbohydrates, will enhance the formation of reduced,
anaerobic conditions by depleting the available 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 to sulfide.
Indirect microbial transformation of metals can occur as a result of sulfate
reduction when anaerobic bacteria oxidize simple carbon substrates with sulfate
serving as the electron acceptor. The net result of the process is the production of
hydrogen sulfide (H2S) and alkalinity (HCO3 ). Sulfate reduction is strictly an anaerobic process and proceeds only in the absence of oxygen. The process requires a
source of carbon to support microbial growth, a source of sulfate, and a population
of sulfate reducing bacteria. Dilute black strap molasses solution is an ideal feed
191
substrate for this purpose since typical black strap molasses contains approximately
20% sucrose, 20% reducing sugars, 10% sulfated ash, 20% organic non sugars, and
30% water.1
Whether formed biotically or abiotically, the metal sulfides result from an interaction between the metal ion and sulfide ion:
Me2+ + S2 MS
(4.20)
It is the source of the sulfide that determines whether a biological agent is

implicated in metal sulfide formation. If the sulfide results from bacterial sulfate
reduction or from bacterial mineralization of organic compounds, it is obviously of
biotic origin. If it is derived from volcanic activity, it is generally of abiotic origin.
The metal sulfides, because of their relative insolubility, form readily at ordinary
temperatures and pressures by interaction of metal ions and sulfide ions. Table 4.9
lists solubility products for some common simple sulfides.83
Table 4.9 Solubility Products for Some Metal Sulfides81

CdS
Bi2S3
CoS2
Cu2S
CuS
1.4 1028
1.6 1072
7 1023
2.5 1050
4 1038
1 1019
1 1029
5.6 1016
1 1045
3 1053
FeS
PbS
MnS
Hg2S
HgS
NiS
Ag2S
SnS
ZnS
H 2S
HS-
3 1021
1 1051
8 1029
4.5 1024
1.1 107
1 1015
The following calculation will show that relatively low concentrations are needed
to form metal sulfides by reacting with H2S at typical concentrations that can be
formed in an anaerobic IRZ.83 Let us examine, for instance, the case of iron. The
dissociation constant for iron sulfide (FeS) is:
[Fe2+][S2] = 1 x 1019
(4.21)
The dissociation constant for H2S is:

H S
[S ] = 1.1 x 10 [H ]
[ ]
(4.22)
[HS ][H ] = 1.1 x 10

[H S]
(4.23)
22
2
+ 2
since,
and,
192
[S ][H ] = 1 x 10
[HS ]
2
15
(4.24)
Therefore,
[Fe
H
]= [ ]
+ 2
2+
[ ](
2
H+
1 x 10 19
9.1 x 10 2
x
=
[H 2S] 1.1 x 10 22 [H 2S]
(4.25)
About 5.08 103 mg of Fe2+ per liter (9.1 108 M) will be precipitated by 3.4
mg of hydrogen sulfide per liter (104 M) at pH 7. The unused H2S will ensure reducing
conditions, which will keep the iron in the ferrous state. Since ferrous sulfide is one
of the more-soluble sulfides, it can be seen that metals whose sulfides have even smaller
solubility products will form even more readily at lower H2S concentrations.
Metal sulfides have been generated in laboratory experiments utilizing H2S from
bacterial sulfate reduction. It has been reported that sulfides of Sb, Bi, Co, Cd, Fe, Pb,
Ni, and Zn were formed in a lactate broth culture of Desulfovibrio desulfuricans to
which sulfate and salts of selected metals had been added.83 Metal toxicity to Desulfovibrio desulfuricans depends in part on the concentration of the metallic ion in
question. Obviously, for the corresponding metal sulfide to be formed, the metal sulfide
must be even more insoluble than the starting compound of the metal. More metals
such as Cu, Ag, Cd, Pb, Zn, Ni, and Co, in addition to Fe and Mn, can also be
precipitated as metallic sulfides. Precipitated metallic sulfides will remain in an insoluble, stable form, unless the subsurface REDOX conditions change dramatically.
The production of alkalinity from sulfate reduction, denitrification, and other
reactions causes an increase in pH, which can result in metal precipitation through the
formation of insoluble metal hydroxides or oxides. This process follows the reaction:
Me2+ + 2H2O Me (OH)2 + 2H+
(4.26)
Chromium Precipitation
In situ microbial reduction of dissolved hexavent chromium Cr (VI) to trivalent
chromium Cr (III) yields significant remedial benefits because trivalent chromium
Cr (III) is less toxic, water insoluble, and, thus, nonmobile, and precipitates out
of solution. In fact, it has been stated that the natural attenuation of Cr (VI) to the
reduced Cr (III) form within an aquifer is a viable groundwater remediation
technique.
In situ microbial reduction of Cr (VI) to Cr (III) can be promoted by injecting
a carbohydrate solution, such as dilute molasses solution. The carbohydrates, which
consist mostly of sucrose, are readily degraded by the heterotrophic microorganisms
present in the aquifer, thus depleting all the available dissolved oxygen present in
the groundwater. Depletion of the available oxygen present causes reducing conditions to develop. The mechanisms of Cr (VI) reduction to Cr (III) under induced
reducing conditions can be 1) likely a microbial reduction process involving Cr (VI)
193
as a terminal electron acceptor for the metabolism of carbohydrates by species such

as Bacillus subtilis; 2) an extra cellular reaction with by-products of sulfate reduction
such as H2S; and 3) abiotic oxidation of the organic compounds including the soil
organic matter such as humic and fulvic acids.84
Cr (VI) is known to be reduced both aerobically and anaerobically in different
bacterial systems. In anaerobic systems, membrane preparations reduce Cr (VI),
which has been shown to serve as a terminal electron acceptor. Aerobic reduction
of Cr (VI) has been found to be associated with soluble proteins. The enzymatic
basis for aerobic chromate reduction is not known, but it has been proposed that
chromate may be reduced by a soluble reductase enzyme with a completely unrelated
primary physiological role. Based on the diversity of Cr (VI) reducing microorganisms in soil, provision of a suitable electron donor such as molasses may be sufficient
and the ORP within the IRZ need not be reduced to 250 to 300 mV as is the case
during ERD applications.85,86
The primary end product of Cr (VI) to Cr (III) reduction process is chromic
hydroxide [Cr (OH)3], which readily precipitates out of solution under alkaline to
moderately acidic and alkaline conditions.87 To ensure that this process will provide
both short term and long term effectiveness in meeting groundwater cleanup objectives, the chromium precipitates must remain immobilized within the soil matrix of
the aquifer, and could not be subject to Cr (OH)3 precipitate dissolution or oxidation
of Cr (III) back to Cr (VI) once groundwater conditions revert back to natural
conditions. Based on the results of significant research being conducted on the in
situ chromium reduction process, it is readily apparent that the Cr (OH)3 precipitate
is essentially an insoluble, stable precipitate, immobilized in the soil matrix of
the aquifer.
Contrary to the numerous natural mechanisms that cause the reduction of Cr
(VI) to Cr (III), there appear to be only a few natural mechanisms for the oxidation
of Cr (III). Indeed, only two constituents in the subsurface environment (dissolved
oxygen and manganese dioxide) are known to oxidize Cr (III) to Cr (VI).88 The
results of studies conducted on the potential reaction between dissolved oxygen and
Cr (III) indicate that dissolved oxygen will not cause the oxidation of Cr (III) under
normal groundwater conditions. However, studies have shown that Cr (III) can be
oxidized by manganese dioxides, which may be present in the soil matrix. However,
only one phase of manganese dioxides is known to oxidize appreciable amounts of
Cr (III) and this process is inversely related to groundwater pH. Hence, the oxidation
of Cr (III) back to Cr (VI) in a natural aquifer system is highly unlikely.
The Cr (OH)3 precipitate has an extremely low solubility (solubility product,
Ksp = 6.7 1031) and thus, very little of the chromium hydroxide is expected to
remain in solution. It has been reported that aqueous concentration of Cr (III), in
equilibrium with Cr (OH)3 precipitates, is around 0.05 mg/L within the pH range
of 5 to 12 (Figure 4.30). The pH range of natural aquifer systems will be within 5
to 12 and, hence, the potential for the chromic hydroxide to resolubilize is unlikely.
Furthermore, the potential for co-precipitation with Ferric ions will further decrease
the solubility of Cr (OH)3.
Dissolved Cr (VI) can be also precipitated as Cr (OH)3 in a reactive zone by the
injection of ferrous sulfate solution into a reactive zone at appropriate concentrations.
194
-2
log [Cr(lll)]
Cr(OH)3(am)
-4
MCL
-6
-8
10
12
14
pH
Figure 4.30
Cr (III) concentration in equilibrium with Cr (OH)3.
Cr (VI) exists as chromate, CrO42 , under neutral or alkaline conditions and dichromate, Cr2O72 , under acidic conditions. Both species react with ferrous ion:
Acidic conditions:
Cr2O72 + 6Fe2+ + 14H+ 2Cr3+ + 6Fe3+ + 7H2O

(4.27)
Neutral or alkaline condition: CrO42 + 3Fe2+ + 4H2O Cr3+ + 3Fe3+ + 8OH

(4.28)
Both Cr (III) and Fe (III) ions are highly insoluble under natural conditions of
groundwater (neutral pH or slightly acidic or alkaline conditions).
Fe3+ + 3OH Fe (OH)3
(4.29)
Cr3+ + 3OH Cr (OH)3
(4.20)
The addition of ferrous sulfate into the reactive zone may create acidic conditions and, hence, the zone downgradient of the ferrous sulfate injection zone
may have to be injected with soda ash or caustic soda to bring the pH back to
neutral conditions.
Arsenic Precipitation
Soluble arsenic occurs in natural waters only in the pentavalent, As (V) and
trivalent, As (III), oxidation states. Although both organic and inorganic forms of
arsenic have been detected, organic species (such as methylated arsenic) are rarely
195
present at concentrations greater than 1 ppb and are generally considered of little
environmental significance compared with inorganic arsenic species. Thus, this
discussion focuses exclusively on the behavior of inorganic arsenic.
Thermodynamics provides useful insight into the equilibrium chemistry of inorganic arsenic species. In oxygenated waters, As (V) is dominant, existing in anionic
forms of either H2AsO4 , HAsO42 , or AsO43 over the pH range of 5 to 12, which
covers the range encountered in natural groundwater. Under anoxic conditions, As
(III) is stable, with nonionic (H3AsO3) and anionic (H2AsO3 ) species dominant
below and above pH 9.22, respectively. In the presence of sulfides, precipitation of
AsS (realgar) or As2S3 (orpiment) may remove soluble As (III) and exert considerable
control over trace arsenic concentrations. The thermodynamic reduction of As (V)
to As (III) in the absence of oxygen could be chemically slow and may require
bacterial mediation.13 As noted in the previous section, injection of dilute solution
of blackstrap molasses will create the reducing conditions for As (V) to be reduced
to As (III) and also provide the sulfide ions for As (III) to precipitate as As2S3. These
reactions are described by the following equations:10
Reduction of As (V) to As (III) under anaerobic conditions:
HAsO42 HAsO2
In the presence of S under anaerobic conditions:
HAsO2 + S As2S3
Within oxygenated zones in the aquifer, oxidation of Ferrous ion (Fe (II)) and
Mn (II) leads to formation of hydroxides that will remove soluble As (V) by
coprecipitation or adsorption reactions. The production of oxidized Fe-Mn species
and subsequent precipitation of hydroxides are analogous to an in situ coagulation
process for removing As (V).
4.2.2.2 Aquifer Parameters and Transport Mechanisms
REDOX processes can induce strong acidification or alkalinization of soils and
aquifer systems. Oxidized components are more acidic (SO42 , NO3) or less basic
(Fe2O3) than their reduced counterparts (H2S, NH3). As a result, alkalinity and pH
tend to increase with reduction and decrease with oxidation. Carbonates are efficient
buffers in natural aquifer systems in the neutral pH range.
Many events can cause changes in REDOX conditions in an aquifer. Infiltration
of water with high dissolved oxygen concentration, fluctuating water table, excess
organic matter, introduction of contaminants that are easily degradable, increased
microbial activity, and deterioration of soil structure can impact the REDOX
conditions in the subsurface. However, there is an inherent capacity to resist REDOX
changes in natural aquifer systems. This inherent capacity depends on the availability
of oxidized or reduced species. REDOX buffering is provided by the presence of
various electron donors and electron acceptors present in the aquifer.
196
An engineered in situ reactive zone has to take into consideration how the target
reactions will impact the REDOX conditions within and downgradient of the reactive
zone, in addition to degrading the contaminants with the available residence time.
Furthermore, careful evaluation should be performed regarding the selectivity of the
injected reagents towards the target contaminants and the potential to react with
other compounds or aquifer materials. Careful monitoring, short term and long term,
should be performed 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 reoccurrence of contaminants.
4.2.2.3 Contaminant Removal Mechanisms
As noted earlier, the mechanisms used to reduce the toxicity of dissolved contaminants can be grouped into two major categories: transformation and immobilization. Examples of some of these mechanisms have been discussed earlier. Conversion of chlorinated organic compounds to innocuous end products such as CO2,
H2O, and Cl by either biotic or abiotic reaction pathways is an example of transformation mechanisms. Precipitation of Cr (VI) as Cr (OH)3 by either abiotic or
biotic reaction pathways and subsequent filtration by the soil matrix is an example
of immobilization mechanisms.
It can be assumed, in most cases, that the end products of transformation mechanisms will result in dissolved and gaseous species and that the impact of these end
products on the natural REDOX equilibrium will be short term. If the impact is expected
to be significant, it can be controlled by limiting the reaction kinetics and transport of
the end products from the reaction zone. Dilution and escape of dissolved gases will
also help in restoring the natural equilibrium conditions in the reaction zone.
Immobilization mechanisms, which include heavy metals precipitation reactions, in reality transform the contaminant into a form (precipitate) which is much
less soluble. In addition, transport of dissolved heavy metals in groundwater should
be considered a two-phase system in which the dissolved metals partition between
the soil matrix and the mobile aqueous phase.
Metal precipitates resulting from an in situ reactive zone may move in association
with colloidal particles or as particles themselves of colloidal dimensions. The term
colloid is generally applied to particles with a size range of 0.001 to 1 m. The
transport of contaminants as colloids may result in unexpected mobility of low
solubility precipitates. It is important to remember that the transport behavior of
colloids is determined by the physical/chemical properties of the colloids as well as
the soil matrix.
Generally, when fine particles of colloid dimensions are formed, 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.
Metal precipitates may be pure solids (e.g., PbS, ZnS, Cr (OH)3) or mixed solids
(e.g., (Fex, Cr1x) (OH)3, Ba(CrO4, SO4)). Mixed solids are formed when various
elements co-precipitate or due to interaction with aquifer materials.
197
Colloidal precipitates larger than 2 m in the low flow conditions common in

aquifer systems will be removed by sedimentation. Colloidal precipitates are more
often removed mechanically in the soil matrix. Mechanical removal of particles
occurs most often by straining, a process in which particles can enter the matrix,
but are caught by the smaller pore spaces as they traverse it.
Colloidal particles below 0.1 m will be subjected more to adsorptive mechanisms 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 composition of the soil matrix, and flow
velocity of the groundwater. Higher levels of total dissolved solids (TDS) in the
groundwater encourage colloid deposition.
In aquifer systems with high Fe concentrations, the amorphous hydrous ferric
oxide 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
cation or ion exchange, respectively. Adsorption behavior is primarily related to pH
(within the typical range of 5.0 to 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 pounds of
metals as cations or metallic complexes. This phenomenon is extremely useful for
the removal of As and Cr.
4.2.3
In Situ Denitrification
Nitrogen can form a variety of compounds due to its different oxidation states.
In the natural ecosystem, most changes from one oxidation state to another are
biologically induced. The nitrogen forms in Table 4.10 are of interest in relation to
the subsurface environment.
Table 4.10 Nitrogen Forms Present in the
Subsurface Environment
Nitrogen Compound
Ammonia
Ammonium ion
Nitrogen gas
Nitrite ion
Nitrate ion
Formula
Oxidation State
NH3
NH+4
N2
NO2
NO3
3
3
0
+3
+5
The unionized, 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, synthesis, nitrification, and denitrification.
Ammonification refers to the change from organic nitrogen to the ammonium
form. In general, ammonification occurs during decomposition of animal and plant
tissue and animal fecal matter and can be expressed as follows:
198
Organic Nitrogen + Ammonifying Microorganisms NH3 /NH+4
(4.31)
Nitrification refers to the biological oxidation of ammonium ions under aerobic

conditions by the chemoautotrophic organisms called nitrifiers. Two specific
chemoautotrophic bacterial genera are involved, using inorganic carbon as their
source of cellular carbon:
NH 4+ + O 2
Nitrosomonas
Nitrobacter
NO 2 + O 2
NO 3
bacteria
bacteria
(4.32)
The transformation reactions are generally coupled and proceed rapidly to the
nitrate form.
In situ denitrification can be accomplished by organisms belonging to the genera
Micrococcus, Pseudomonas, Denitrobacillus, Spirillum, Bacillus, Achromobacter,
Acinetobacter, Gluconobacter, Alcaligens, and Thiobacillus, which are present in the
groundwater environment. Denitrifying organisms will utilize nitrate or nitrite in the
absence of oxygen as the terminal electron acceptor for their metabolic activity. If
any oxygen is present in the environment, it will probably be used preferentially.
The energy for the denitrifying reactions is released by organic carbon sources that
act as electron donors. The microbial pathways of denitrification include the reduction of nitrate to nitrite and the subsequent reduction of nitrite to nitrogen gas.
NO3 NO2 N2
(4.33)
In biological wastewater treatment processes employing denitrification, a cheap,

external carbon source such as methanol is added as the electron donor. It has long
been known that NO3 can be converted to N2 gas in anaerobic groundwater zones
in the presence of a labile carbon source.
In situ microbial denitrification is based on the same principle as conventional
biological wastewater treatment systems, 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, sucrose or sugar solution is
an optimum substrate to be injected.
It should be noted that in the hierarchy of REDOX reactions, NO3 is the most
favored electron acceptor after dissolved oxygen. Hence, considerable attention
should be focused in maintaining the REDOX potential in the optimum range, so
that Mn (IV), Fe (III), sulfate reduction conditions or methanogenic conditions are
not formed in the subsurface. Furthermore, since denitrification is a reduction reaction, alkalinity and pH tend to increase in the aquifer. Since the end product N2 gas
will escape into the vadose zone and, hence, the aquifer system is not a closed
system, increased alkalinity will be observed in the groundwater. If the NO3 concentration is not very high, this concern will be short lived.
L1282_C04-C_frame Page 199 Thursday, March 6, 2003 11:42 AM
4.2.4
199
Perchlorate Reduction
Perchlorate has been widely used as a propellant in solid rocket fuel and has
recently been identified as a contaminant in both groundwater and surface waters.
Perchlorate is recognized by the USEPA as a potential health risk; California has
set a drinking water action level of 18 ppb.
Most of the perchlorate contamination in groundwater appears to have come
from the legal discharge decades ago 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 dissolving in water:
NH4 ClO4 NH4+ + ClO4
(4.34)
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.89
The persistence of perchlorate in groundwater aquifers results primarily from a
combination of aerobic conditions and lack of an electron donor. A number of
bacteria that contain nitrate reductases are capable of dissimilatory reduction of
perchlorate.89,90 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.90 Chlorate reductase has been isolated from microorganisms that also possess nitrate reductase. 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 laboratory
studies.90,91
The conversion of chlorine in perchlorate to chloride requires the overall transfer
of eight electrons. The sequence of intermediates involved in perchlorate reduction
is as follows:
ClO 3- ClO 2- O 2 + Cl ClO -4
(chloride)
( perchlorate) (chlorate) (chlorite)
(4.35)
In situ bioremediation, via an IRZ, appears to be 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. Anaerobic respiration is an
energy yielding process in which the oxidation of an electron donor, such as an
easily degradable organic substrate, is coupled to the reduction of an electron acceptor, such as perchlorate and chlorate. Chlorite can be inhibitory to microbial activity,
and the transformation of chlorite to chloride and O2 is believed to be a nonenergy
L1282_C04-C_frame Page 200 Monday, June 18, 2001 9:44 AM
200
yielding enzymatic detoxification mechanism that protects the cell and allows the
bacterium to use perchlorate and chlorate as electron acceptors.90,91
Implementation of an IRZ with the introduction of easily biodegradable electron
donors such as hexoses, acetate, or lactate (without the presence of other electron
acceptors such as SO42 ) should be able to reduce the concentrations of ClO4 present
in the groundwater. A tenfold reduction of perchorate was achieved in column
experiments at residence times of less than 48 hours. Laboratory column experiments
have demonstrated that perchlorate degradation can be achieved at influent levels
ranging from 0.1 to 1000 mg/L.91 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 author and his colleagues are currently involved in initiating
field scale testing to implement in situ biodegradation of perchlorate.
Since most of the perchlorate plumes are decades old and also due to its high
solubility, there are significantly large sized groundwater plumes of this contaminant.
Hence, it is very important to select the cheapest electron donor to create an in situ
reactive zone (IRZ) to achieve perchlorate degradation in situ. The persistence of
perchlorate itself is enhanced by the oxidative poise available within these plumes.
Hence, it is equally important to select the cheapest electron donor to overcome the
oxidative poise within these large plumes.
4.3
4.3.1
ENGINEERED AEROBIC SYSTEMS
Direct Aerobic Oxidation
The majority of the compounds in petroleum products are biodegradable at

significantly faster rates under aerobic conditions. The amount of oxygen required
for complete aerobic mineralization of one gram of hydrocarbon ranges from three
to three and a half grams. In simplistic volumetric terms, 300,000 kilograms of
oxygen-saturated water must be delivered and mixed in order to mineralize one
kilogram of petroleum hydrocarbons. This illustrates the need to select the technically and economically most effective method of delivering O2 into the groundwater
and also to maximize the efficiency of O2 utilization by the microorganisms in the
subsurface. The total cost of a pound of dissolved O2 delivered into the subsurface
could range from 0.80 to $10.00, depending on the method selected and the geologic
and hydrogeologic conditions encountered at a site. The cheapest method of delivering dissolved O2, if hydrogeologic conditions are conducive, is by injecting dilute
hydrogen peroxide (at about 1001000 ppm concentrations) into the contaminated
zone. Other methods of oxygen delivery include various methods of air injection
and expensive methods such as oxygen release compounds.
In addition to the petroleum hydrocarbons, other compounds more conducive
for aerobic biodegradation are: nonchlorinated phenolic compounds, alcohols,
ketones, aldehydes, etc. Among the chlorinated compounds chlorobenzene, methylene chloride, and vinyl chloride are among the commonly encountered contaminants
that are biodegradable faster under aerobic conditions.
201
The most significant biological mechanism for the degradation of chlorinated

solvents is when they are used as a primary substrate. In direct oxidation reactions,
the chlorinated compound acts as an electron donor and the microorganism uses
molecular oxygen as an electron acceptor. The microorganism obtains energy and
organic carbon from the degraded chlorinated compound. The more chlorinated
compounds, PCE, carbon tetrachloride (CT), and hexachloroethane (HCA), are
neither susceptible to aerobic oxidation nor degraded under anaerobic oxidizing
conditions when used as a primary substrate.14 TCE undergoes slow aerobic degradation to trichloroethanol and then to acetic acid, but the reaction is not thermodynamically favorable. Therefore, discussion of aerobic oxidation and mineralization
has always been focused on DCE and vinyl chloride (VC).
Rates of aerobic oxidation are more rapid for the less chlorinated organics (DCE
and VC) when compared to their reductive dechlorination rates. It has been well
documented in literature that VC is oxidized directly to carbon dioxide and water.
Aerobic oxidation of cis-1,2 DCE has been speculated. However, it could not be
ascertained whether DCE was reduced to VC and then direct oxidation of VC produced
carbon dioxide or direct oxidation of DCE occurred to produce carbon dioxide.
Under aerobic conditions, chlorinated aliphatic compounds with one or two
carbons per molecule can be transformed by three types of microbial enzymes:13
dehalogenases, hydrolytic 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-choloralkyl-gluthathione, 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 halogenated compounds; the products could be alcohols, aldehydes, or epoxides,
depending on the structure of the compound. Numerous chlorinated short-chain
aliphatic hydrocarbons have been demonstrated to undergo aerobic transformation.
However, compounds that have all the available valences on their carbon atoms
substituted by chlorine, such as PCE or carbon tetrachloride, have never been shown
to transform through any other but reductive pathways. Generally, as the degree of
chlorination increases, the likelihood of aerobic transformation decreases (Figure
4.31); the opposite is true for anaerobic (reductive) transformations.
Among the methane compounds, methylene chloride (MC) and chloromethane
have been found to be amenable to aerobic microbial transformation. Pure cultures
of the genera Pseudomonas and Hyphomicrobium have been isolated that can grow
on methylene chloride as the sole carbon and energy source.13,15
Alkylhalides (haloalkanes), such as 1,2-dichloroethane (1,2-DCA), are frequently hydrolytically dehalogenated. Xanthobacter autotrophicus utilizes 1,2-DCA
as sole carbon source. Complex communities consisting of methanotrophs and
heterotrophs, which inhabit groundwater aquifers, mineralize 1,2-DCA. A
Pseudomonas fluorescens strain isolated from water and soil contaminated by chlorinated 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.13,15
202
Relative Rate of Oxidation
Relative Rate of Reduction
0
0
0
CM
CA
VC
Figure 4.31
MC
CF
1,2DCA 1,1DCA
1,1,2TCA
1,2DCE 1,1DCE
TCE
Increasing Extent of Chlorination
CT
TCA
HCE
PCE
Methanes
Ethanes
Ethenes
Relative rates of oxidation and reduction from a range of C1 and C2 chlorinated

compounds (adapted from Semprini et al., 1992).
4.3.1.1 Aerobic Cometabolic Oxidation

Chloroalkanes, such as TCE, cis- and trans-1,2-DCE, 1,1,-DCE, and VC, are
also transformed by several different physiological groups of aerobes. Methanotrophic communities consisting of methanotrophs that initiate the oxidative transformation, and heterotrophs which utilize the products of oxidation and hydrolysis,
are very active in this respect, and 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 transform
TCE, trans-1,2-DCE, and cis-1,2-DCE.13,14,15 Other microorganisms capable of
transforming chlorinated alkenes belong to the genera Pseudomonas, Alcaligenes,
Mycobacterium, and Nitrosomonas. All of these microorganisms, except the genus
Nitrosomonas, are heterotrophs which grow on various organic substrates (e.g.,
toluene, cresol, phenols, propane, etc.); Nitrosomonas is a chemolitotroph which
derives energy from oxidation of ammonia. All of them cometabolize chlorinated
compounds such as TCE or 1,2-DCE while growing on their respective growth
substrates; the haloalkenes are only fortuitously transformed, not utilized for growth.
However, vinyl chloride seems to be an exception: it has been demonstrated that a
Mycobacterium strain isolated from soil contaminated by VC could grow on VC as
a sole carbon and energy source.92
Aerobic cometabolism of chlorinated compounds at low concentrations by methane- and propane-utilizing bacteria is well documented. In comparison, butaneutilizing bacteria are less susceptible to the toxic effects of elevated chlorinated
203
compound concentrations. Butane is approximately four times more soluble in

groundwater than methane. Butane injection results in large radii of influence at
injection wellheads. The difficulty of utilizing alkanotrophic bacteria stems from the
low solubility of alkanes and the difficulty of maintaining homogeneous concentration of the dissolved alkane within the reactive zone.
Methanotrophs grow on C1 compounds as sole carbon and energy sources. Their
catabolic oxygenases are methane monooxygenases (MMO) that incorporate one
atom of oxygen from the oxygen molecule into methane to yield methanol.12,14,92
This alcohol is further oxidized via a series of dehydrogenation steps, through
formaldehyde and formic acid, to CO2 that is the final product of catabolism. MMO
enzymes utilize molecular oxygen as a reactant, and require a reduced electron
carrier to reduce the remaining oxygen atom to water. 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, as well as chlorinated alkanes, alkenes,
and aromatics.13,93
Two types of MMO have been suggested: a particulate (membrane-bound) and
a soluble enzyme.13 The soluble MMO (purified from Methylosinus trichosporium
OB3b and Methylococcus capsulatus [bath]), produced under 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 methanotrophs
may be as effective in the transformation of chlorinated 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 significant
potential for in situ bioremediation.
Thus TCE can be transformed (upon the induction of the oxygenase enzyme by
its substrate) in the presence of the microorganismal growth substrate (cometabolism), or in its absence (resting cells transformation). However, TCE is not utilized
by the bacteria as a carbon, energy, or electron source; this transformation is only
fortuitous. Based on the findings with methanotrophs, it can be concluded that TCE
is most likely oxygenated to TCE-epoxide (Figure 4.32).13,15,93 The epoxide is unstable and is quickly nonenzymatically rearranged in aqueous solution to yield various
products including carbon monoxide, formic acid, glyoxylic acid, and a range of
chlorinated acids. Recent findings with purified MMO from Methylosinus 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
prominently heterotrophs) occurs, TCE can be completely mineralized to carbon
dioxide, water, and chloride.
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 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 present, however, bacterial growth substrates need to be injected into the site in
204
Methane oxidation (normal reaction) with methane monooxygenase

H
OH
MMO
H C H
H C H
CO 2
H
NADH2, O
NAD, H2O
3NAD, H2O
3NADH 2
TCE epoxidation (cometabolic dechlorination reaction) with MMO

Cl
Cl
C C
Cl
Cl
MMO
Cl
NADH2, O2
NAD, H O
2
O Cl
C C
H
2CO2, 3Cl , 3H
2NAD, 3H2O
2NADH 2
(other microorganisms)
Figure 4.32
The top reaction shows how methanotrophs (methane eaters) produce the
enzyme methane monooxygenase (MMO) in the process of converting methane
(CH4 ) to CO2. The bottom reaction shows how MMo then causes the conversion
of TCE to CO2 and HCl. NADH2 serves as the carrier of electrons released from
methane and TCE. Note: NAD = nicotinamide adenine dinucleotide; NADH =
reduced nicotinamide adenine dinucleotide.
order to stimulate the transformation of chlorinated solvents. In this situation, methanotrophs become more attractive agents of bioremediation because methane, their
preferred substrate, is a nontoxic and inexpensive chemical. Once methane and
oxygen are injected into the site, methanotrophs (if present) will start cometabolizing
chlorinated solvents, as well as a great number of other contaminants (see below),
and the accompanying heterotrophs will mineralize their transformation products.
As mentioned earlier it is important to maintain reasonably high and uniform O2
and CH4 concentrations to achieve significant methanotrophic degradation.
4.3.1.2 MTBE Degradation
There is a growing body of evidence from laboratory and field studies that MTBE
can be degraded under aerobic conditions either by direct metabolism (when MTBE
serves as the carbon and energy source for microbial growth) or cometabolism.
Evidence on natural attenuation of MTBE is presented in Chapter 3.
Microbes capable of MTBE degradation under aerobic conditions may be present
at most sites, but perhaps under nonoptimum biogeochemical conditions to significantly reduce the migration of MTBE. Furthermore, these aerobic processes would
be expected to be limited at many sites since the MTBE plume is migrating down
a largely anaerobic path. Thus any approach to initiating or enhancing in situ aerobic
biodegradation of MTBE must overcome at least two major hurdles: 1) creating
steady aerobic conditions over the long term and 2) generating enough microbial
biomass to accomplish the treatment at a reasonable rate.
In situ chemical oxidation of MTBE has not been very successful due to the
incomplete oxidation and formation of undesirable byproducts such as tertiary-butyl
formate, tertiary-butyl alcohol, methyl acetate, acetone, and formic acid. Hence,
enhanced biodegradation of MTBE has to be optimized and engineered based on
the positive evidence found recently.
205
A pure culture that degrades MTBE has been isolated;94 however, the proliferation of this organism in the natural environment may be questionable. Two recent
field tests, at Pt. Hueneme, CA, and Vandenburg AFB, CA, have provided positive
results to the point that the previously held notion that MTBE is not aerobically
biodegradable is not true anymore. At Pt. Hueneme, controlled testing was done in
plots where pure oxygen only, and pure oxygen with bioaugmentation of enriched
cultures were injected in addition to a control plot where only natural conditions
were allowed to exist. The bioaugmented plot showed significant reductions of
MTBE at ppm range concentrations within a very short time period. The plot where
only O2 was injected also showed similar reductions in MTBE concentrations
after a lag period of months, however. The question still to be answered is whether
the microorganisms responsible for MTBE degradation are obligate aerobes and thus
a reasonably high DO concentration has to be maintained in the groundwater.
The Vandenburgh AFB field test also provided positive results and raised the
possibilities of implementing engineered in situ aerobic biodegradation of MTBE.
In two separate long term field tests, dissolved oxygen was released to the MTBE
plume through pressurized tubing via controlled interception trenches acting like
permeable walls. In both field tests, significant MTBE reductions took place in the
presence of increased levels of oxygen. MTBE degradation ceased when O2 injection
stopped, thus indicating that degradation was conclusively aerobic.
Others have reported reductions in MTBE concentrations during in situ air
sparging projects.54 Stripping may be the dominant mechanism of MTBE removal
from groundwater in these projects; however, the contribution by enhanced biodegradation due to increased levels of O2 in the groundwater cannot be discounted,
albeit at low levels compared to the mass removal by stripping.
At the Pt. Hueneme and Vandenburgh AFB field tests the means of O2 injection
was achieved by injecting pure O2. However, scaling up such a system to implement
an engineered aerobic IRZ to address large MTBE plumes will be uneconomical,
particularly when many of these plumes have migrated beyond property lines. Testing
the injection of dilute hydrogen peroxide to sustain the reasonably higher levels of
DO, which seems to be a requirement for aerobic MTBE degradation, will occur
soon. Another means of providing enhanced levels of DO is through the implementation of in-well sparging. Injecting hot air into the well will also enhance the mass
removal by air stripping at reasonable air to water ratios. Recirculated water saturated
with oxygen will create an in situ aerobic zone around the well and thus enhance
the aerobic degradation of MTBE (Figure 4.33).
Based on recent field observations, enhancing MTBE degradation within
engineered anaerobic zones may be a viable option. These zones have to be maintained under methanogenic conditions.
4.4
IN SITU CHEMICAL OXIDATION SYSTEMS
Chemical oxidation processes have been widely used for treatment of organic
contaminants in wastewaters. Because they are aggressive and applicable to a wide
variety of compounds, using these processes, coupled with delivery technologies for
206
Heater
Air to
treatment
Air
compressor
an
Cle er
wat
Water
table
Enhanced
biodegradation
Packer
Air injection
pipe
Contaminated
groundwater
Figure 4.33
Heated in-well sparging for enhanced stripping and aerobic biodegradation of

MTBE.
in situ remediation of contaminated groundwater or subsurface soils, has received

increased attention. In situ chemical oxidation is an innovative technology with
widely varying opinions regarding its effectiveness on a range of contaminant types.
The oxidants frequently used for this purpose are hydrogen peroxide, permanganate,
and ozone.
In situ chemical oxidation is achieved by delivering potent chemical oxidants to
contaminated media so that the contaminants are almost completely oxidized into
H2O, CO2, and chloride ions or converted into innocuous compounds commonly
found in nature. In situ chemical oxidation will most likely be selected to address
remediation of what may be considered difficult sites having one or more of the
following characteristics:77 low permeability soils, highly stratified soils, low-volatility target compounds, target compounds with low in situ degradation kinetic
constants, and dense nonaqueous phase liquids (DNAPLS).
4.4.1
Advantages
The primary advantages of in situ chemical oxidation (ISCO) technologies is their

relatively high speed destruction of contaminants. The cost of reagents is relatively
high compared to biological systems, so application is generally far more costly than
bioremediation systems, but significantly lower than other active source removal technologies, such as in situ thermal treatment or flushing using surfactants or cosolvents.
Since the reaction is nearly immediate, treatment is far more rapid than biological
techniques and can be faster than thermal or vapor recovery technologies.
207
The advantages of in situ chemical oxidation can be summarized as follows:

The ability to oxidize dense nonaqueous phase liquids (DNAPLs) if targeted
properly
A reduction in overall treatment time, allowing the site to reach closure relatively
sooner
The elimination of capital intensive pump and treat systems
The ability to address contamination in situ without disturbing above ground
structures
In situ chemical oxidation can be used as a stand alone treatment or in conjunction with other technologies such as bioremediation. The nature and location of the
contamination, size of the source zone, type of soil, and hydrogeology play a
significant role in choosing the most effective type of ISCO treatment system. In
situations where contamination covers a vast area, economics will dictate the extent
to which ISCO is used, but, in many cases, this is a cost effective pretreatment to
bioremediation and natural attenuation.
4.4.2
Concerns
The primary concern is ensuring the health and safety of workers. Chemical
oxidation is an exothermic reaction generating heat that can increase temperature
and pressurize gases depending on loading and reaction rates. Strong oxidants are
corrosive and potentially explosive. The design and operation of any ISCO system
must take into account the hazards of the chemicals and the potential for vigorous,
uncontrolled, exothermic reactions in the subsurface. Site conditions that would
warrant particular attention in the planning stage include paved sites for which vapor
pressures could build up under the pavement, sites with preferential flow paths, or
utility corridors through which vapors could migrate.
A significant performance concern is that the oxidation reaction is not complete,
and significant DNAPL accumulations remain in untreated areas in the subsurface.
Even a small percentage of the original DNAPL mass can result in a rebound in the
groundwater concentrations after treatment to levels similar to those measured before
treatment, or at least above levels of regulatory concern. In addition, the migration
of contamination to previously uncontaminated areas due to thermal gradients caused
by exothermic reactions and to trapping contaminants in gas bubbles created by the
reactions should be taken into account.
Another concern is the possibility of increased volatile emissions of volatile
organic compounds. Oxidation can cause significant heat generation and water vapor
production. As a result, in situ steam stripping is a potential mechanism for contaminant loss, particularly for highly volatile compounds like chlorinated solvents. For
example, in cases where the hydrogen peroxide concentration exceeds approximately
11%, enough thermal energy can be released to cause water to boil, leading to a
significant concern regarding vaporization losses.95
208
4.4.3
Oxidation Chemistry
The oxidation chemistry of chlorinated solvents is relatively well understood.

Oxidants attack the C-C bonds in these molecules. The double bonds that characterize chlorinated ethenes are far more reactive than the single bonds of chlorinated
ethanes, and hence PCE and TCE are far more susceptible to oxidation than TCA,
for example. However, the chloroethanes are often claimed to be susceptible to
oxidation as well.93,95,96 Current theory is that the oxidants cause formation of an
unstable epoxide that then breaks down to yield ketones and aldehydes. These
products may also be susceptible to further oxidation, eventually yielding carbon
dioxide, water, and chloride.
Several oxidants have been employed in the recent past for ISCO applications.
For DNAPL sites, the most common oxidants used have been hydrogen peroxide
(H2O2) and potassium permanganate (KMnO4). Permanganate is more expensive
than hydrogen peroxide, but it is also more stable and effective over a broad pH
range. Ozone (O3) is the strongest oxidant available, with an oxidation potential (E)
of 2.07 v. However, ozone is a gas and therefore most suitable for treating the vadose
zone, or possibly LNAPL accumulations in the capillary fringe. Persulfate (S2O82 )
salts are also available, with an E of 2.01v, but these oxidants are relatively expensive and require thermal activation.93,95 The relative reaction kinetics of the different
oxidants are shown in Figures 4.34 and 4.35.
Hydrogen peroxide apparently works through two mechanisms: free radical
generation and direct oxidation. The direct oxidation has an E of 1.76 v, and free
radical formation (H2O2 2OH + 2H+ + 2e) has an E of 2.76 v. The latter relies
Resistance to
Oxidation
Oxidant
Strength
High
Perchloroethylene
Hydroxyl Radical
Trichloroethylene
Permanganate
Vinyl Chloride
Ozone
Phenanthrene
Hydrogen Peroxide
Benzene
Hypochlorite
Hexane
Oxygen
Low
Figure 4.34
Relative strength of oxidants and relative resistance of some common contaminants to chemical oxidation.
Figure 4.35
209
Relative reaction kinetics of various oxidants.
on so-called Fentons chemistry, in which iron acts as a catalyst; therefore, iron is

often added with the hydrogen peroxide. In addition, pH adjustment is common
because oxidation is more rapid under acidic conditions.
Permanganate has an E of 1.70 v and yields MnO2 as an insoluble precipitate
under most conditions.93,95 Catalysts and pH control are not needed for permanganate
oxidation. The stoichiometry of complete oxidation reactions yields the following
weight ratios for permanganate (expressed as KMnO4:contaminant): PCE (1.3:1);
TCE (2.4:1); DCE (4.4:1); and VC (8.5:1). Of course, this stoichiometry ignores the
significant oxidant demand due to other reduced and natural organic compounds in
the subsurface, which can be significant.
Optimal use of the in situ chemical oxidation technology is very much dependent
on understanding oxidant demand from contaminant oxidation and matrix oxidant
demand. Matrix oxidant demand refers to oxidant consumption that can be attributed
to background soil and groundwater conditions (Figure 4.36). Matrix demand can
be derived from oxidation of natural organic matter (NOM), reduced metals, carbonates, sulfides, etc. Matrix demand can be highly variable (depending on the
reductive poise of the contaminated zone), influenced by background geochemical
conditions, and, since permanganate reaction rates are second order, also will depend
on the permanganate solution concentration.
The oxidant demand caused by the nontarget compounds can range from 10 to
100 times (or even higher) of the stoichiometric demand caused by the target
contaminants. Hence, it is more important to look at the chemical oxidation demand
of the system than at the total organic carbon (TOC) as an evaluation parameter for
chemical oxidation.
It should be noted that destruction of natural organic matter can release additional
contaminants, adsorbed to the organic matter, into the dissolved phase (Figure 4.37)
before being completely destroyed by the oxidant. This phenomenon is the primary
factor contributing to the rebound effects of the target contaminants during chemical
oxidation.
The most commonly observed mobilization of metals, during ISCO, is oxidation
of precipated Cr3+ to the dissolved Cr6+. The amount of Cr6+ mobilized will obviously
depend on the background chromium concentration in the soils. Literature reports
indicate that this dissolved Cr6+ will reattenuate within a short time frame and distance.
The advantages of peroxide as an oxidant include relatively low regulatory
resistance, more field experience in its use than permanganate, and a sparcity of
210
Figure 4.36
Oxidative poise of natural environment and increased potential demand of

oxidants.
Chemical oxidation
demand
Natural and non-target

organic matter
NOM
destruction
effect
Initial dissolved phase

target contaminant
Residual level of NOM
Progress of treatment
Figure 4.37
Natural organic matter destruction releases additional dissolved phase

contaminants.
211
byproducts of oxidation. Disadvantages include the need for pH control in some

cases and difficulties in controlling in situ heat and gas production. Permanganate
is more expensive and more stable than peroxide, and is effective over a broad pH
range. Oxidation also produces manganese levels, which will precipitate and potentially cause reduced porosity. Increases in dissolved manganese levels are also a
potential regulatory concern depending on the geochemistry, as is the purple color
of groundwater containing unreacted permanganate. Ozone has been used mostly
for vadose zone treatment. It is less costly than permanganate or peroxide, but the
most significant factor in choosing ozone is that it must be applied as a gas. Gases
may disperse further in the unsaturated zone than liquids, but vapor recovery and
possible treatment can add considerable cost.
4.4.3.1 Hydrogen Peroxide
Hydrogen peroxide (H2O2) is typically used together with Fe (II) to form Fentons
reagent. In Fentons reagent, H2O2 is decomposed by Fe (II) to produce highly
reactive hydroxyl radicals as expressed by Equation 4.36:
Fe2+ + H2O2 Fe3+ + OH + OH
(4.36)
The hydroxyl radical can nonselectively attack the C-H bonds of organic molecules and is capable of degrading many solvents, chloroalkenes, esters, aromatics,
and pesticides. The major advantages over other oxidation processes of using Fentons reagent to treat hazardous wastes can be summarized as:95 1) there are no
chlorinated organic compounds formed during the oxidation process as in chlorinating; 2) both iron and hydrogen peroxide are inexpensive and nontoxic; 3) there are
no mass transfer limitations because the reaction is homogeneous; 4) no light is
required as a catalyst and, therefore, the design is much simpler than ultraviolet light
systems; and 5) H2O2 can be electrochemically generated in situ, which may further
increase the economic feasibility and effectiveness of this process for treating contaminated sites. During treatment, particulates can be generated and the pore size
and continuity can, therefore, be modified with fine-grained media. As a result, the
permeability can be impacted.
In Fentons mechanism, reactions with H2O2 cycle iron between the +II and +III
oxidation states, yielding OH and other byproducts. Because OH is a powerful
indiscriminate oxidant that reacts with many compounds at near diffusion-controlled
rates,97,98 H2O2 and iron have been used to generate OH and oxidize undesirable
contaminants in soils and aquifers.93,95 A wide range of organic compounds (TCE,
BTEX, PCP, naphthalene, and pesticides) that are common contaminants of groundwater and soil have moderate to high reaction rate constants with OH (108
1010M1s1). The stability of H2O2 increases with decreasing pH in Fenton systems,
and oxidation efficiency is optimum under acidic conditions.95,97
Under acidic conditions and with an excess of Fe2+, the hydroxyl radical generated can further react with Fe2+ to produce Fe3+ (Figure 4.38a):76
Fe2+ + OH Fe3+ + OH
(4.37)
212
H2O 2
Fe2 +
R'H + CO 2
RED
RED
OX
OX
Fe3 +
H++R OH - + OH -
OX
RED
OH RH
Figure 4.38a
Fentons reagent idealized reactions.76
By properly controlling experimental conditions, ferric iron can be regenerated

back to ferrous iron by a subsequent reaction with another molecule of H2O2:
Fe3+ + H2O2 Fe2+ + HO2 + H+
(4.38)
The HO2 radicals produced (Equation 4.38) have been shown also to participate
in oxidation of some organic compounds, although they are much less reactive than
OH. Based on Equation 4.38, a low pH range of 2 to 4 is preferred to facilitate the
generation of hydroxyl radicals, although the reaction is feasible up to neutral pH.99
Almost all organic compounds can be treated in situ by this technology.
Limitations to Fenton-based remediation strategies arise from excessive H2O2
decomposition via nonproductive reactions (those that do not result in OH production), reaction of OH with nontarget species (scavenging), insufficient iron or
H2O2 for radical production, and slow reaction of OH with the target compound.93,95 For example, REDOX cycling of manganese between the +II and +IV
oxidation states consumes H2O2, but does not yield OH. Common groundwater
anions (NO3 , SO42 , C1, HPO42 , HCO3 , CO32 ) react with OH and may be a
source of treatment inefficiency. Furthermore, because H2O2 is generally present
at high concentrations in Fenton systems and has a moderate rate constant for
reaction with OH (2.7 107M1s1), peroxide is itself a primary source of inefficiency in Fenton-driven systems.95
213
Idealized reactions of Fentons reagent and potential reduction in efficiencies

due to disproportionation are shown in Figures 4.38b and c, respectively.76 The
contaminants of particular interest include chlorinated solvents (e.g., TCE, PCE),
polyaromatic hydrocarbons (e.g., naphthalene), PCP, and petroleum products (e.g.,
BTEX). Some of these chemicals are very difficult to biodegrade or may take
exceedingly long time in many subsurface settings.
H2O 2
OX
H2O + O 2
Fe2 +
RED
Fe3 +
OH - + OH Figure 4.38b
Fentons reagent failures Fe3+ catalyzes disproportionation.76
Major concerns for this technology are related to potential ecological effects and
chemical handling. The introduction of acid solution can have potential effects on
the ecosystem. During the reactions, both OH and H+ can be produced; however,
their quantities are relatively small compared with the acid introduced and thus
would have no significant effect on the pH of the media. Because large quantities
of chemicals are required for the treatment, it could be hazardous to handle them.
In addition, special measures may be taken during the delivery process because H2O2
can easily break down into H2O vapor and O2, leading to fugitive emissions of VOCs
and pressure buildup. One benefit of decomposition of H2O2 is that the released O2
can stimulate aerobic biological activity.
4.4.3.2 Potassium Permanganate
Potassium permanganate (KMnO4) has been used in treatment of drinking water
and wastewater for decades because it can effectively oxidize many water impurities,
including phenol, Fe2+, S2, and taste and odor-producing compounds. Only within
the past few years has it been used more frequently as an alternative chemical oxidant
for ISCO. KMnO4 is a dry crystalline material that turns bright purple when dissolved
214
H2O 2
Fe2 +
OX
RED
Fe3 +
Precipitate
Figure 4.38c
OH - + OH -
Fentons reagent failures Fe3+ is lost to precipitation.76
in water. The purple color acts as a built-in indicator for unreacted chemical. Reacted
KMnO4 is black or brown, indicating the presence of the MnO2 precipitate a
natural compound present in soil. Other KMnO4 oxidation byproducts include CO2,
H2O and the potassium ion K+. Limitations of KMnO4 include its low solubility (65
g/l at 68F) and its inability to oxidize petroleum compounds effectively.
Sodium permanganate (NaMnO4) is an oxidant that performs very similarly to
KMnO4; its attributes and limitations are much the same as KMnO4. However,
NaMnO4 has a much higher solubility in water, allowing it to be used for ISCO at a
much higher concentration. NaMnO4 is more expensive than KMnO4 on a pound-perpound basis and users have to be concerned about safety during handling and storage.
Reaction of KMnO4 with organic compounds produces manganese dioxide
(MnO2) and carbon dioxide or intermediate organic compounds. The kinetics of
reaction between permanganate and contaminants are obviously an important factor
in the overall treatment success achieved. It has been reported that oxidation of TCE
by KMnO4 is second order, with a fast second order constant.
An apparent limitation with the reactive hydroxyl radical (OH) is that it strongly
reacts with common inorganic species in groundwater such as carbonate and bicarbonate. However, permanganate, a metal-oxo reagent, does not apparently rely on
generating a hydroxyl radical to oxidize chlorinated ethenes as the other oxidants
do. Experience indicates that metal-oxo reagents can attack a double carbon-carbon
bond powerfully through direct oxygen transfer.76
[Org] + MnO4 MnO2 + CO2 or [Org]ox
(4.39)
215
where [Org]ox is the oxidized intermediate organic compound. Permanganate ions

preferentially attach carbon-carbon double bonds, in a manner similar to the attack
of ozone.76 A manganate ester forms in the first stage of the reaction and rapidly
decomposes to form a glycol, as shown in Figures 4.39a and b. Manganese dioxide
(MnO2) precipitates from the oxidizing aqueous solution. The glycol is cleaved under
high permanganate concentration or acidic conditions to form aldehydes or ketones.
Aldehydes are likely to be further oxidized to carboxylic acids.76,96
O
Mn
Mn
H+
C
OX
H
O
OH O
MnO 4
C
H
HO
MnO 4
H
H
C
H
Glycol Aldehyds
Cyclic Hypomangnate
Ester
Mn
OH O
C
MnO 4
HO
Glyoxylic Acid
O
H
OH O
C
O OH
Oxalic Acid
O
H
Formaldehyde
Figure 4.39b
nd n
bo tio
C nta
C- me
g
fra
Ethylene
O
Mn
O O
O
C C
Permanganate oxidation of an alkene.
H+
RED
Figure 4.39a
HO
OH
Formic Acid
The oxidation of ethylene in a neutral to weak acidic condition.
When permanganate is used to oxidize chlorinated ethenes, chlorinated intermediates such as phosgene or formyl chloride might be produced. However, it
was observed that rapid dechlorination of the manganate ester took place when
216
permanganate ion was used to dechlorinate TCE and other chloroethenes.76,93,95,96

For tests run at pH ranging from 4 to 8, oxidation of the manganate ester to carbon
dioxide was more rapid than the permanganate attack on the solvents. It was also
noted that only the permanganate ion, MnO4 , participated in oxidation, and that
manganese dioxide (MnO2) was the only manganese-bearing product of the several
reactions.
Several studies have been published describing permanganate oxidation of chlorinated ethenes, including reports of both field and laboratory applications.76,93-95 A
common element of these studies is the focus on oxidation of the contaminant compounds, without evaluation of oxidation byproducts that may result from reaction of
permanganate with naturally occurring compounds and organic species associated with
solvent wastes.
One particular problem in laboratory studies is that permanganate is typically
applied as an excess reagent an approach that simplifies analysis of reactions that
are first-order in both reactants. But the excess permanganate oxidizes many potential
reaction byproducts. In field applications, permanganate cannot be applied as an
excess reagent across the entire aquifer and the appearance of ketones, aldehydes,
and other reaction byproducts cannot be ruled out.95
Even when permanganate is applied as an excess reagent, byproducts such as
acetone and butanone may accumulate during oxidation of contaminated aquifer
soils. In an unpublished bench-scale study, a 3% potassium permanganate solution
was applied to aquifer soils contaminated by an oil-solvent mixture. The application
continued until permanganate depletion, during passage through the aquifer soils,
to negligible levels. Newly formed acetone, 2-butanone and other oxidation products
were measured in aqueous-phase samples throughout the test application.76
The compounds that can be oxidized by permanganate in addition to alkenes
include aromatics, PAHs, phenols, pesticides, and organic acids. The optimum pH
range is 7 to 8, but they are effective over a wide range.
Because Mn is an abundant element in the Earths crust and MnO2 is naturally
present in soils, introduction of KMnO4 to soils as well as production of MnO2
would not be an environmental concern. KMnO4 is as effective as or more effective
than H2O2 in oxidizing organic compounds. Furthermore, KMnO4 is more stable
and easier to handle. The potential problem is that MnO2 particles will be generated
and permeability loss is possible.
4.4.3.3 Ozone
Like hydrogen peroxide and permanganate, ozone is a strong oxidant that can
quickly oxidize organic compounds once in contact. Compared to other technologies,
in situ ozonation offers several advantages:76,93
It is much easier to deliver ozone to the contamination zone than aqueous oxidants.
No volatilization of target chemicals is required and, therefore, mass transfer
limitations associated with soil venting can be overcome.
In situ ozonation would likely be more rapid than biodegradation or soil venting
processes, and thus reduce the remediation time and treatment costs.
217
Ozone can be electrically generated from air on site.

In situ ozonation is conceptually similar to soil venting processes.
Both vertical and horizontal wells can be used to inject ozone.
Little degradation of ozone occurs during injection and on-site handling is relatively easy.
Similar to H2O2 and permanganate, ozone can be used to treat a variety of organic
compounds.
Ozone is very reactive and corrosive to materials.
Ozone reacts quickly in the subsurface and does not migrate long distances from
the point of delivery. Currently, ozone is used to treat chlorinated solvents, polyaromatic hydrocarbons, and petroleum products in situ.
Ozone is unstable in water. The degradation of ozone involves a complex cyclic
process that may be promoted or inhibited by various substances. In natural systems,
the degradation of ozone may be initiated by various substances including the
hydroxide ion OH, and natural organic matter (NOM). Bicarbonate and carbonate
ions and other hydroxyl radical scavengers will inhibit the degradation by ozone.
Many organic compounds are able to initiate, promote, or inhibit the chain-reaction
processes of ozone decomposition and degradation.
Zwitterions, also known as dipolar ions, are neutrally charged but strongly
polarized molecules that behave as ions.76 Many molecules exhibit a degree of dipolar
behavior zwitterions can be sufficiently dipolar to confer substantial reactivity.
Another zwitterion behavior is exemplified by glycine, an amino acid:glycine acts
as a base when titrated with acid, and acts as an acid when titrated with base.
Ozone is a zwitterion comprised of three oxygen atoms, as shown in Figure 4.40.
A resonant double bond concentrates negative charge in the terminal oxygen atom
bound by the single bond.76 Although the diagram suggests a concentration of
positive charge in the central portion of the molecule, the central atom exerts a pull
on the electrons from the resonant double bond, transferring some of the positive
charge to the double-bonded terminal oxygen.
O
+
Figure 4.40
Zwitterion behavior.
The double-bonded terminal oxygen atom in ozone can initiate electrophilic

attack on carbon-carbon double bonds, as shown in Figure 4.41. As the electron pair
from the alkene migrates toward the electrophilic oxygen atom, the opposite carbon
atom becomes electrophilic, attracting the singly bonded oxygen atom into a molozonide bridge. This highly unstable compound breaks and reforms as an ozonide,
218
O
O
O
O
C
C
O
O
O
C
O
Figure 4.41
C
O
Ozonation of an alkene.
which also decomposes spontaneously. The reaction is completed by the formation

of two ketones (or aldehydes) and water. The kinetics of ozone attack on chlorinated
ethenes is highly influenced by the steric hindrance caused by chlorine atoms.76
The dramatic increase in reactivity to ozone from tetrachloroethene to trichloroethene is due to two factors: the reduction in steric hindrance that follows from
elimination of a chlorine atom, and the reduction of the carbon atom from C (II) to
C (I), making the electron pair more available to electrophilic attack (oxidation).
Reaction rates of ozone and simple alkenes such as styrene are very high, while
alkanes, alcohols, aldehydes, and ketones are only slightly reactive to ozone
(Table 4.11).
The final decomposition products of the ozonation of chlorinated ethenes are
formaldehyde (CH2O), and phosgene (CCl2O). Formyl chloride (CHClO) is a theoretical product which is unreported in the chemical literature and presumable is unstable. Phosgene decomposes rapidly in water and is not expected to be observed; and
formaldehyde rapidly biodegrades in the highly aerobic post-ozonation environs.76
4.4.4
Application
In general, more than a single application of oxidant is required to meet most

cleanup standards. Several reinjections at periodic intervals have been used for more
thorough treatment. Recently, continuous injection using recirculation of amended
waters has been used to maximize the utilization efficiency of the oxidant as well
219
Table 4.11 Kinetic Constants for

Ozonation of Various
Organic Compounds76,98
Compound
Ko3 (M1s1)
Tetrachloroethene
Trichloroethene
1,1-Dichloroethene
1,1-Dichloroethane
Cis-1,2-Dichloroethene
Trans-1,2-Dichloroethene
Styrene
Formaldehyde
Acetaldehyde
0.1
17
110
0.12
800
5700
3 105
0.1
1.5
as to augment the distribution rate within the reactive zone. A comparison of the
properties of the three commonly used oxidants is presented in Table 4.12.
Table 4.12 Comparison of Oxidants
Fentons
Reagent
Physical State
Molecular Composition
OH formation
Liquid
OH
Yes
Oxidation Potential
Reaction Times
Contaminant Range
Potential to Entrance
2.76 V
Very Fast
Many Organics
Yes If the pH
Conditions Are
Not Low
Yes
Metal Mobilization/Potential
Permanganate
Ozone
Liquid
MnO4
Under Very
Limited
Conditions
1.70 V
Slow
Few Organics
Unlikely
Gas
O3
Under Certain
Conditions
2.07 V
Fast
Some Organics
Yes
Cr3+ Cr6+
Yes
For single or multiple injections, permanent or temporary injection points are

established, and an aqueous solution containing the oxidant and any needed catalysts
is injected under pressure. The oxidant (and catalyst) concentration, the target pH,
the injection well spacing (i.e., radius of influence), the number of injections, and
the injection pressure are all important design parameters affecting cost and performance. The oxidation reactions occur in the aqueous phase, and NAPL and sorbed
phases must be targeted and treated either by interfacial contact with or mass transfer
to the aqueous phase (Figure 4.42).
Successful prediction of overall rates of mass removal would require rate expressions both for nonequilibrium dissolution and oxidation. In the conceptual model
(Figure 4.43a), dissolution mass transfer, driven primarily by aqueous phase
chlorinated contaminant concentration gradients, is enhanced by the oxidation reaction that increases these gradients (Figure 4.43b). The efficiency of chemical oxidation for treatment of NAPLs is based on the conceptual model that attributes an
220
Adsorbed DNAPL
Pooled DNAPL
Figure 4.42
Chemical oxidation systems to address DNAPLs will have to target the mass of
DNAPL.
Concentration
Without Oxidant
CO
With
Oxidant
DNAPL
Phase
Oxidant
Concentrations
Dissolved Phase
Mass Flux
Figure 4.43a
Conceptual model describing mass removal by in situ oxidation.
increased rate of DNAPL mass transfer to chemical oxidation within the stagnant
film boundary layer. As the aqueous solvent gradient is increased, the dissolution
mass flux is increased. Simultaneously, the concentration gradient of the oxidant
would be increased, causing an increase in oxidant mass flux towards the
DNAPL/water interface.
DNAPL
221
GW / Oxidant solution
Boundary layer
Figure 4.43b
Conceptual model of interface mass transfer effects of chemical oxidation.
Permanganate oxidation of a DNAPL can yield manganese oxide solids that may
deposit on the interface and could result in a reduced interface mass transfer rate
and DNAPL oxidation rate. This is a complex process that is not fully understood.
The use of recirculation, with injection and extraction wells, is intended to
increase subsurface mixing. Many investigators have tried this approach with some
apparent success. The costs are likely to be higher than even multiple injections
without groundwater extraction and reinjection (with possible treatment and filtration
of MnO2 required). However, the degree of mixing and, therefore, contact between
contaminants and oxidant, will be greater, leading to more complete treatment,
especially in heterogeneous subsurfaces. Also, utilization efficiency of the oxidant
will be enhanced by recirculating the unused portion of the oxidant.
In some cases, mixing has been encouraged by use of injection arrays with thin
screen intervals at different depths to fully saturate the target zone and limit the need
for vertical migration of the oxidant (Figure 4.42). High injection pressures have
also been used to create fractures in tighter subsurface materials, again to encourage
migration and mixing of the reactants. Mixing has also been encouraged through
the use of air injection, to push peroxide solutions out into the aquifer. Finally, in
some cases, vapor extraction has been used in conjunction with in situ oxidation in
the vadose zone to relieve off-gas pressures, to encourage oxidant migration, and/or
to capture any volatile emissions. Oxygen concentrations in the soil air can reach
close to 100% and thus create explosive concentrations near the points of injection.76
The presence of colloidal materials, precipitation, and gas binding can cause
reduced permeability of the aquifer near injection points. If the geologic materials
have excessive amounts of CaCO3 in the formation gas, binding during the injection
of Fentons reagent could be a significant problem.
There do not seem to be well-developed guidelines for the design operation and
cost estimation of ISCO systems particularly when DNAPL is present (Figure 4.44).
The data needs for determining well spacing, screen intervals, or oxidant mass to
be injected are not clear. There is a need for guidance to estimate the ROI under
different conditions (soil texture, groundwater velocity, injection pressure, etc.). The
efficiency of use of oxidants is not well established, and guidance for determining
the mass needed at a specific site does not seem to be available. Recommendations
222
Reduction of aqueous phase concentrations

to below regulated clean-up levels
100%
Degree of Mass Removal
Complete DNAPL removal
Reduction of aqueous phase mass flux
Stabilization of pooled DNAPL
Partial DNAPL removal
0%
Conceptual Remediation End-point

Figure 4.44
Conceptual description of increased remediation cost due to the presence of

DNAPL.
regarding operations and monitoring to prevent undesirable reactions (explosions,

volatile emissions, or foaming) are also not clear.
4.4.4.1 Oxidation of 1,4-Dioxane by Ozone
Ozone is a powerful oxidant that can degrade contaminants via two mechanisms.
The first, commonly referred to as the direct mechanism, involves the reaction of
molecular ozone with the contaminant. Secondary oxidants, particularly the hydroxyl
radical, can also oxidize the contaminants present. The oxidation of compounds by
hydroxyl radical or other secondary oxidants is referred to as an indirect oxidation
(since ozone is not directly involved in the oxidation). OH is a nonselective oxidant,
that is, it oxidizes many substances; consequently, in natural systems it may not be
a very efficient oxidant, as it will react not only with contaminants of interest, but
also with other substances present, e.g., the natural organic matter.
In waters that contain carbonate, hydroxyl radical scavenging is greater at higher
pH. Therefore the effectiveness of ozonation systems tends to decrease at elevated
pH. For substances such as 1,4-dioxane that are not very reactive with molecular
ozone, the optimal pH for removal is typically around 8.76
Ozone could be used to treat groundwater extracted from the aquifer. For ex situ
treatment systems a treatment time of approximately 20 minutes would be needed
for 99% removal of 1,4-dioxane.76
The use of ozone for in situ treatment of groundwaters may be particularly useful
for the treatment of contaminants that are strongly sorbed to the aquifer materials
(e.g., PAHs) or where the aquifer materials exert relatively little ozone demand.
1,4-dioxane is infinitely soluble in water and is not strongly sorbed to solids. In this
case, in situ ozonation may be desirable as it avoids the cost of removal of the
223
groundwater and of the expense and problems associated with construction of an

ozone contractor to treat the extracted groundwater at the site. In situ ozonation can
be implemented using techniques developed for in-well air sparging.
The relative cost of in situ vs. ex situ treatment will depend very much upon how
effectively these systems can be implemented. Ozone is sometimes used in combination with UV light or hydrogen peroxide to treat groundwaters. Both UV light and
hydrogen peroxide catalyze the decomposition of ozone to produce hydroxyl radical.
The rapid decomposition of ozone can enhance the rate of degradation of compounds
like 1,4-dioxane, which are not very reactive with molecular ozone.
4.4.4.2 Biodegradation Enhanced by Chemical Oxidation Pretreatment
Many experimental efforts have been carried out to evaluate the enhanced biodegradation of many recalcitrant compounds such as PCBs, polychlorinated phenols, and
PAHs with limited success. With increased attention to the cleanup of sites with
known DNAPLs and manufactured gas plant (MGP) sites with coal tars, pretreatment
with chemical oxidation for certain compounds may be a viable technology.
4.5
NANO-SCALE FE (0) COLLOID INJECTION WITHIN AN IRZ
Considerable research during the past several years has focused on the transformation of chlorinated solvents to harmless end products by exploiting the use of
zero valent elemental metals for reductive dechlorination. In addition, elemental
metals can be used to reduce soluble metals such as Cr (VI) to insoluble Cr (III) or
metalloids such as As (V) and Se (VI) to As (III) and Se (IV), respectively.
The most common metal utilized for this purpose is elemental iron, Fe (0).
Although met with initial skepticism, the transformation process is surface-based
and is now widely accepted as abiotic reductive dechlorination, involving corrosion
of Fe (0) by chlorinated hydrocarbon. Other metals including tin, zinc, and palladium
have also been shown to be effective.100 The process can be described best as
anaerobic corrosion of the metal by the chlorinated hydrocarbon. During this process,
the contaminant is adsorbed directly to the metal surface where the dechlorination
reactions occur.
In waters contaminated with chlorinated solvents, three oxidants are available
to drive corrosion of metals: water, dissolved oxygen, and the chlorinated contaminant. The corrosion reaction involving water (Equation 4.40) is slow but presumably
ubiquitous, whereas corrosion of Fe (0) by reaction with dissolved oxygen (Equation
4.41) is very rapid as long as O2 is available. The reaction rates with the chlorinated
contaminant (Equation 4.42) are assumed to be between the two. Under aerobic
conditions, dissolved oxygen is usually the preferred electron acceptor and will
compete with the chlorinated contaminant as the favored oxidant (PCE and carbon
tetrachloride may be comparable).
Fe (0) + 2H2O Fe2+ + H2 + 2OH
(4.40)
224
2Fe (0) + O2 + 2H2O 2Fe2+ + 4OH
(4.41)
Fe (0) + RX + H+ Fe2+ + RH + Cl
(4.42)
When sufficient oxygen is present, the Fe2+ generated in Equation 4.40 can
precipitate as ferric hydroxide or (oxy) hydroxides at an elevated pH typical of
corroding Fe systems. In carbonate rich waters FeCO3 precipitation will also
occur. These precipitates can exert significant additional chemical and physical
effects within the surface-based Fe (0) reactive system by coating the reactive
iron metal.
Recent research on Fe (0) systems indicates that other mechanisms also may be
involved in the reductive process. The reductive processes can be summarized as
below:100
Fe (0) can act as a reductant by supplying electrons directly from the metal surface
to the adsorbed chlorinated contaminant (Figure 4.45).
Metallic Fe (0) may act as a catalyst for the reaction of H2 with the chlorinated
contaminant. The hydrogen is produced on the surface of the iron metal as the
result of corrosion with water (Figure 4.45).
A
H
Cl
Cl
Cl
Cl -
Cl
Cl
cis-1,2-DCE
TCE
2e - + H +
2e - + H +
2e -
Cl
2Cl Chloroacetylene
Cl
Vinyl chloride
2e - + H +
2e - + 2H +
Cl
Cl -
2e - + 2H +
Acetylene
H
H C C Cl
H C C H
Ethene
2e - + 2H +
H H
Ethane
H H
Figure 4.45
Abiotic reductive dechlorination mechanisms by Fe (0).
L1282_C04-C_frame Page 225 Thursday, March 6, 2003 11:45 AM
225
The rate of reaction of Fe (0) with chlorinated contaminants is dependent upon

the reactivity of individual chemical compounds and the amount of reactive surface
area on the Fe (0) particles. For degradation of a contaminant by zero-valent iron
metal, the reaction model can be represented as:102
-
dC
= K SA ra [C]
dt
(4.43)
where
C
= reacting contaminant concentration
KSA = specific reaction constant
ra
= the amount of iron surface area
Based on the reported values of KSA in the literature, there seems to be an order
of magnitude variability for an individual chlorinated hydrocarbon.102 It is important
to note, however, that the variability in KSA for individual compounds is modest relative
to the five orders of magnitude variability among the various chlorinated hydrocarbons.
In addition to the primary effects of contaminant reactivity and metal surface
area, several other factors influence the kinetics (KSA) of chlorinated contaminant
degradation. One factor is the saturation of reactive surface area with increasing
contaminant concentration. Another factor is metal type, which is the variable
most commonly invoked to rationalize otherwise unexplained variability in degradation rates by iron. The ra term in Equation 4.43 characterizes quantity of iron
surface area, but does not address differences in the reactivity of the surface. It is
important to note that as the size of the metallic iron is reduced, surface area goes
up as well as chemical reactivity.
High surface areas can be attained either by fabricating smaller particles or
clusters where the surface to volume ratio of each particle is high, or by creating
materials where the void surface area (pores) is high compared to the amount of
bulk material. If a metal is continually reduced in size it will eventually reach what
is known as superfine particle or nano-scale particle. Such particles can be distinguished from their corresponding bulk solid form by the size of their surface areas
in relation to their weight.
Initial applications of this technology in the mid 1990s used iron filings. Due to
size limitations (not small enough to be injected directly) of the commercially
available iron filings (Table 4.13), the process had to be implemented in the subsurface as a permeable reactive barrier (PRB). In a PRB, reactive material is placed in
the subsurface where a plume of contaminated groundwater must move through it
as it flows, typically under its natural gradient, and treated water comes out the other
side. The placement of the iron filings into the PRB was usually achieved by
hydraulic fracturing (Figure 4.46), or via a funnel and gate system where the gate
was filled with iron filings, or by mixing the iron filings with sand in a permeable
interception trench (Figure 4.47). It is obvious that in all these methods the peripheral geotechnical cost for the placement of iron filings in the subsurface can be
226
Table 4.13 Examples of the Surface Area of

Different Metallic Iron [Fe (0)]
Products103-105
Iron Type
Iron turnings
Electrolytic iron
Iron granules
Commercial iron filings
Nano-scale iron particles
Surface Area in M2/g

0.019
0.057
0.287
0.900
33.50
M2/g
M2/g
M2/g
M2/g
M2/g
up to two orders of magnitude higher than the actual cost of the iron filings. As a
result, more recent applications have used iron colloids in the micron size range to
cut down on the peripheral geotechnical cost and directly inject the iron colloids
into the contaminated zone.
Figure 4.46
Placement of Fe (0) filings as a reactive barrier via hydraulic fracturing.
The author and a few others have advanced metallic Fe (0) reduction technology
by incorporating nano-scale particles ranging in size from 1 to 999 nanometers (.001
to .999 m). A particle of this size has several advantages in application for in situ
groundwater remediation. These advantages include:
High surface area result in greater reaction kinetics.
The increase in kinetics allows for a lower mass loading of iron in the treatment
zone or reactor because the residence time required for complete dechlorination
is decreased.
The small size and greater reactivity of the superfine particle allows for the
application of the technology through direct in situ injection into the subsurface
(Figures 4.48 and 4.49).
227
Treated Groundwater
Groundwater flow
Contaminated
plume
Sand/
Fe o
mixture
Interceptor
Trench
Figure 4.47
Placement of Fe (0) filing as a permeable reactive barrier in an interceptor trench.
Fe / Molasses slurry
Injection well
Contaminated zone
In Situ reactive zone

filled with nano scale iron
Figure 4.48
Direct injection of nano-scale Fe (0) particles into the contaminated zone.
228
In Situ mixing
o
Mixed zone with Fe
Figure 4.49
Injection of nano-scale Fe (0) particles into the contaminated zones in the

unsaturated and shallow saturated zones.
The smaller size allows for advective particle transport.

The greater reactivity due to the small size allows for much lower overall iron
mass requirements.
Conceptually, destruction of the contaminant is an interfacially controlled process, and thus the efficacy of destruction is dominated by the exposed surface area
of the superfine particle. The exposed surface area is easily determined by BET
nitrogen adsorption, for which the surface area can be related to an equivalent
spherical diameter (desd):
SSA = 6/.desd
(4.44)
where
SSA = specific surface area determined by BET
= material density
In addition to the beneficial effects of increased surface area of the superfine
particles, coupling of a catalyst such as palladium or platinum will lead to increased
reaction rates which are multiplicative (Figure 4.50).
4.5.1
Production of Nano-Scale Iron Particles
Over the last decade, research, driven primarily by needs in the field of materials
science (hi-tech electronic chips or component industry products), has contributed
Figure 4.50
229
Nano-scale bimetallic clusters.
to general technologies designed to produce nano-scale particles. Generally, the

research has been in the area of colloids composed of ceramic or other nonmetallic
inorganic materials and not metal colloids. A significant part of the development
effort for the technology is the adaptation of nonmetallic nano-scale production
methods to the production of metallic nano-scale particles.
The method for production of metal particles in the nano-scale range may be
divided into two primary approaches: 1) bottom up, in which colloids of the
appropriate size are produced by being assembled from individual atoms; and 2)
top down, in which colloids of the appropriate size are produced by attrition of
larger existing particles of the metal.
The bottom up approach has a greater number of potentially applicable methods
including100:
Chemical reduction using sodium borohydride; various soluble metal salts (such
as ferrous or ferric chloride for iron) in suspensions of water, or various organic
hydrocarbon solvents; this process may or may not be enhanced with sonification
during reaction processes
Other chemical precipitation reactions in aqueous or hydrocarbon solutions capable of producing metals from soluble salts that may or may not include sonification
during reaction processes
Various methods of metal volatilization and subsequent deposition, typically under
vacuum
The top down approach uses two primary variations of milling or mechanical
comminuation that include:
230
Using mechanical agitation of a mixture of the desired colloidal metal, a grinding

media, and an organic or aqueous suspension fluid; examples include ball mills
and rod mills
Systems similar to the above where the mechanical agitation is provided by high
speed gas jets
There are methods available to produce superfine particles that have distinct
morphology and internal crystal structure to further enhance the surface reactivity.106
In addition, it is important to recognize that, in the nano-scale range, quantum size
effects begin to become apparent. For example a colloid of 10 nm diameter has
about 30% of its atoms in grain boundaries (which are highly reactive and subject
to quantum effects). These features have an effect on the physical/chemical behavior
of the particle in use which falls into one of two broad categories reflecting on
production by bottom up or top down methods.100
A colloid produced by chemical precipitation or reduction, or through the various
vapor deposition methods, will be nano-structured. This means that the colloid
will have nano-scale crystal domains with sharp boundaries between crystals. The
grain boundaries are typically only 1 atom thick and there is low dislocation
density in the crystal structures.100
The reactivity of a colloid of this type can be controlled primarily through the
selection of an appropriate overall colloid size and resulting surface area. Smaller
size means greater surface area and reactivity; larger size means lower surface
area and reactivity.100
A colloid produced by mechanical attrition will be nano-crystalline. The crystal
domains in the colloid are small, relative to the overall colloid size. The individual
crystal domains are separated by wide amorphous transition regions that exhibit
a very high dislocation density. These transition regions may be as large as the
crystal domains, but are still termed grain boundaries.100
The amorphous transition regions will be highly reactive. The reactivity of the
colloid will be dominated by the size and intensity of dislocation density of the
amorphous boundary regions rather than the absolute size of the colloid. A relatively large colloid produced by this method could have reactivity the same as or
greater than a much smaller colloid produced by bottom up methods.100
Control of the reactivity of the colloid is a critical feature. The iron undergoes
anaerobic corrosion, reacting directly with halogenated solvents as well as with
water to produce hydrogen. As the reactivity of the colloid increases, the hydrogen
production rate increases as well. By controlling the rate of hydrogen production
using the methods described above, it will be possible to design reactive metal
colloids with reactivity that will generate hydrogen at the rate required for the desired
dehalogenation processes rather than being consumed at excessively higher rates
(with just water) at which the iron colloid would be consumed (by the water) without
reacting with the halogenated solvents undergoing treatment. Controlling the type
of nano-scale particle produced is particularly important for in situ applications in
order to maximize the rate of hydrogen production needed to achieve the remediation
objectives.
4.5.2
231
Injection of Nano-Scale Particles in Permeable Sediments
Injection of nano-scale particles into intragranular pore space of the geologic

matric is the preferred mode of application for directly addressing microemulsions
of contaminants in source areas or for treating dissolved phase contaminants. Diffusion of contaminants and hydrogen generated by Fe (0) and advection of Fe (0)
particles should provide the intimate contact between contaminants and Fe (0). The
mobility of colloids is governed by mechanical filtration and adsorptive processes
within the porous media; it is always preferable to achieve the largest reactive zone
from each injection point for economic reasons.
Colloids and nano-scale particles can be mechanically removed by the soil
matrix. The key parameter to this process is the pore entrance size, which is a
function of grain size. In fine- to coarse-grained silts, pore entrance (throat) sizes
range from 0.7 to 7 m, in fine- to coarse-grained sands from 24 to 240 m, and
in fine- to coarse-grained gravels from 720 to 7,200 m. It is obvious from this
information that nano-scale particles will travel further from the point of injection
than typical colloids, particularly within more permeable formations.
Injection of nano-scale particles with shear thinning fluids also will enhance the
injectability of Fe (0) particles into the porous media. In contrast to Newtonian
fluids, whose viscosities are constant with shear rate, certain non-Newtonian fluids
are shear thinning, that is, the viscosity of these fluids decreases with increasing
shear rate.108 The primary benefit of using these fluids for this application is that
they increase the viscosity of the aqueous phase without adversely decreasing the
hydraulic conductivity. A suspension formulated with a shear thinning fluid will
maintain a relatively high viscosity in solution near Fe (0) particles (where the shear
stress is low) relative to locations near the surfaces of the porous media, where the
shear stress is high. The increased viscosity decreases the rate of gravitational settling
of the Fe (0) particles while maintaining a relatively high hydraulic conductivity
that permits injecting the Fe (0) suspension into the porous media at greater flow
rates and distances. If an easily biodegradable shear thinning fluid is selected, it will
also provide an additional benefit in the form of scavenging the dissolved oxygen
present within the reactive zone and ensuring that the reactive iron is consumed
primarily by the degradation of the contaminant mass. Above ground engineering
controls to prevent agglomeration of the Fe (0) particles in injection solution will
also enable the injected particles to travel farther in the porous media. This will
entail control of the ionic state of the suspension fluid to prevent agglomeration, use
of surfactants, and determination of the optimum colloidal concentration for the
suspension.
4.5.3
Organic Contaminants Treatable by Fe (0)
Tables 4.14 and 4.15 present a list of organic contaminants that are treatable and
not treatable by Fe (0) based on the current state of science. Table 4.16 presents a
list of compounds with unknown reactivity with Fe (0).
232
Table 4.14 Contaminants Treatable by Zero Valent Iron, Fe (0)101

Organic Compounds
Inorganic Compounds
Methanes
tetrachloromethane
trichloromethane
dichloromethane
Dissolved Metals
Ethanes
hexachloroethane
1,1,1-trichloroethane
1,1,2-trichloroethane
1,1-dichloroethane
tetrachloroethene
trichloroethene
cis-1,2-dichloroethene
trans-1,1-dichloroethene
1,1-dichloroethene
vinyl chloride
1,2,3-trichloropropane
1,2-dichloropropane
benzene
toluene
ethylbenzene
hexachlorobutadiene
1,2-dibromoethane
freon 113
N-nitrosodimethylamine
Anion Contaminants
Ethenes
Propanes
Aromatics
Other
Table 4.15 Contaminants Presently Not

Treatable by Fe (0)101
Organic Compounds
Inorganic Compounds
dichloromethane
1,2-dichloroethane
chloroethane
chloromethane
heavier PAHs
chloride
perchlorate
Table 4.16 Contaminants with Unknown

Treatability
Organic Compounds
Inorganic Compounds
chlorobenzenes
chlorophenols
certain pesticides
PCBs
mercury
Chromium
Nickel
Lead
Uranium
Technetium
Iron
Manganese
Selenium
Copper
Cobalt
Cadmium
Zinc
Sulphate
Nitrate
Phosphate
Arsenic
233
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CREDIT
Figure 4.9 is adapted from Van Briesen, J.M. and Rittmann, B.E.,Natural Attentuation Consideration and Case Studies: Remediation of Chlorinated and Recalcitrant Compounds, Wickramanayake, G.B., Gavaskar, A.R., and Kelley, M.E. (Eds),
Battelle Press, Columbus, OH. With permission.
CHAPTER
Phytoremediation
CONTENTS
5.1
5.2
Introduction ..................................................................................................240
Chemicals in the SoilPlant System............................................................241
5.2.1 Metals..................................................................................................241
5.2.2 Organics ..............................................................................................242
5.3 Types of Phytoremediation ..........................................................................244
5.3.1 Phytoaccumulation ...........................................................................245
5.3.2 Phytodegradation..............................................................................248
5.3.3 Phytostabilization .............................................................................250
5.3.4 Phytovolatilization............................................................................251
5.3.5 Rhizodegradation..............................................................................252
5.3.6 Rhizofiltration...................................................................................256
5.3.7 Phytoremediation for Groundwater Containment ...........................259
5.3.8 Phytoremediation of Dredged Sediments ........................................260
5.4 Phytoremediation Design .............................................................................261
5.4.1 Contaminant Levels .........................................................................265
5.4.2 Plant Selection..................................................................................265
5.4.3 Treatability .......................................................................................266
5.4.4 Irrigation, Agronomic Inputs, and Maintenance .............................266
5.4.5 Groundwater Capture Zone and Transpiration Rate .......................267
References..............................................................................................................267
many accepted agricultural techniques for cultivating, harvesting, and processing plants have now been adapted for phytoremediation. Overall, the application of phytoremediation is being driven by its technical and economic advantages over conventional approaches .phytoremediations future is not a
scientific issue, but rather a scientific sociology issue.
239
240
5.1 INTRODUCTION
Phytoremediation is defined as the engineered use of plants in situ and ex situ
for environmental remediation. The technology involves removing or degrading
organic and inorganic contaminants and metals from soil and water. The processes
include all plant-influenced biological, chemical, and physical processes that aid in
the uptake, sequestration, degradation, and metabolism of contaminants, either by
plants or by the free living organisms that constitute a plants rhizosphere. Phytoremediation takes advantage of the unique and selective uptake capabilities of plant
root systems, together with the translocation, bioaccumulation, and contaminant
storage and degradation capabilities of the entire plant body.
The concept of using plants to alter the environment has been around since plants
were first used to drain swamps. What is new within the context of this new
technology called phytoremediation is the systematic, scientific investigation of how
plants can be used to decontaminate soil and water.1 Interest in phytoremediation
has been growing in the U.S. during the past few years with potential applicaton of
this technology at a wide range of sites contaminated with heavy metals, pesticides,
explosives, and solvents.
The potential benefits of phytoremediation seem to be as numerous as the
problems it might address. One reason this technology is gaining attention is because
it is potentially cheaper than conventional treatment approaches for contaminated
soils and traditional pump and treat systems for contaminated groundwater, such as
incineration or soil washing. Another attraction of this technology is that it may
leave topsoil in usable condition, keeping soil fertility and structure intact while
reducing contamination levels at the same time. Phytoremediation is well suited for
applications in low permeability soils, where most currently used technologies have
a low degree of feasibility or success, as well as in combination with more conventional remediation technologies.
The main advantages of phytoremediation are the low capital costs, aesthetically
pleasing technique, minimization of leaching of contaminants, and soil stabilization.
The operational cost of phytoremediation is also substantially less than that of conventional treatments and involves mainly fertilization and watering for maintenance of plant
growth. In the case of heavy metals remediation, additional operational costs include
harvesting, disposal of contaminated plant mass, and repeating the plant growth cycle.
It should be emphasized that there is more to phytoremediation than merely
putting plants in the ground and letting them do the work. Phytoremediation also
has its drawbacks, which even its ardent champions are quick to acknowledge. First
of all, it is a time-consuming process that can take several growing seasons to clean
a site. Vegetation that absorbs toxic heavy metals will have to be harvested and
managed as a waste. This vegetation containing high concentrations of toxic metals
and organics may also pose a risk to wildlife. The shutdown of plant activity during
winter months and the seasonal variation of plant metabolic activity is a drawback
for application of this technology in colder climates. Other limitations of phytoremediation are that contaminants present below rooting depth will not be treated or
extracted and that the plant or tree may not be able to grow in soils at heavily
contaminated sites due to plant toxicity.
PHYTOREMEDIATION
241
Phytoremediation as a technology is still in its early stages. While many scientists, engineers, and regulators are optimistic that it will eventually be used to clean
up organic and metallic contaminants, at least two or three more years of field tests
and analyses are necessary to validate the initial, small-scale field tests.1,2 Issues like
soil characteristics and length of the growing season will need to be taken into
account and scientists must also determine what sites are most amenable to phytoremediation. Other issues such as the potential impact on wildlife remain to be
fully explored. Simultaneously, researchers working in the lab are trying to better
understand the processes behind phytoremediation to possibly improve its performance during cleanup applications.
This chapter will not do justice to this technology by claiming that it will cover
the rapidly progressing state of the science and also describe how these scientific
advances are being applied in the field for efficient remediation. Instead it will serve
as a brief state of the science summary that will allow the reader to understand the
current status of the technology and its applications, as well as activities of the
research community to further enhance this technology.
5.2
5.2.1
CHEMICALS IN THE SOILPLANT SYSTEM
Metals
Elements occur in the soil in a variety of forms more or less available for uptake
by plants. Many of the contaminants of concern at waste sites are metals or metalloids. Availability is determined by characteristics of the elements, such as behavior
of the ion as a Lewis acid (electron acceptor) which determines the predominant
type of strength of bond created (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 toxicity characteristic leaching procedure (TCLP) sometimes are used to describe metal behavior
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 vegetations 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 in 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
242
by way of metabolically controlled membrane transport systems often meant to take

up a nutrient which 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,
physiological 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 above ground parts in
xylem as organic or 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 availability in the soil and soil solution media.
They may alter or inhibit enzyme activity, interfere with deoxyribonucleic acid
(DNA) synthesis or electron transport, or block uptake of essential elements.2 Availability in response to toxic levels of metals by different plants is due to a number
of defenses. These include exclusion from the root, translocation in nontoxic form,
sequestering in nontoxic form, sequestering in nontoxic 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., As
replacing P).
5.2.2
Organics
Organic compounds of environmental concern include nonionic compounds

(such as PAHs, chlorinated benzenes, polychlorinated biphenyls (PCBs), BTEX
compounds, and many pesticides), ionizable compounds (chlorophenols, carboxylic
acids, surfactants, and amines), and weakly hydrophobic volatile organic compounds
(trichloroethene). 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 compounds in soil can be predicted by the organic matter-water
coefficient, Kom, as estimated by the octanol-water coefficient, Kow.3 Absorption onto
colloidal organic matter in solution 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 compounds may be degraded by microorganisms in the soil to
metabolites with greater or lesser toxicity. Very stable compounds, like highly chlorinated PCBs, may persist in essentially 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.1-4 More water-soluble
molecules pass through the root epidermis and translocate throughout the plant. The
less soluble compounds (like many polycyclic aromatic hydrocarbons) seem to have
limited entry into the plant and minimal translocation once inside. Highly lipophilic
PHYTOREMEDIATION
243
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 the hydrophobicity (or lipophilicity) of the target compounds. This
parameter is often expressed as the log of the octanol-water partioning 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 compounds log Kow, the greater the root uptake.
Hydrophobicity also implies an equal propensity to partition 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 optimum log Kow value for a compound
to be a good candidate for phytoremediation (as an example, log Kow = 0.53.0; log
Kow = 1.54.0).2,13 It has also been reported that compounds that are quite water
soluble (log Kow < 0.5) are not sufficiently sorbed to the roots or actively transported
through plant membranes.
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 tissue 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 tissue, which also functions in mechanical support. A
complex, cross-linked, polymeric matrix of cellulose, pectins, and proteins 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 lignin, that 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 mammalian 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 slow a rate. The result is the death of the weed species
without the metabolic capacity to rid itself of the toxin.
244
The shear volume and porous structure of a trees wood provide an enormous
surface area for exchange or biochemical reactions. Some researchers are attempting
to augment the inherent metabolic capacity of plants by incorporating bacterial,
fungal, insect, and even mammalian genes into the plant genome.
5.3
TYPES OF PHYTOREMEDIATION
A review of where pyhtoremediation fits into the scheme of hazardous waste

remediation enables us to differentiate the various types and mechanisms of phytoremediation (Figure 5.1). The scientific understanding of plant, soil and rhizosphere biochemistry, and contaminant fate and transport must be contrasted with
field and pilot studies that represent the current proof of concepts. The technology
is summarized below as those approaches ready for application, promising treatments
expected to be tested soon, and concepts of phytoremediation requiring intensive
development. Finally, the intrinsic strengths of phytoremediation as a technology
and the future potential of this technology must be reviewed for regulatory acceptance in terms of hazardous waste remediation.1,2
Mechanisms
for Organics
Mechanisms
for Inorganics
Atmosphere
Plant
Contaminant
in the plant
Phytodegradation
Soil
Rhizofiltration
Contaminant
in the root-zone
(Rhizosphere)
Rhizodegradation
Phytostabilization
Impacted Media
Figure 5.1
Phytovolatilization
Phytovolatilization
Remediated
Contaminant
Contaminant
in the air
Phytoaccumulation
Rhyzofiltration
Phytostabilization
Impacted Media
Potential contaminant fates during phytoremediation in the soilplantatmosphere

continuum.
Phytoremediation approaches can be summarized as follows based on current

understanding of the technology:
Phytoaccumulation, phytoextraction, hyperaccumulation

Phytodegradation or phytotransformation
Phytostabilization
Phytovolatilization
Rhizodegradation, phytostimulation, or plant assisted bioremediation
Rhizofiltration or contaminant uptake
Optimal performance of the technology is an important key to phytoremediations ability to gain wider acceptance as a presumptive remediation technique. With
PHYTOREMEDIATION
245
the possible exception of some of the above mechanisms that are already widely
studied and understood, all of phytoremediations major applications require further
basic and applied research in order to optimize field performance. Significant
research and development should be carried out to 1) obtain a better understanding
of mechanisms of uptake, transport, and accumulation of contaminants; 2) improve
collection and genetic evaluation of hyperaccumulating plants; and 3) obtain a better
understanding of interactions in the rhizosphere interactions among plant roots,
microbes, and other biota.
Short of true regulatory reform, phytoremediations ability to make further
inroads will depend on how quickly federal, state, and local regulators become
convinced of the technologys efficacy. While not involved in every decision making
process, the public is sometimes a key constituency as well. One can expect public
interest groups to be more concerned about efficacy and safety issues than cost or
other economic factors. However, phytoremediation seems to be faring well with
the general public and, according to many practitioners, has already proven popular
with neighbors and other interested parties at field remediation sites.
5.3.1
Phytoaccumulation
Remediation of contaminated soils using nonfood crops, called phytoaccumulation, has attracted a great deal of interest in recent years. Also called phytoextraction,
phytoaccumulation, refers to the uptake and translocation of metal contaminants in
the soil by plant roots into the above ground portions of plants.2 Certain plants,
called hyperaccumulators, absorb unusually large amounts of metals in comparison
to other plants and the ambient metals concentration (Table 5.1).
Table 5.1 The Number of Taxonomic
Groups of Hyperaccumulators
Varies According to Which Metal
is Hyperaccumulated2
Metal
Ni
Co
Cu
Zn
Mn
Pb
Cd
Number of Taxonomic Groups

of Hyper Accumulators
>300
26
24
18
8
5
1
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
246
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 phytoaccumulation applications
because they take up very large amounts of a specific metal. They are often endemic
and of a specific population (genotypes/clones) of a species.5 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.6
There are also high accumulators that accumulate somewhat lower metal concentrations than hyperaccumulators but much more than normal plants. They
usually have high biomass production. In these plants, there is no uniform distribution 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 and cost. Planting and
harvesting of plants may be repeated as necessary to bring soil contaminant 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 hazardous 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 phytoaccumulation is as follows:7
Botanical prospecting dating to the 1950s in the former USSR and U.S. is available
to practitioners.
Over 400 species of hyperaccumulators worldwide have been cataloged.
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 continuous research is being performed to develop
further understanding.
The hyperaccumulator plants can contain toxic element levels in the leaf and
stalk biomass (LSB) about 100 times more than nonaccumulator plants growing in
the same soil, with some species and metal combinations exceeding conventional
plant levels by a factor of more than 1000.8
Many hyperaccumulator plants, which are nonwoody (not a tree), have been
identified as having the capacity to accumulate metals. Thlaspi caerulascens was
found to accumulate Zn up to 20004000 mg/kg.9 The Indian mustard plant Brassica
juncea, grown throughout the world for its oil seed, was found to accumulate
significant amounts of lead.10 One planting of mustard in a hectare of contaminated
land was found to soak up two metric tons of lead. If three plantings could be
squeezed in per year, six tons of lead per hectare can be extracted. Both hemp
dogbane (Apocynum sp.) and common ragweed also have been observed to
PHYTOREMEDIATION
247
accumulate significant levels of lead. Aeollanthus subcaulis var lineris and Papsalum
notatus are other hyperaccumulator plants known to accumulate Cu and Cs, respectively. Hyperaccumulator plants can address contamination in shallow soils only, up
to 24 inches in depth. If contamination is deeper, 610 feet, deep-rooted poplar trees
can be used for phytoextraction of heavy metals. These trees can accumulate the
heavy metals by sequestration. However, there are concerns specifically for trees
that include leaf litter and associated toxic residues being blown off site. This concern
may be tested in the laboratory to see whether uptake and translocation of the metals
into the leaves exceed standards.
Hyperaccumulators have metal accumulating characteristics that are desirable,
but lack the biomass production, adaptation to current agronomic techniques, and
physiological adaptations to climatic conditions required at many contaminated sites.
It has been reported that harvesting at different seasons in a year had pronounced
differences in accumulation levels. In the future, genetic manipulation techniques
may provide better hyperaccumulator 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.
Chelates have been used not only to enhance metal uptake but also to avoid
metal toxicity. Metal accumulator plants have been studied extensively for organometallic complexes. It has been suggested that there is a relationship between metal
tolerance and carboxylic acids. Organo-metallic complexes increase the translocation
and tolerance of plants to the toxic effects of metals. For example, in Sebertia
acuminata citrate seems to be a detoxifying agent as well as an agent in transporting
phytotoxic Ni from root systems to the leaves until leaf fall.5,6 It has also been
suggested that in copper (Cu) and cobalt (Co) accumulator plants, Co existed as an
oxalate complex within the leaf. The formation of Zncitrate complexes in Zntolerant plants was the reason for high levels of organic acid accumulation. Reports
have indicated that histidine was responsible for accumulation, tolerance, and transport to shoots in nonaccumulating and hyperaccumulating (Ni) plant species.11 In
Thlaspi, a Zn hyperaccumulator plant species, it has been determined that the
majority of Zn in the roots was coordinated with histidine, whereas organic acids
were involved in xylem transport and Zn storage in the shoots. Similarly in a Craccumulating plant, Leptospermum scoparium, it was found that soluble Cr in leaf
tissue was present as the trioxalatochromium (III) ion, [Cr (C2O4)3]3. The function
of the Cr-organic acid complex was to reduce the cytoplasmic toxicity of Cr.5
Adding ethylenediaminetetraacetic (EDTA) acid, citric acid, or oxalic acid to
metal contaminated soils will significantly increase the metal concentrations in plant
shoots and roots.5 However, the application of these chelates during a full scale
remediation application has to be carefully controlled; if not, the increased solubility
of the metal chelates formed could drive these contaminants to migrate further
downward by leaching when plant uptake rates are not adequate. Controlling the
pH and conditioning the soils for optimum pH is an important factor when dealing
with metals-contaminated soils.
PHYTOREMEDIATION
Figure 5.2
248
Process schematic describing the various processes during phytoaccumulation of

heavy metals.
The schematic of the process involved in heavy metal phytoextraction is shown

in Figure 5.2. Translocation from the root to the shoot must occur efficiently for
ease of harvesting. After harvesting, a proper, regulartorily acceptable biomass
processing step or disposal methods should be implemented.
5.3.2
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 compounds
(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 rereleased to the environment depending on the contaminant and plant
species (phytovolatilization) (Figure 5.3).
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 adaptation and/or tolerance to adverse
PHYTOREMEDIATION
249
Photosynthesis
O2
H2O Transpiration and

Volatilization of VOCs
CO 2
Phloem
Photosynthates
+O2
Xylem
H2O, Nutrients
Dark Respiration
CO2, H O
Phytodegradation
- Metabolism within the plant
- Production of enzymes which
help to catalyze degradation
O2
Lignification,
Metabolites
Sequestration
H2O, Nutients, O 2
Transpiration
Root Respiration
CO2, H O
O2
Contaminent
Uptake
Exudation
O2, CH3COOH, C4H5OH
Cometabolism
Figure 5.3
Contaminant
CO2, H2O, Cl
Mineralization
Phytodegradation and phytovolatilization mechanisms associated with some other

mechanisms essential for plant life.
growth conditions resulting from contamination of the soils. Plant-formed enzymes

that are useful for phytodegradation are nitroreductases (for munitions and pesticides); dehalogenases (for chlorinated solvents and pesticides); phosphatases (for
pesticides); peroxidases (for phenols); laccases (for aromatic amines); cytochrome
P-450 (for pesticides and chlorinated solvents); nitrilase (for herbicides).
Plant transformation pathways can be of many different 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 metabolic pathways of herbicides, pesticides, explosives, and other nitroaromatic compounds. Contaminant degradation by
plant-formed enzymes can occur in an environment free of microorganisms (for
example, an environment in which the microorganisms have been killed by high
contaminant levels). Thus, phytodegradation potentially could occur in soils where
biodegradation cannot.
The current state of science in phytodegradation (phytotransformation) is summarized below:1,2
Plant-formed enzymes that degrade organic contaminants 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.
250
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 vs. multicultures found in wetlands and terrestrial communities is being further investigated.
Organic contaminants are the main category of contaminants with the highest
potential of phytodegradation. Inorganic nutrients are also consumed through plant
uptake and metabolism. Phytodegradation outside 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 (Myrioplillum 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 metabolites and in complete mineralization of a
small portion of the applied TCE.12,14 Poplars have been used to remove atrazine
and inorganic nutrients.2 Black willow (Salix nigra), yellow poplar (Liriodendron
tulipifera), bald cypress (Taxodium diskchum), river birch (Betula nigra), cherry bark
oak (Quercus falcata), and live oak (Quercus viginiana) have been known to support
degradation of herbicides.13 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 14C-labeled TCE were found to generate 14C-labeled carbon dioxide. Intermediate
compounds generated during oxidation are thought to be 2,2,2-trichloroethanol, and
di- and 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 concentrations of up to 20 ppm.22 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.
5.3.3
Phytostabilization
Phytostabilization is the use of certain plant species to immobilize contaminants

in the soil and groundwater through absorption and accumulation by roots, adsorption onto roots, or precipitation within the root zone and physical stabilization of
soils. It is also used as a means to stabilize contaminated soil by decreasing wind
PHYTOREMEDIATION
251
and water erosion and to decrease water infiltration and the subsequent leaching of
contaminants. This process reduces the mobility of the contaminant and prevents
migration to the groundwater or air. This technique can be used to re-establish a
vegetative cover at sites where natural vegetation is lacking due to high metal
concentrations. Metal-tolerant species may be used to restore vegetation to such
sites, thereby decreasing the potential migration of contamination through wind
erosion, transport of exposed surface soils, and leaching of soil contamination to
groundwater.
Implementation of phytostabilization involves reduction in the mobility of heavy
metals and high molecular weight organics by minimizing soil erodibility, decreasing
the potential for wind blown dust, and reduction in contaminant solubility by the
addition of soil amendments. Containment using plants either binds the contaminants
to the soil, renders them nonavailable, or essentially immobilizes them by removing
the means of transport.
Erosion leads to the concentration of heavy metals because of selective sorting
and deposition of different size fractions of the soil. Eroded material is often transported over long distances, thus selectively extending the effects of contamination
and increasing the risk to the environment. Erosion can, therefore, cause the build
up of concentrations of normally nontoxic contaminants to toxic levels at locations
where transported material is deposited.
Planting of vegetation at contaminated sites, particularly abandoned strip mining
sites, will significantly reduce the erodibility of the soils by water and wind; density
of vegetation will effectively hold the soil and provide a stable cover against erosion.
An excellent example of phytostabilization is everyones family garden where plants
help to minimize erosion and enhance the stability of the soil.
Another element of phytostabilization 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 character 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.
5.3.4
Phytovolatilization
Phytovolatilization is the uptake and transpiration of a contaminant 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 (Figure 5.3). Many organic compounds transpired by a plant are subject to phytodegradation.
252
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.2 The state of science with respect
to phytovolatization can be summarized as follows:2,17
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, alfalfa (Medicago sativa), and black locust species have been studied to
evaluate phytovolatilization.
Indian mustard and canola have been used in phytovolatilization studies of Se.2
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.2
Groundwater must be within the influence of plant (usually a tree) roots and soil
must be able to transmit sufficient water to the plant.
Climatic factors such as temperature, precipitation, humidity, solar radiation, and
wind velocity can affect transpiration rates and thus the rate of phytovolatilization.
Improved methods for measuring phytovolatilization, diurnal and seasonal variations, and precipitation vs. groundwater use need to be developed.
Significant research needs to be focused on modeling impacts of vegetation such
as transpiration stream concentration factors, canopy effects, and root concentration factors.
5.3.5
Rhizodegradation
Rhizodegradation (also called phytostimulation, rhizosphere biodegradation,

enhanced rhizosphere biodegradation, or plant-assisted bioremediation/degradation)
is the breakdown of contaminants in the soil through microbial activity enhanced
by the presence of the rhizosphere (Figure 5.4). 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 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 such
as breaking apart clods and transporting atmospheric oxygen to the root zone.
Soil adjacent to the root contains increased microbial numbers and populations.15
It is common knowledge that the number of bacteria in the rhizosphere is as much
as 20 times that normally found in nonrhizosphere soil (Figure 5.4). Short gram
negative rods (specifically Pseudomonas, Flavobacterium, and Alcaligens) are most
PHYTOREMEDIATION
253
Enhanced rhizosphere biodegradation

- Supply of nutrients, cometabolites
- Transport and retention of water
- Aeration
Soil dessication
Root respiration
Root intrusion
Sloughing
Enzymes
dehalogenase
nitroductase
Figure 5.4
Uptake
Rhizodegradation and associated processes in the root zone.
commonly found in the rhizosphere.15 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, carboxylic acids, carbohydrates, nucleic acid derivatives, growth
factors, and enzymes. The activity of microorganisms in the root zone stimulates
root exudation further stimulating microbial activity.16
Several studies have evaluated the effect of plants and the associated rhizosphere
on the fate of petroleum contaminants.2,4,15 For the most part, the presence of plants
enhanced the degradation of contaminants. Also, in studies using 14C-labeled contaminants in closed plant chambers, mineralization was greater in rhizosphere soils
than in unvegetated soils, indicating that the bioavailability of the contaminant was
higher in the rhizosphere.15
Studies using deep rooted prairie grasses to remediate soils contaminated with
PAH suggest 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), switch grass (Panicum virgatum),
Canada wild rye (Elymus canadensis), little bluestem (Schizachyrium scoparius),
side oats grama (Bouteloua curtipendula), western wheatgrass (Agropyron smithic),
and blue grama (Bouteloua gracilis) are some of the species known to enhance
degradation of petroleum compounds. Crested wheatgrass (Agropyron desertorum)
is known to degrade PCP contaminated soils.15 Alfalfa (Meticago sativa), fescue
(Festuca anundinacea), big bluestem (Andropogon gerardii), and sudan grass
254
(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.2 Wherever significant cometabolic transformations took place, the following enzyme systems were present: dehalogenase, nitroreductase, peroxidase, laccase, nitrylase, and oxygenase.
The rhizosphere is often divided into two general areas: the inner rhizosphere
at the very root surface and the outer rhizosphere embracing the immediately adjacent
soil. The microbial population is larger in the inner zone where biochemical interactions are most pronounced and root exudates are concentrated. 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 strategies 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 without obvious detrimental effects on the host plant. Increased root mass
has the apparent advantage of increasing the surface area available for microbial
colonization. Root exudation may be increased in proportion to increase in root area.
Such rhizosphere enhancements could improve bioremediation potential of the plantmicrobial system. It is suggested that when water is not freely available in unlimited
quantities, 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 5.5). The differences are attributed to variations in rooting habits, tissue
composition, and excretion products of the plant. The primary root population is
Poplar Trees 15 ft.
Alfalfa 4-6 ft.

Grasses 2 ft.
Figure 5.5
Examples of different root depths.
Indian
Mustard 1 ft.
PHYTOREMEDIATION
255
determined by the habitat created by the plant; the secondary 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 rhizosphere comprise: 5 106 bacteria, 9 105 actinomycetes, and 2 103
fungi per gram of air dried soil.
The state of science in phytodegradation can be summarized 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 phytoremediation techniques since degradation takes place at the source
of contamination.
There are low installation and maintenance cost(s) since no harvesting and disposal
are required.
Various microorganism species and enzymes have been isolated which degrade
different contaminants.
Analytical methods to better quantify treatment efficiency 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.2
Degradation of various pesticides (atrazine, metolachlor, parathion, diazinon, and
2,4-D, 2,4,5-T herbicides) has been studied, again with mixed results.2
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 towards plants, biodiversity in the rhizosphere, biogeochemical optimization in the rhizosphere, and interrelation between biological, chemical
and physical characteristics of the rhizosphere.
The following plants, in addition to the ones discussed previously, have been
used for successful implementation of phytodegradation at field sites:2 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. Growth
of hybrid poplar trees for the application of phytodegradation and rhizodegradation
is shown in Figures 5.6a, b, and c.
256
Figure 5.6a
Phytoremediation System, August 6, 1998.
Figure 5.6b
Phytoremediation System, September 13, 1999.
5.3.6
Rhizofiltration
Rhizofiltration is the adsorption or precipitation of contaminants onto plant roots

or the absorption of contaminants into the roots when contaminants are in solution
PHYTOREMEDIATION
Figure 5.6c
257
Phytoremediation System, August 22, 2000.
surrounding the root zone. In some applications, the plants are raised in greenhouses
hydroponically (with their roots in water rather than in soil). Once a large root system
has been developed, contaminated water is diverted and brought in contact with the
plants or the plants, are moved and floated in the contaminated water. The plants
are harvested and disposed as the roots become saturated with contaminants. Plant
uptake, concentration and translocation might occur, depending on the contaminant.
Exudates from the plant roots might cause precipitation of some metals. Rhizofiltration first results in contaminant containment, in which the contaminants are
immobilized or accumulated on or within the plant; contaminants are then removed
by removing the plant.
Aquatic plants and algae are known to accumulate metals and other toxic elements from solution.18 There are large differences in bioremoval rates due to species
and strain differences, cultivation methodology, and process control techniques. In
the past, commercial systems have used immobilized algae biomass for removing
radionuclides and other heavy metals in the aqueous phase.19
Naturally immobilized, plants such as attached algae and rooted plants, and those
easily separated from suspension, such as filamentus microalgae, macroalgae, and
floating plants, have been found to have high adsorption capacities. In a recent study,
one blue green filamentous alga of the genus Phormidium and one aquatic rooted
plant, water milfoil (Myriophyllum spicatum), exhibited high specific adsorption for
Cd, Zn, Ph, Ni, and Cu.18
It has been reported that porous beads containing immobilized biological materials such as sphagnum peat moss can be used for extracting metals dissolved in the
aqueous phase.20 The beads designated as BIO-FIX beads readily adsorbed Cd, Pb,
and other toxic metals from dilute waters. In one recent study, it was reported that
258
Saccharomyces cerevisiae yeast biomass, when treated with a hot alkali, exhibited
an increase in its biosorption capacity for heavy metals.21 It was also reported that
caustic treated yeast immobilized in alginate gel could be reactivated and reused to
remove Cu, Cd, and Zn in a manner similar to the ion exchange resin.
Phytoremediation applications are summarized in Tables 5.2a and b based on
contaminant fate, degradation, extraction, containment type, or a combination of
these applications. In the soilplantatmosphere continuum, a specific contaminant
can be remediated at specific points along this continuum by different phytoremediation mechanisms.
Table 5.2a Types of Phytoremediation for Organic Constituents
Type of Phytoremediation
1.
Phytostabilization
2.
Rhizodegradation
(phytostimulation,
rhizosphere
bioremediation, or
plant-assisted
bioremediation)
3.
Rhizofiltration
(contaminant uptake)
4.
Phytodegradation
(phytotransformation)
5.
Phytovolatilization
Process Involved
Plants control pH, soil gases, and
redox conditions in soil to
immobilize contaminants.
Humification of some organic
compounds is expected.
Contaminant Treated
Expected for phenols,

chlorinated solvents
(tetrachloromethane and
trichloromethane) and
hydrophobic organic
compounds
Plant exudates, root necrosis, and Polyaromatic hydrocarbons,
other processes provide organic
BTEX, and other
carbon and nutrients to spur soil
petroleum hydrocarbons,
bacteria growth by two or more
perchlorate, atrazine,
orders of magnitude. Exudates
alachlor, polychlorinated
stimulate degradation by
biphenyl (PCB), and other
mycorrhizal fungi and microbes.
organic compounds
Live roots can pump oxygen to
aerobes and dead roots may
support anaerobes.
Compounds are taken up or
Hydrophobic organic
sorbed by roots (or sorbed to
chemicals
algae and bacteria).
Aquatic and terrestrial plants take Munitions (TNT, DNT, HMX,
up, store, and biochemically
nitrobenzene, picric acid,
degrade selected organic
nitrotoluene), atrazine,
compounds to harmless
halogenated compounds
byproducts, products used to
(tetrachloromethane,
create new plant biomass, or
trichloromethane,
byproducts that are further
hexachloroethane, carbon
broken down by microbes and
tetrachloride, TCE,
other processes to less harmful
tetrachloroethane,
products. Reductive and
dichloroethant), DDT and
oxidative enzymes may be used
other chlorine and
in series in different parts of the
phosphorus based
plant.
pesticides, phenols, and
nitrites
Volatile organic compounds are
Chlorinated solvents
taken up and transpired. Some
(trichloroethane), organic
recalcitrant organic compounds
VOCs, BTEX, MTBE
are more easily degraded in the
atmosphere (photodegradation).
PHYTOREMEDIATION
259
Table 5.2b Types of Phytoremediation for Inorganic Constituents

Type of Phytoremediation
1.
Phytostabilization
2.
Rhizofiltration
(contaminant uptake)
3.
Phytoaccumulation
(phytoextraction or
hyperaccumulation)
4.
Phytovolatilization
5.3.7
Process Involved
Contaminant Treated
Plants control pH, soil gases,

and redox conditions in soil
to immobilize contaminants.
Humification of some organic
compounds is expected.
Compounds are taken up or
biosorbed by roots (or
sorbed to algae and
bacteria).
Metals and organic chemicals
taken up by the plant with
water, or by cation pumps,
sorption and other
mechanisms.
Volatile metals are taken up,
changed in species, and
transpired.
Proven for heavy

metals in mine tailing
ponds
Heavy metals and

radionuclides
Nickel, zinc, lead,

chromium, cadmium,
selenium, other heavy
metals radionuclides
Mercury and selenium
Phytoremediation for Groundwater Containment
Phytoremediation can be applied for containment of contaminated groundwater

under the right hydrogeologic conditions such as sites with shallow groundwater
depths. In general, favorable economics is one factor in phytoremediations favor,
particularly in contrast to the high cost of operation and maintenance of conventional
groundwater treatment systems. Furthermore, the high pumping rates of many deep
rooted trees may make them more efficient at removing water at low permeability sites.
Phreatophytes (like willows, cottonwood, and hybrid poplar), which take up and
process large volumes of soil water are good candidates for phytoremediation
applications specifically for groundwater containment. For example, a single willow
tree on a hot summer day transpires more than 5000 gallons of water, and a hybrid
poplar can transpire about 50 to 350 gallons per day.23
Phytoremediation of groundwater plumes is preferred when the contaminants
are water soluble, leachable 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 groundwater during planting.23
The primary considerations for selecting phytoremediation for hydraulic control
as the method of choice are the depth and concentration of contaminants that affect
plant growth. Soil texture and degree of saturation are also influential factors.
Planning technique and materials can extend the influence of plants through nonsaturated zones to water-bearing layers.
As mentioned earlier, phreatophytes such as poplars are capable of extending
their roots into aerobic water tables. For example, the roots of poplars growing
260
alongside streams can easily be observed intertwined in the stream bottom. The
degree to which poplar roots would penetrate the saturated 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 saturated aquifer. Evapotranspiration
will draw down the water table below the trees similar to a pump and treat system
(Figures 5.7a and b). Simulations of a proposed design can be carried out based on
extent of contamination, hydrogeological data, past precipitation and infiltration
records, and evapotranspiration 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 minimally or
not at all by the pump and treat system. In the case of phytoremediation, the roots
can penetrate these micropores for contaminant removal.
Above
Capillary
Fringe
At Capillary
Fringe
In Capillary Fringe
and Groundwater Table
Figures 5.7a
5.3.8
Placement of root ball with time due to maturation of the tree.
Phytoremediation of Dredged Sediments
Dredged material is nothing more than displaced topsoil that enters and is
eventually removed from navigable waterways. Contaminant discharges into waterways over time result in contamination of bottom sediment. Dredged sediments are
usually stored in confined disposal facilities (CDF).24
The application of phytoremediation to dredged material presents some challenges unique to dredged material. Dredged sediments come from an aquatic environment and are initially wet and anaerobic after placement in a CDF. Subsequent
drying and oxidation depend on dewatering and management techniques. Drying
and oxidation of surface layers may result in physicochemical changes that may
affect plant establishment and contaminant mobility. Although the surface layer of
PHYTOREMEDIATION
261
31.0
Groundwater
flow
Zone of tree plantation
28.0
29.0
30.5
30.0
30.0
Groundwater table elevation contours

Figures 5.7b
Predicted groundwater flow conditions at maturation of tree growth.
dredged sediments in a CDF may be dry and aerobic, deeper layers may remain
anaerobic. Saltwater dredged sediments provide another level of difficulty for vegetation and in most cases must be leached to reduce soluble salt levels. Dredged
material management is further complicated by the potential of elevated concentrations of multiple contaminants. The selection of plant species and methods of
establishment will be determined by these factors. Common contaminants present
in dredged sediments are metals, PAHs, polychlorinated phenols, PCBs and other
heavy molecular weight compounds. The current state of knowledge indicates that
phytoremediation of dredged sediments would not be as readily effective as application to more heavily contaminated industrial sites.
5.4
PHYTOREMEDIATION DESIGN
The design of a phytoremediation system varies according to 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 remediation
system. Clearly, phytoextraction has different design requirements from phytostabilization or rhizodegradation. Nevertheless, it is possible to specify a few design
considerations that are part of most phytoremediation efforts (Figures 5.8a, b, and
c). Site characterization 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 clean-up time required.
Other factors to be considered during the evaluation, design, and implementation
phases of phytoremediation at a contaminated site are:
262
Figure 5.8a
Decision tree for phytoremediation in soil.
Soil Water The most crucial factor in a plants life is water, which links it to
the soil via roots and serves as a vehicle for nutrient transport. Water also controls
the exchange of gases and moderates soil temperature 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 maintain hydrostatic pressure in the elongating
PHYTOREMEDIATION
263
Decision Tree for Phytoremediation

Groundwater
YES
NO
YES
YES
Will the climate support the proposed plants?
YES
Is time or space a constraint?
Is the contaminant physically within the range of the proposed plant (typically less
than 10- 20 feet bgs for Salix species - willows, cottonwoods, poplars) ?
Will the plants be used for hydraulic

control ONLY (prevent water from
REACHING the contaminated zone)?
Is the contaminant at phytotoxic

concentrations (this may require a
greenhouse dose-response test)?
YES
YES
Will state regulations allow this

type of phytoremediation?
Will the rhizosphere microbes and plant-exuded enzymes degrade the target
contaminants in the rhizosphere and are the metabolic products acceptable?
YES
YES
Will the plants transpire the contaminant

or metabolic products?
Are the quantity and rate of transpiration

acceptable for this site?
YES
YES
Can engineering controls make it

acceptable?
Is the final disposition of the contaminant
or metabolic products acceptable?
NO
YES
Will the plant degrade the contaminant

after uptake and are the metabolic
products acceptable?
NO
YES
Is the level of accumulation acceptable for

this site throughout the growth of the plant?
NO
Can controls be put in place to prevent the

transfer of the contaminant or metabolic
products from a plant to humans/animals ?
NO
YES
Can the contaminant or metabolic product

be immobilized to acceptable levels ?
NO
YES
NO
NO
NO
Does the plant material constitute a waste if harvested?
Can the plant waste be economically disposed?
Phytoremediation has the potential to

be effective at the site
Figure 5.8b
NO
YES
YES
YES
NO
Will the plant accumulate the contaminant

or metabolic products after uptake?
NO
NO
NO
YES
Is the log Kow of the contaminant or

metabolic poducts between 1 and 3.5
(will uptake occur)?
NO
NO
Will the water be mechanically pumped

and applied to the phytoremediation
system?
NO
YES
NO
NO
YES
NO
Phytoremediation is NOT an option

at the site;consider other options
Decision tree for phytoremediation groundwater.
cells of the root, and metabolites for cell wall construction. Water flows radially
into elongating root cells only when the cells total water potential is lower than
the combined osmotic and matric potentials of the soil. Soil water content will
influence plant biomass growth.
264
Decision Tree for Phytoremediation

Sediments
Will the climate support the proposed plants?
YES
NO
YES
YES
Is time or space a constraint?
NO
Can the sediments be treated in place (wetlands)?
YES
YES
Is there strong public support to treat the sediment as a soil?
Is the contaminant at phytotoxic concentrations (this

may require a greenhouse dose-response test)?
YES
NO
YES
YES
YES
YES
Will the plants transpire the

contaminant or metabolic products?
Are the quantity and rate of

transpiration acceptable for this site?
Will the plant accumulate the contaminant

or metabolic products after uptake?
YES
NO
Is the level of accumulation acceptable for

this site throughout the growth of the plant?
NO
YES
YES
Can controls be put in place to prevent the

transfer of the contaminant or metabolic
products from a plant to humans/animals?
NO
NO
NO
NO
YES
Can the contaminant or metabolic products

be immobilized to acceptable levels ?
Does the plant material constitute a waste if harvested?
Can the plant waste be economically disposed?
Phytoremediation has the potential to

be effective at the site
Figure 5.8c
NO
YES
Is the final disposition of the contaminant

or metabolic products acceptable?
YES
NO
NO
Will the plant degrade the

contaminant after uptake and are
the metabolic products acceptable?
YES
Can engineering controls make it

acceptable?
NO
NO
Are there hotspots that can be

removed or treated?
YES
YES
NO
NO
Will the rhizosphere microbes and plant-exuded enzymes degrade the target
contaminants in the rhizosphere and are the metabolic products acceptable?
Is the log Kow of the contaminant or metabolic

products between 1 and 3.5 (will uptake occur)?
NO
NO
Is the contaminant physically within the range of the proposed plant (typically less than
1- 2 feet bgs)?
YES
NO
Are the sediments

to be dredged?
Will the regulatory statutes allow the dredged sediments to be treated as a soil?
YES
NO
NO
YES
NO
Phytoremediation is NOT an option at

the site; consider other options
Decision tree for phytoremediation sediments.
Soil Air Plants need molecular oxygen to respire and convert carbohydrates to
CO2 and H2O. This is an exothermic reaction and releases respiratory energy
utilized for many plant processes. The disappearance of O2 triggers a sequence
of changes in the biogeochemical properties of the soil; the absence of O2 alone
is sufficient to alter plant metabolism profoundly. Suboptimal concentrations of
PHYTOREMEDIATION
5.4.1
265
O2 in the soil occur because of interactions 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 processes at the cellular level,
such as osmotic potential, hydration of ions, stomatal activity and transpiration,
Gibbs free energy available for work, membrane 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, sometimes called mechanical impedance or excessive soil strength, can severely affect normal root growth patterns. 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
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 erosion increases
manifold with increasing degree and length of slope. Contaminated sites with
slopes greater than 10% are often not suitable for phytoremediation 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 phytoremediation applications 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.
Contaminant Levels
During the site characterization phase the concentration level of the contaminants
of concern will be established. High levels of contamination 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 weathering and
boiling point range) and degree of adsorption are important factors in phytoremediation. It is important to understand the range of contaminants that can be treated
using phytoremediation. In addition to knowing contaminants and their concentrations, the depth of the contaminants must be known. The primary consideration in
this area is that the contaminant concentrations cannot be phytotoxic or cause
unacceptable impacts on plant health or yield. Higher concentrations of contaminants
might be tolerated more readily by plants than by soil microorganisms.
5.4.2
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
266
phytoremediation. 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 contaminants of concern. For phytotransformation of
organic compounds, the design requirements are that vegetation is fast growing and
hardy, easy to plant and maintain, utilizes a large quantity of water by evapotranspiration, and transforms the contaminants of concern 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 rooting ability
down to the level of groundwater, large transpiration rates, and the fact that they are
native throughout most of the country. 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 transpires 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.
5.4.3
Treatability
Treatability or plant screening studies are recommended prior to designing a

phytoremediation system. If the decision tree flowcharts indicate phytoremediation
is an applicable technology for a site, a plant scientist should assist in the treatability
studies which assure concerned parties that the phytoremediation 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. Volatile organic compounds are often
transpired to the atmosphere by plants; calculations will predict the amount and type
of material transpired.
5.4.4
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 conditions. Irrigation should be withdrawn if the area receives
sufficient rainfall to sustain the plants. Agronomic inputs include the nutrients necessary for vigorous growth of vegetation and 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 phytoremediation 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.
PHYTOREMEDIATION
5.4.5
267
Groundwater Capture Zone and Transpiration Rate
For applications involving groundwater remediation, a capture zone calculation

can be used to estimate whether the phytoremediation pump (trees) can be effective
at entraining the plume of contaminants. The goal is to create a water table depression
where contaminants will flow to the vegetation for uptake and treatment. Organic
contaminants are not taken up at the same concentrations in the soil or groundwater
because membranes at the root surface reduce the uptake rate. Although it is possible
to estimate the uptake rate of contaminants, the calculation is beyond the scope of
this chapter.
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and Burris, D. R., Eds., Battelle Press, Columbus, OH, 1995.
22. Susarla, S. et al., Phytotransformation of perchlorate using parrot feather, Soil and
Groundwater Cleanup, March, 1999.
23. Gatliff, E., personal communication, 2000
24. DOE, Phytoreclamation of dredged material; a working group summary, Technical
Note, DOER-C9, November, 1999.
CREDIT
Figures 5.1, 5.8a,b,c, and Tables 5.2a,b were reproduced from Phytoremediation
Decision Tree, prepared by Interstate Technology and Regulatory Cooperation Work
Group, Phytoremediation Work Team, November 1999.
L1282/C06/frame Page 269 Monday, June 18, 2001 9:29 AM
CHAPTER
Constructed Treatment Wetlands

CONTENTS
6.1
6.2
6.3
6.4
Introduction ..................................................................................................270
6.1.1 Beyond Municipal Wastewater ........................................................272
6.1.2 Looking Inside the Black Box .....................................................273
6.1.3 Potential Attractive Nuisances......................................................274
6.1.4 Regulatory Uncertainty and Barriers ...............................................275
Types of Constructed Wetlands ...................................................................276
6.2.1 Horizontal Flow Systems.................................................................276
6.2.2 Vertical Flow Systems......................................................................277
Microbial and Plant Communities of a Wetland.........................................278
6.3.1 Bacteria and Fungi ...........................................................................278
6.3.2 Algae ................................................................................................279
6.3.3 Species of Vegetation for Treatment Wetland Systems...................279
6.3.3.1 Free-Floating Macrophyte-Based Systems.......................282
6.3.3.2 Emergent Aquatic Macrophyte-Based Systems ...............284
Subsurface Flow ...............................................................285
Subsurface Flow ...............................................................285
6.3.3.5 Submerged Macrophyte-Based Systems ..........................285
6.3.3.6 Multistage Macrophyte-Based Treatment Systems..........287
Treatment-Wetland Soils..............................................................................287
6.4.1 Cation Exchange Capacity...............................................................289
6.4.2 Oxidation and Reduction Reactions ................................................290
6.4.3 pH .....................................................................................................292
6.4.4 Biological Influences on Hydric Soils.............................................292
6.4.5 Microbial Soil Processes..................................................................292
6.4.6 Treatment Wetland Soils ..................................................................293
269
270
6.5
Contaminant Removal Mechanisms ............................................................294

6.5.1 Volatilization ....................................................................................294
6.5.2 Partitioning and Storage...................................................................295
6.5.3 Hydraulic Retention Time................................................................297
6.6 Treatment Wetlands for Groundwater Remediation....................................299
6.6.1 Metals-Laden Water Treatment........................................................300
6.6.1.1 A Case Study for Metals Removal ..................................302
6.6.2 Removal of Toxic Organics .............................................................306
6.6.2.1 Biodegradation ..................................................................306
6.6.3 Removal of Inorganics .....................................................................309
6.6.4 Wetland Morphology, Hydrology, and Landscape Position............309
References..............................................................................................................310
Creating or constructing a natural wetland sounds like an oxymoron, but this

doesnt mean that an unnatural wetland is by definition bad. It doesnt mean
we cant mimic Mother Nature in giving natural birth to a desirable wetland.
Constructed rice paddies have been responsible for feeding more people than
any other enterprise on earth.
6.1
INTRODUCTION
Natural wetlands are land areas that are wet during part or all of the year because
of their location in the landscape. Historically, wetlands were called swamps,
marshes, bogs, fens, or sloughs, depending on existing plant and water conditions
and on geographic setting. Wetlands are frequently transitional between uplands
(terrestrial systems) and continuously or deeply flooded (aquatic) systems. They are
also found at topographic lows (depressions) or in areas with high slopes and low
permeability soils (seepage slopes). In other cases, wetlands may be found at topographic highs or between stream drainages when land is flat and poorly drained
(blanket bogs). In all cases, the unifying principle is that wetlands are wet long
enough to alter soil properties because of the chemical, physical, and biological
changes that occur during flooding, and to exclude plant species that cannot grow
in wet soils.1
The structural components of natural wetland ecosystems are shown in Figure
6.1. These components are highly variable and depend on hydrology, underlying
sediment types, water quality, and climate. Starting with the unaltered sediments or
bedrock below the wetlands, these typical components are1
Underlying strata unaltered organic, mineral, or lithic strata, typically saturated
with or impervious to water and below the active rooting zone of the wetland
vegetation
Hydric soils the mineral-to-organic soil layer of the wetland, infrequently to
continuously saturated with water and containing roots, rhizomes, tubers, funnels,
burrows, and other active connections to the surface environment
CONSTRUCTED TREATMENT WETLANDS
271
Canopy
Tree
Subcanopy
Tree
Emergent
Vegetation
Shrub
Seasonal
High Water
Rhizomes
Detritus
Hydric Soils
Cypress Kness
Buttressed
Stem
Seasonally
Flooded Zone
Seasonal
Low Water
Unaltered
Sediment
Figure 6.1
Structural components of natural wetland ecosystems (adapted from Kadlec et

al., 1996).
Detritus the accumulation of live and dead organic material in a wetland,

consisting of dead emergent plant material, dead algae, living and dead animals
(primarily invertebrates), and microbes (fungi and bacteria)
Seasonally flooded zone the portion of wetland seasonally flooded by standing
water and providing habitat for aquatic organisms including fish and other vertebrate animals, submerged and floating plant species that depend on water for
buoyancy and support, living algae, and populations of microbes
Emergent vegetation vascular, rooted plant species containing structural components that emerge above the water surface, including both herbaceous and
woody plant species
Natural wetlands have been used as convenient wastewater discharge sites for
as long as sewage has been collected (at least 100 years in some locations). Examples
of old treatment wetland sites can be found in Massachusetts, Wisconsin, Florida,
and Ontario.
Judging by the growing number of wetlands built for wastewater treatment
around the world, this natural technology seems to have firmly established roots.
After almost 30 years of use in wastewater treatment, constructed treatment
wetlands now number over 1000 in Europe and in North America.1 Marsh-type
surface flow systems are most common in North America, but subsurface flow
wetlands, where wastewater flows beneath the surface of a gravel-rock bed, predominate in Europe. This inexpensive, low-maintenance technology is reportedly
in high demand in Central America, Eastern Europe, and Asia. New applications,
272
from nitrate-contaminated groundwater to effluent from high-intensity livestock

operations, are also increasing.
In the U.S., treatment-wetland technology has not yet gained universal regulatory
acceptance; projects are approved on a case-by-case basis. Some states and EPA
regions are eager to endorse them, but others are wary of this nontraditional method
of treating wastewater and contaminated groundwater. In part, this reluctance exists
because the technology is not yet completely understood. Knowledge of how the
wetland works is not far enough advanced to provide engineers with detailed predictive models. Because wetlands are natural systems, their performance is variable,
subject to the vagaries of changing seasons and vegetative cycles. These treatment
wetlands also pose a potential threat to wildlife attracted to this new habitat within
an ecosystem exposed to potentially toxic compounds.
When utilized for benign, pretreated wastewaters, wetlands do not generally pose
a threat to human or wildlife health. In these circumstances, there may be significant
ancillary benefits in terms of habitat creation and beneficial human use. In those
situations where a potentially hazardous condition exists, the extra expense of a
gravel media is warranted.1 Water and associated particulates, organisms, and sediments are then located below ground, and thus out of reach of human and wildlife
contact. Subsurface wetland waters are typically anoxic or anaerobic, which is
optimal for some processes such as sulfide precipitation or denitrification, but unsatisfactory for other processes, such as nitrification of ammonium nitrogen.
New efforts are underway, however, to place the technology onto firmer scientific
and regulatory ground. Long-term demonstration and monitoring field studies are
currently probing the inner workings of wetlands and their water quality capabilities
to provide better data on how to design more effective systems. Researchers are
documenting the fate of toxic compounds in wetlands and the extent to which wildlife
may be exposed to them. A recent study of U.S. policy and regulatory issues
surrounding treatment wetlands has recommended that the federal government
actively promote this technology and clear the regulatory roadblocks to enable wider
use. Proponents argue that the net environmental benefits of constructed wetlands,
such as restoring habitat and increasing wetland inventory, should be considered. A
federal interagency work group is grappling with that recommendation, trying to
balance the benefits and shortcomings of this increasingly popular technology.
6.1.1
Beyond Municipal Wastewater
Constructed wetland systems in North America have been designed predominantly for large-scale treatment of municipal wastewater, ranging from 100,000 to
15 million gallons per day.1,2 The use of treatment wetlands is well established in
Europe, where the technology originated with laboratory work in Germany 30 years
ago.3 Subsurface-flow systems are the norm because they provide more intensive
treatment in a smaller space than marsh-type wetlands an important design
constraint in countries where open space is limited. The European thrust has been
for small-scale systems primarily for domestic wastewater treatment; for example,
Denmark alone has 150 systems, most in small villages handling domestic wastewater. The term reed beds is commonly used for treatment wetlands in Europe.
273
Since the 1980s, constructed wetlands have also been built to treat other types
of wastewaters, including acid mine drainage, industrial wastewater, agricultural and
storm water runoff, and effluent from livestock operations.1,2 The petroleum industry
is using constructed wetlands to treat a variety of wastewaters from refineries and
fuel storage tanks. Food processing and pulp and paper industries are relative newcomers to treatment wetlands. Stormwater runoff also has recently become a focus
of research in using constructed wetlands as a treatment method.
While many of the early acid mine drainage treatment systems were marsh-like
surface flow systems, the most recent projects are passive treatment systems that
link several different types of cells vertical limestone drain as well as vegetated
cells to sequentially treat particularly nasty wastewater with low pH and high
metals content.2 A wetland system for the treatment of runoff from coal piles at
coal-fired power plants with a pH of 2 and high levels of metals uses a series of
successive alkalinity-producing systems, a rich organic layer over an anoxic limestone drain, to reduce the acidity in the wastewater before it flows into wetland cells.
Landfill leachates are a subset of polluted waters requiring substantial levels of
treatment. Leachates vary considerably, depending upon the materials accepted at
the landfill. They may contain large concentrations of volatile and toxic organics,
both as individual compounds and as COD, chlorinated organics, metals, and nitrogenous compounds.2 Wetland treatment of landfill leachates has been successfully
tested at several locations. Cold climate systems are functioning properly in Norway,
as well as at several locations in Canada; reed beds are used to treat leachate in the
United Kingdom, Slovenia, and Poland.4
Based on current understanding of the effectiveness of wetland treatment of
leachates, several U.S. projects are in planning and design phases. In addition, there
are about a half-dozen other projects in various locations, such as Mississippi,
Indiana, Pennsylvania, and West Virginia. Wetlands have been proposed for control
of stormwater runoff from capped landfills.1,2
Continued growth in the use of treatment wetlands is expected as a result of new
regulatory initiatives on nutrient management, including the Clean Water Acts total
maximum daily load (TMDL) program. Small- to medium-sized communities trying
to meet new TMDLs in sensitive watersheds for phosphorus or ammonia need
something that is cost-effective, and wetlands are a good option.
6.1.2
Looking Inside the Black Box
The rapid spread and diversification of treatment-wetland technology are running

ahead of the mechanistic understanding of how they work. These complex natural
systems are still, somewhat, a black box, according to many in the field. For
example, the role of plants in transporting oxygen into the root zone to promote
nitrification has been demonstrated in the laboratory but not convincingly in the
field, according to many researchers. There is very little data to say whether that is
an important factor or whether the plants are more or less passive. It is likely,
according to some researchers, that the ratio of open water to vegetated areas is
more important in creating aerobic conditions in a wetland.
274
Another issue quite often debated is how important the volume of water in a
wetland is to treatment performance. Is it the bottom of the wetland or the volume
of water that is more important? The data coming in now are on the side of the
wetland bottom:1,2 it apparently does not matter how deep the water is as long as
the soil is wet. That is a surprise to civil engineers, who, for years, have designed
treatment systems based on their volume and hydraulic residence time.
Numerous research efforts, both broad based and focused, are currently generating a great deal of new information on treatment-wetland function.1,2,5 The extensive research activities include gathering conventional water quality data; measurements of metals, biotoxicity, and organics; bird surveys; and macroinvertebrate
sampling. Expanding the species pallet of plants used in treatment wetlands is
another focus of research among researchers in this field. Most constructed wetlands
for treatment have been built around herbaceous species so far, and many researchers
are experimenting with a greater variety of plants to see how water quality changes
when multispecies systems are used. Many have found that pathogen removal is
higher in a multispecies system than in a single species system. One of the things
that may be important in pathogen removal is having multiple types of wetland
components, for example, a duckweed system followed by a subsurface wetland.5
Looking deeper into the wetland, to the microbes in the soil and around the root
systems of wetland plants, some researchers are studying the role that bacteria play
in trace element removal. Researchers have found that bacteria in the root zone of
bulrush increase the plants ability to accumulate and volatilize selenium twofold.
They are now working to identify which bacteria are most responsible, and will soon
move to mesocosm studies to see whether seeding the soil with those bacteria
increases trace element removal.
Some researchers are experimenting with an innovative wetland design a
vertical flow system to solve the oxygen depletion problem and boost nitrification.1,2 Effluent flows over a porous surface and percolates through a vegetated sand
filter, which is periodically allowed to dry to reintroduce oxygen to the system.
6.1.3
Potential Attractive Nuisances
Aside from research issues surrounding the design and performance of the
treatment wetlands black box, another scientific issue looms large for the future of
the technology: do treatment wetlands pose a threat to wildlife?1,5 This question is
an important one, since many wetland projects are designed with habitat creation
as one of their primary beneficial objectives. It is easier to justify the land use for
a constructed wetland if it is also used for habitat restoration.
Research is also being directed toward several critical issues. Some researchers
are working to find out exactly where toxic trace elements from wastewater end up
in a treatment wetland. They are completing laboratory studies documenting trace
element uptake potential of various wetland plants and identifying where the elements go in the plants: roots, stems, leaves, or plant litter. They are also monitoring
several active treatment wetlands to track trace elements in the ecosystem: sediment,
water, air, plant tissues, and animal tissues.
275
To address similar habitat-related issues, influent and effluent water have been
analyzed for potential bioaccumulation and mutagenic activity from organic compounds.5 Toxicity tests were designed to look for physiological impacts on biota
living in the system. Work also continues on the control of an unplanned threat to
human health: mosquitoes. Fish have been introduced to the wetlands to consume
mosquito larvae, but the density of the particular bulrush variety used may prevent
the fish from reaching certain parts of the wetland. Sections of the wetlands can be
reconfigured and replanted to raise the water level and give the fish greater access.
6.1.4
Regulatory Uncertainty and Barriers
Treatment wetlands do not appeal to all wastewater engineers because they lack
the traditional handles of engineered pollution control systems, are not easy to
control, and may be hard to predict. Regulators in the U.S. have similar problems
with treatment wetlands because they do not fit easily into existing regulatory
categories. Surface-flow treatment wetlands can be a point source discharge and a
protected environment at the same time.
No national guidance on the use of treatment wetlands and no uniform acceptance
of them by states exist, according to researchers and consultants. In this atmosphere
of regulatory uncertainty, questions abound. Concerns have been expressed that under
a strict reading of the Clean Water Act, certain treatment wetlands could be considered
waters of the U.S., and thus discharges into them could be tightly regulated.
USEPAs environmental technology initiative (ETI) treatment wetland policy and
permitting team of representatives from federal, state, and local agencies issued a
report in January, 1997, that recommended changes in regulation and/or policy that
would facilitate, where appropriate, implementation of beneficial treatment wetland
projects.6,7 It also advocated that net environmental benefits of habitat creation,
reduced use of energy and treatment chemicals, and recreational value not just
the water quality impact of a treatment wetland project should be considered in
approving it.
The report catalogued numerous regulatory and policy issues. Should disinfection of effluent be done at the inlet rather than the outlet of a wetland? When should
a wetland be lined to protect groundwater? Should treatment wetlands be allowed
to mitigate for permitted wetland losses? Under what conditions should constructed
treatment wetlands be considered waters of the U.S.? The report also noted that
more research is needed concerning the fate and effect of potential wastewater
toxins and ecological risks in treatment wetlands.
The federal interagency work group, including representatives from USEPA
wetlands and wastewater offices, the U.S. Army Corps of Engineers, the National
Oceanic and Atmospheric Administration, the Bureau of Reclamation, and the U.S.
Fish and Wildlife Service, was created to take up these issues.6,7
The question of where treatment wetlands should be sited has been a particularly
difficult regulatory issue, and consensus must be reached on the need to handle
wetland systems differently depending on whether their primary purpose is water
treatment or habitat restoration. There is still some disagreement about the habitat
276
value of treatment wetlands and concerns about the negative impact they could have
on the environment.
USEPA currently is not developing the type of specific guidance documents and
formal agency actions recommended in the ETI study to promote the use of treatment
wetlands. Nevertheless, wetlands experts are encouraged because the issues are now
being discussed at the national level.
6.2
6.2.1
TYPES OF CONSTRUCTED WETLANDS
Horizontal Flow Systems
The purposeful construction of treatment wetland ecosystems is a relatively new

technology. Constructed wetlands for pollution control, wastewater treatment, and,
recently, for contaminated groundwater treatment are divided into two basic types:
free water surface (FWS) and subsurface flow (SSF) wetlands. Both types consist
of a channel or a basin with some sort of barrier to prevent seepage and utilize
emergent aquatic vegetation as part of the treatment system. The difference between
FWS and SSF wetlands is that SSF uses some kind of media as a major component
(Figures 6.2a and b). In an FWS treatment wetland, soil supports the roots of the
emergent vegetation; water at a relatively shallow depth of 6 to 24 inches flows
through the system with the water surface exposed to the atmosphere. Oxygen is
provided by diffusion through the water surface.
Inlet
Outlet
Weir
Figure 6.2a
Free water surface (FWS) wetland.
An SSF treatment wetland bed contains a suitable depth (1.5 3.0 feet) of
permeable media, such as coarse sand or crushed stone, through which the water
flows. The media also support the root structure of the emergent vegetation. The
surface of the flowing water is beneath the surface of the top layer of the medium,
determined by proper hydraulic design and appropriate flow control structures. In
both systems the polluted water undergoes physical, biological, and chemical treatment processes as it flows through the wetlands.
The rate at which organic contaminants move through wetlands can be determined by several transport mechanisms. These mechanisms often act simultaneously
on the organics and may include such processes as convection, diffusion, dispersion,
and zero- or first-order production or decay.
277
Inlet
Effluent
Porous Media
Figure 6.2b
Subsurface flow (SSF) wetland.
Currently, constructed wetlands for municipal wastewater treatment are designed

based on the assumptions of plug-flow hydrodynamics and first-order biochemical
oxygen demand (BOD) removal kinetics. The first assumption implies that dispersion
in the system is negligible and all the fluid particles have a uniform detention time
traveling through the system. The plug-flow model seems to give a reasonably
accurate estimate of the performance of SSF-constructed wetlands.
However, some designers have recognized the limitation of using the plug-flow
model for constructed wetlands design. Three types of hydraulic inefficiencies may
occur in treatment wetlands: one caused by internal islands and topographical features,
a second caused by preferential flow channels on a large-distance scale, and a third
caused by mixing effects, such as water delays in litter layers and transverse mixing.
6.2.2
Vertical Flow Systems
Vertical flow constructed wetlands are vegetated systems in which the flow of
water is vertical rather than horizontal as in FWS and SSF wetlands (Figure 6.3).
Figure 6.3
Vertical flow constructed wetland.
278
Polluted water is applied at time intervals over the entire surface of the wetland.
The water flows through a permeable medium and is collected at the bottom. The
intermittent application allows the cell to drain completely before the next application. This type of operation allows for much more oxygen transfer than typical SSF
systems and thus may be a good option for treatment of wastewaters with a relatively
high oxygen demand. This type of system has been recommended for removal of
high levels of ammonia through nitrification. High BOD levels may cause clogging
due to biomass buildup; mineral buildup may also cause clogging. Intermittent
application gives the advantage of greatly increasing the oxygen available for microbial reactions, but also greatly increases the mechanical and operational requirements
of the system over the more traditional wetland treatment processes.
6.3
MICROBIAL AND PLANT COMMUNITIES OF A WETLAND
Because of the presence of ample water, wetlands are typically home to a variety
of microbial and plant species. This biological diversity, from the smallest virus to
the largest tree, creates interspecies interactions resulting in greater diversity, more
complete utilization of energy inflows, and ultimately, emergent properties of the
wetland ecosystem.1,6,7 The treatment wetland system designer should not expect to
maintain a system with just a few known species. The successful wetland designer
creates the gross environmental conditions suitable for groups or guilds of species,
seeding the wetland with diversity by planting multiple species, using soil seed
banks, and inoculating from other similar wetlands, and then using minimum external
control to guide the wetland development.1 This form of ecological engineering
results in lower initial cost, lower operation and maintenance costs, and the most
consistent system performance.
6.3.1
Bacteria and Fungi
Wetland and aquatic habitats provide suitable environmental conditions for the
growth and reproduction of microorganisms, two important groups of which are
bacteria and fungi. These organisms are important in treatment wetland systems
primarily because of their role in the assimilation, transformation, and recycling of
chemical constituents present in contaminated waters.
Bacteria and fungi are typically the first organisms to colonize and begin the
sequential decomposition of contaminants and wastes. Also, microbes typically have
first access to dissolved constituents in the wastewater or contaminated groundwater.
Some bacteria are sessile, while others are motile by use of flagella. In wetlands,
most bacteria are associated with solid surfaces of plants, decaying organic matter,
and soils. Bacteria also play a significant role in altering the biogeochemical environment because they are responsible for processes such as nitrification, denitrification, sulfate reduction and methanogenesis, etc.
Fungi represent a separate kingdom of eucaryotic organisms and include yeasts,
molds, and fleshy fungi. Most fungal nutrition is saprophytic, which means it is
279
based on the degradation of dead organic matter. Fungi are abundant in wetland
environments and play an important role in treatment.
6.3.2
Algae
Algae are unicellular or multicellular photosynthetic bacteria and plants that lack
the variety of tissues and organs of higher plants. Algae are a highly diverse assemblage of species that can live in a wide range of aquatic and wetland habitats. Major
algae life forms typical in wetland environments are unicellular, colonial, filamentous, and macroscopic forms.
For the most part, algae depend on light for their metabolism and growth and
serve as the basis for an autochthonous food chain in wetland habitats. Organic
compounds created by algae photosynthesis contain stored energy which is used for
microbial respiration or which enters the aquatic food chain and provides food to a
variety of microbes. Alternately, this reduced carbon may be directly deposited as
detritus to form organic peat sediments in wetlands.
When light and nutrients are plentiful, algae can create massive populations and
contribute significantly to the overall food web and nutrient cycling of a treatment
wetland ecosystem. When shaded by the growth of macrophytes, algae frequently
play a less important role in wetland energy flows and treatment (Figure 6.4).
Filamentous algae mats are sometimes a dominant component of the plant
biomass in wetland systems. The mats are made of a few dominant species of green
or blue-green filamentous algae in which individual filaments may include thousands
of cells. Filamentous algae mats first develop below the water surface on the substrate
of wetland in areas with little emergent vegetation. During the day, entrained gas
bubbles (primarily pure oxygen resulting from photosynthesis) may cause the mats
to move up through the water column and float at the surface. During the night, the
mats sink again to the wetland substrate.1
Filamentous algae that occur in wetlands as periphyton or mats may dominate
the overall productivity of the wetland, controlling DO and CO2 concentrations
within the treatment wetland water column. Wetland water column DO can fluctuate
diurnally from near zero during the early morning following a night of high respiration to well over saturation (>15 mg/L) in high algae growth areas during a sunny
day. Dissolved carbon dioxide and consequently the pH of the water varies proportionally to DO because of the corresponding use of CO2 by plants during photosynthesis and release at night during respiration. As CO2 is stripped from the water
column by algae during the day, pH may rise by 2 to 3 pH units (a 100- to 1000fold increase in H+ concentration). These daytime pH changes are reversible, and
the production of CO2 at night by algae respiration frequently returns the pH to the
previous days value by early morning (Figure 6.5.)1
6.3.3
Species of Vegetation for Treatment Wetland Systems
The term macrophyte includes vascular plants with tissues that are easily visible.
Vascular plants differ from algae through their internal organization into tissues
resulting from specialized cells (Figure 6.6). The U.S. Fish and Wildlife Service has
280
Figure 6.4
Major energy sources and ecological niches affecting the occurrences of algae
in wetlands (adapted from Kadlec and Knight, 1996).
10
pH
10
pH
Dissolved Oxygen (mg/L)
20
DO
0
12
MN
6
AM
12
NOON
6
PM
12
MN
TIME
Figure 6.5
Typical diurnal plots of DO concentration and pH in a wetland dominated by

filamentous algae.
281
Cattail
Duck Potato
Emergent
Herbaceous
a.
Buttonbush
Shrub
Emergent
Woody
b.
Water Lilly
c.
Floating Leaved
Hydrilla
d.
Figure 6.6
Submerged
Growth forms of rooted wetland and aquatic vascular plants (adapted from
Kadlec and Knight, 1996).
more than 6700 plant species on their list of obligate and facultative wetland plant
species in the U.S. Obligate wetland plant species are defined as those which are
found exclusively in wetland habitats, while facultative species are those that may
be found in upland or in wetland areas.1
Wetland macrophytes are the dominant structural component of most wetland
treatment systems. The vascular macrophytes can be categorized morphologically
L1282/C06/frame Page 282 Tuesday, June 19, 2001 1:10 PM
282
by descriptors such as woody, herbaceous, annual, perennial, emergent, floating, and

submerged. Woody species have stems or branches that do not contain chlorophyll.
Since these tissues are adapted to survive for more than one year, they are typically
more durable or woody in texture. Herbaceous species have aboveground tissues
that are leafy and filled with chlorophyll-bearing cells that typically survive only
one growing season. Woody species include shrubs that attain heights of up to six
to ten feet and trees that are generally more than ten feet in height when mature.1
The terms emergent, floating, and submerged refer to the predominant growth
form of a plant species. In emergent plant species, most of the aboveground part of
the plant emerges above the waterline and into the air. These emergent structures
may be self-supporting or may be supported by other physical structures. Emergent
plant species are important because they provide surface area for microbial growth
important in many of the contaminant assimilation processes in treatment wetland
systems.1,2 Floating species have leaves and stems buoyant enough to float on the
water surface. Submerged species have buoyant stems and leaves that fill the niche
between sediment surface and the top of the water column. Floating and submerged
species may appear in treatment wetlands when water depths exceed the tolerance
range for rooted, emergent species.
Aquatic macrophyte-based wetlands treatment systems may be classified according
to the life form of the dominating macrophyte into 1) free-floating macrophyte-based
treatment systems; 2) rooted emergent macrophyte-based wastewater treatment systems;
3) submerged macrophyte-based wastewater treatment systems; and 4) multistage systems consisting of a combination of the above-mentioned concepts and other kinds of
low-technology systems (e.g., oxidation ponds and sanitary filtration systems).
6.3.3.1 Free-Floating Macrophyte-Based Systems
Free-floating macrophytes are highly diverse in form and habit, ranging from
large plants with rosettes of aerial and/or floating leaves and well-developed submerged roots (e.g., water hyacinth, Eichhornia crassipes) to minute surface-floating
plants with few or no roots (e.g., duckweeds, Lemna, Spirodella, Wolffia sp.)
(Figure 6.7a).2
Influent
Effluent
Figure 6.7a
Schematic description of a free-floating water hyacinth-(Eichhornia crassipes)

based treatment wetland system.
Water Hyacinth-Based Systems: The water hyacinth is one of the most prolific
and productive plants in the world. This high productivity is exploited in wetland
treatment facilities. Two different concepts are applied in water hyacinth-based
283
wastewater treatment systems: 1) tertiary treatment systems (i.e. nutrient removal) in

which nitrogen and phosphorus are removed by incorporation into the water hyacinth
biomass, which is harvested frequently to sustain maximum productivity and to remove
incorporated nutrients. Nitrogen may also be removed as a consequence of microbial
denitrification; and 2) integrated secondary and tertiary treatment systems (i.e., BOD
and nutrient removal) in which degradation of organic matter and microbial transformations of nitrogen (nitrification-denitrification) proceed simultaneously in the water
hyacinth ecosystem. Harvesting of water hyacinth biomass is only carried out for
maintenance purposes. The latter system should include aerators, that is, areas with a
free water surface where oxygen can be transferred to the water from the atmosphere
by diffusion and where algal oxygen production can occur. The retention time in the
systems varies according to wastewater characteristics and effluent requirements, but
is generally on the order of from 5 to 15 days.2
The role of water hyacinths in the process of suspended solids removal is well
documented. Most suspended solids are removed by sedimentation and subsequent
degradation within the basins, although some sludge might accumulate on the sediment surface. The dense cover of water hyacinths effectively reduces the effects of
wind mixing and also minimizes thermal mixing. The shading provided by the plant
cover restricts algal growth, and hyacinth roots impede the horizontal movement of
particulate matter. Furthermore, electrical charges associated with hyacinth roots are
reported to react with opposite charges on colloidal particles such as suspended
solids, causing them to adhere to plant roots, where they are removed from the
wastewater stream and slowly digested and assimilated by the plant and microorganisms. The efficiency of water hyacinths in removing BOD and in providing good
conditions for microbial nitrification is related to their capability of transporting
oxygen from the foliage to the rhizosphere. The extensive root system of the water
hyacinth provides a huge surface area for attached microorganisms, thus increasing
the potential for decomposition of organic matter.1,2
Water hyacinth-based wetland treatment systems are sufficiently developed to
be applied successfully in tropics and subtropics. Water hyacinths are severely
affected by frost; the growth rate is greatly reduced at temperatures below 10C.
Consequently, in temperate regions, water hyacinth-based systems can only be used
in greenhouses or outdoors during summer. Pennywort (Hydrocotyle umbellate), on
the other hand, has a high growth rate and a high nutrient uptake capacity even
during relatively cold periods in subtropical areas.2 It has been suggested that water
hyacinths and pennywort can be alternately cultured, winter and summer, in order
to maintain performance at a high level year-round.
Duckweed-Based Systems: Duckweeds (Lemna, Spirodella, and Wolffia sp.)
have not been investigated as much as water hyacinths for use in wetlands treatment.
Duckweeds, have a much wider geographic range than water hyacinths, however,
as they are able to grow at temperatures as low as 1 to 3C. Compared to water
hyacinths, duckweeds, play a less direct role in the treatment process because they
lack extensive root systems and therefore provide a smaller surface area for attached
microbial growth.2 The main use of duckweeds is therefore in recovering nutrients
from secondary treated wastewater. A dense cover of duckweed on the surface of
water inhibits both oxygen entering the water by diffusion and the photosynthetic
284
production of oxygen by phytoplankton because of poor light penetration. The water

consequently becomes largely anaerobic, which in turn favors denitrification. The
light absorption of duckweed cover restricts growth of phytoplankton and therefore
the production of suspended solids.
Duckweed-based systems may be plagued by problems, as high winds can pile
the duckweed into thick mats and eventually completely sweep the plants from the
water. Therefore, in large systems, it is necessary to construct some kind of barrier
on the water surface to prevent this. The retention time in duckweed-based wetland
treatment systems depends on wastewater quality, effluent requirements, harvesting
rate, and climate, but it varies typically from 30 days during summer to several
months during winter.
6.3.3.2 Emergent Aquatic Macrophyte-Based Systems
Rooted emergent aquatic macrophytes are the dominant life form in wetlands
and marshes, growing within a water table ranging from 18 inches below the soil
surface to a water depth of 60 inches or more. In general, they produce aerial stems
and leaves, and an extensive root and rhizome system. The depth penetration of the
root system, and thereby the exploitation of sediment volume, is different for different species. Typical species of emergent aquatic macrophytes are the common
reed (Phragmites australis), cattail (Typha latifolia), and bulrush (Scirpus lacustris).2
All species are morphologically adapted to growing in a waterlogged sediment by
virtue of large internal air spaces for transportation of oxygen to the roots and
rhizomes. Most species of emergent aquatic macrophytes possess an extensive internal lacunal system that may occupy 50 to 70% of the total plant volume. Oxygen
is transported through the gas spaces to the roots and rhizomes by diffusion and/or
by convective flow of air. Part of the oxygen may leak from the root system into
the surrounding rhizosphere, creating oxidized conditions in the otherwise anoxic
sediment and stimulating both decomposition of organic matter and growth of
nitrifying bacteria. Emergent macrophyte-based wetland treatment systems can be
constructed with different designs; see Figure 6.7b for an example. These types of
systems are also currently applied for the precipitation and removal of dissolved
heavy metals under anaerobic conditions as a sulfide or carbonate precipitate.
Figure 6.7b
Emergent macrophyte treatment wetland system with surface flow (adapted from
Mohiri, 1993).
285

Subsurface Flow
Design typically consists of a bed planted with the common reed Phragmites
australis and underlain by an impermeable membrane to prevent seepage if required.
The medium in the bed may be soil or gravel. During the passage of wastewater or
contaminated groundwater through the rhizosphere of the reeds, organic matter is
decomposed microbiologically, nitrogen may be denitrified, and phosphorus and heavy
metals may be fixed in the soil. The reeds have two important functions in the process:
1) to supply oxygen to the heterotrophic microorganisms in the rhizosphere, and 2) to
increase and stabilize the hydraulic conductivity of the soil. The quantitative significance of the uptake of nutrients in the plant tissue is negligible, as the amount of
nutrients taken up during a growing season constitutes only a few percent of the total
content introduced with the wastewater. Moreover, nutrients bound in the plant tissue
are recycled in the system upon decay of the plant material. Surface runoff is a general
problem in soil-based treatment facilities because it prevents the wastewater from
coming into contact with the rhizoshere. Furthermore, the oxygen transport capacity
of the reeds seems to be insufficient to ensure aerobic decomposition in the rhizosphere
and deliver the oxygen needed for quantitatively significant nitrification.
Subsurface Flow
In a vertical flow system the requirements for sufficient hydraulic conductivity
in the bed medium and improved rhizosphere oxygenation can be established. A
design consisting of several beds laid out in parallel with percolation flow and
intermittent loading will increase soil oxygenation several-fold compared to horizontal subsurface flow systems. During the loading period, air is forced out of the
soil; during the drying period, atmospheric air is drawn into the porespaces of the
soil, thus increasing soil oxygenation. Furthermore, diffusive oxygen transport to
the soil is enhanced during the drying period, as the diffusion of oxygen is approximately 10,000 times faster in air than in water. This design and operational regime
provides alternating oxidizing and reducing conditions in the substrate, thereby
stimulating sequential nitrificationdenitrification and phosphorus adsorption (Figure 6.7c). The limited information available on the treatment performance of such
systems indicates good performance with respect to suspended solids and aerobically
biodegradable organics, ammonia, and phosphorus.
6.3.3.5 Submerged Macrophyte-Based Systems
Submerged aquatic macrophytes have their photosynthetic tissue entirely submerged (Figure 6.7d). The morphology and ecology of the species vary from small,
rosette-type, low-productivity species growing only in oligotrophic waters (e.g.,
Isoetes lacustris and Lobelia dortmanna) to larger eloedid-type, high-productivity
species growing in eutrophic waters (e.g., Elodea canadensis).
286
Figure 6.7c
Emergent macrophyte based treatment wetland system with vertical percolation.
Figure 6.7d
Schematic description of a submerged macrophyte-based treatment wetland

system.
Submerged aquatic plants are able to assimilate nutrients from polluted waters.
However, they only grow well in oxygenated water and therefore cannot be used in
wastewater with a high content of readily biodegradable organic matter because the
microbial decomposition of the organic matter will create anoxic conditions. The
prime potential use of submerged macrophyte-based wastewater treatment systems
is therefore for polishing secondarily treated wastewaters, although good treatment
of primary domestic effluent has been obtained in an Elodea nuttallii-based system.
The presence of submerged macrophytes depletes dissolved inorganic carbon in the
water and increases the content of dissolved oxygen during the periods of high
photosynthetic activity. This results in increased pH, creating optimal conditions for
volatilization of ammonia and chemical precipitation of phosphorus. High oxygen
concentrations also create favorable conditions for the mineralization of organic
matter in the water. The nutrients assimilated by the macrophytes are largely retained
within the rooting tissues of the plants and by the attached microflora. Losses from
the foliage of plant nutrients upon senescence of the macrophyte tissues are readily
taken up by the periphytic community so that very little leaves the littoral detritus
and macrophyte-epiphyte complexes. Much of the detrital matter produced in these
systems will be accumulated and retained in the sediments.
The use of submerged macrophytes for wastewater treatment is still in the
experimental stage, with species like egeria (Egeria densa), elodea (Elodea canadensis and Elodea nuttallii), hornwort (Ceratophyllum demersum), and hydrilla
287
(Hydrilla verticillata) being the most promising. Present knowledge suggests that
their prime area of application will be as a final step in multistage systems.
6.3.3.6 Multistage Macrophyte-Based Treatment Systems
Different types of these macrophyte-based wastewater treatment systems may
be combined with each other or with conventional treatment technologies. For
example, a multistage system could consist of 1) a mechanical clarification step for
primary treatment; 2) a floating or emergent macrophyte-based treatment system for
secondary treatment; and 3) a floating, emergent, or submerged macrophyte-based
step for tertiary treatment. The types of secondary and tertiary treatment step will,
among other factors, depend on wastewater characteristics, treatment requirements,
climate, and amount of available land.
6.4
TREATMENT WETLAND SOILS
Several individual component wetland processes combine to provide the observed

overall treatments. Sedimentation and filtration remove solids. Chemical precipitation
(abiotic or microbially induced), ion exchange, and plant uptake remove metals. Nutrients are utilized by plants and algae, and cycled to newly formed sediments.
The definition of hydric soils indicates that any upland soil utilized for construction of a wetland treatment system will become a hydric soil following a short to
long period of flooding and continuous anaerobiosis.1
Hydric soils are defined as soils that, in their undrained condition, are saturated,
flooded, or ponded long enough during the growing season to develop anaerobic
conditions favoring the growth and regeneration of hydrophylic vegetation.8
Since most wetlands are constructed in former uplands, most constructed wetlands are initially dominated by mineral soils. As constructed wetland treatment
systems mature, the percent of organic matter in the soil generally increases, and in
some systems, soils might eventually cross the arbitrary line between mineral and
organic (Figures 6.8a and b). Mineral soils are classified by particle size distributions,
color, depth, and a number of other factors. The three major mineral soil classes are
clays, silts, and sands.
Clays are soils with very fine particles packed closely together. Because of their
very fine texture and low hydraulic conductivity, clays may function as aquitards.
The existence of many natural wetlands depends on impermeable clay lenses in
sedimentary or wind-blown (loess) deposits. Clays typically have the highest adsorption potential of any soils because of their high surface area to volume ratio resulting
from their small particle size distribution. When water in a wetland is in contact
with underlying clays or when water percolates through the bottom of a clay-lined
wetland, the presence of clays may greatly increase treatment potential for conservative ions such as phosphorus and metals.
Organic soils, called peat, muck, or mucky peat may be classified by their extent
of decomposition. Those soils with the least amount of decomposition (less than
one third decomposed) are called peat. Fibric peats have more than two thirds of
288
Young Plants
Water
Saturated
Mineral Soils
Aerobic
Mildly
Anaerobic
(Positive REDOX)
Figure 6.8a
The types of soils present in a newly planted treatment wetland system (adapted
from Kadlec, 1996).
Figure 6.8b
Types of soil layers developed after a period of maturation in a treatment wetland

system (adapted from Kadlec, 1996).
the plant fibers still identifiable. Saprists or mucks have greater than two thirds of
the original plant materials decomposed. Hemists (mucky peat or peaty mucks) are
between saprists and fibrists.
Due to their fibrous nature, organic soils may shrink, oxidize, and subside when
they are drained. Fire may also accelerate this oxidation process, and agricultural
289
practices (drainage, cropping, harrowing, and burning) are known to result in soil
subsidence in highly organic soils such as those in the Everglades agricultural area
where subsidence rates have been estimated at about 3 cm/yr.
Drying organic soils promotes oxidation and gasifies carbon, but not the mineral
nutrients associated with those soils. Although the available nutrient content of a
peat or muck is often quite low, there are large amounts of nitrogen, phosphorus,
sulfur, and other mineral constituents organically bound in unavailable forms. Oxidation destroys these recalcitrant organics and releases the associated substances.
Upon reflooding, those substances can dissolve and provide relatively high concentrations of nutrients and other dissolved minerals.
Organic soils cannot easily be characterized by grain size because the necessary
act of drying destroys the physical-chemical structure. The general range of hydraulic
conductivity for soils found in sedge, reed, and alder wetlands is 0.1 to 10 m/d,
placing these materials in the range of other mineral soils. However, this is true only
for fully saturated soils; even a slight degree of unsaturation lowers the hydraulic
conductivity by two orders of magnitude, due to the extremely large capillary suction
pressure created in the micropores. This means that organic soils and sediments are
virtually undrainable; they retain a very high percentage of water. Organic soils are
typically dark in color, ranging from black mucks to brown peats.
Soil chemical properties are primarily related to chemical reactivity of soil
particles and the surface area available for chemical reactions. Chemical reactivity
is related to the surface electrical charge of the soil particles, is typically highest in
clays and organic soil particles.
6.4.1
Cation Exchange Capacity
Wetland soils have a high trapping efficiency for a variety of chemical constituents; they are retained within the hydrated soil matrix by forces ranging from
chemical bonding to physical dissolution within the water of hydration. The combined phenomena are referred to as sorption.
A significant portion of chemical binding is cation exchange, which is replacement of one positively charged ion, attached to the soil or sediment, with another
positively charged ion. The humics substances found in wetlands contain large
numbers of hydroxyl and carboxylic functional groups, which are hydrophilic and
serve as cation binding sites. Other portions of these molecules are nonpolar and
hydrophobic in character. The result is the formation of micelles, groups of humic
molecules with their nonpolar sections combined in the center and their negatively
charged polar portions exposed on the surface of the micelle. Protons or other
positively charged ions may then associate with these negatively charged sites to
create electrical neutrality.
Micelles are one form of ligand that can bind metal ions. The cumulative process
of binding a metal ion to a ligand (L) to form a complex may be described by a
chemical equation; here, it is illustrated for the binding of a divalent metal ion (M):1
2HL + M2+ ML2 + 2H+
(6.1)
290
The number of ligands per gram of dry solid is determined from the number of
metal ions that can be sorbed by a fully protonated sample. This is referred to as
the cation exchange capacity (CEC) of the material, usually measured in milliequivalents per gram. Peats have CEC values of approximately 1.0 to 1.5 meq/g. For a
heavy metal such as copper, this can translate to a large binding capacity, on the
order of a few percent by weight.
Clearly, the pH of the soil or sediment has a large influence on the partitioning
of a metal to the ligand because excess hydrogen ions drive Equation 6.1 toward
the ionic form of the metal.
Drying of the organic material will destroy some of the character of the highly
hydrated micellular chemical-physical structures, therefore destroying some of the
sorption capacity of the material. The sorption capacity of dried, harvested peats is
not as large as that of wet, living peats.
6.4.2
Oxidation and Reduction Reactions
Wetlands are ideal environments for chemical transformations because of the

range of oxidation states that naturally occur in wetland soils. Free oxygen decreases
rapidly with depth in most flooded soils because of the metabolism of microbes that
consume organic matter in the soil and through chemical oxidation of reduced
substances. This decline in free oxygen, in other words the depletion of oxidizing
potential, is measured as an increasingly negative electric potential between a standard platinum electrode and the concentration of oxygen in the soil. This measure
of electric potential is called reduction-oxidation or REDOX potential (ORP) and
provides an estimate of soil oxidation or reduction potential (Figure 6.9).
Figure 6.9
Typical depth profile for potential oxidation-reduction reactions taking place in a

treatment wetland system.
291
When ORP >100 mV, conditions are termed aerobic because dissolved oxygen
is available. When ORP <100 mV, conditions are termed anaerobic because there
is no dissolved oxygen. Some authors refer to intermediate conditions (near-zero
DO) as transient or anoxic.
The reduction of ferric iron (Fe3+) to ferrous iron (Fe2+) is a REDOX half reaction
typical of anaerobic sediments:
Fe3+ + e = Fe2+
(6.2)
The typical complementary half reaction for this reduction of ferric to ferrous
iron is the oxidation of reduced sulfur (hydrogen sulfide, H2S) to sulfate (SO42 ) by
the half reaction:
H2S + 4H2O = SO42 + 10H+ + 8e
(6.3)
for an overall oxidation-reduction reaction of:

8Fe3+ + H2S + 4H2O = 8Fe2+ + SO42 + 10H+
(6.4)
However, the real situation in treatment wetlands is far more complicated because
there are more species present and more REDOX routes than those used here for
illustration. For instance, iron reduction can be accompanied by sulfate reduction
not sulfate production and the ferrous ion, Fe (II), will be precipitated out
as FeS.
The REDOX potential of many wetland soils decreases with vertical depth into
the sediments because the only source of free oxygen is from atmospheric diffusion
at the top of the sediment layer (Figure 6.9). The typical oxygen gradient in wetland
sediments includes a thin (less than a few centimeters) oxidized surface horizon at
the sediment-water interface, underlain by increasingly reduced conditions with
depth based on the amount of biological and chemical reducing activity in the
sediments. Vertical REDOX gradients in treatment wetland soils will vary in response
to distance from the point of wastewater loading.
Northern wetlands are sometimes sealed by an ice cap in winter that prevents
supply of oxygen to the water and/or soils. This then shifts the REDOX profile to
much lower Eh values, causing sulfate reduction and methanogenesis to dominate
even the upper soil horizons. Gaseous sulfur compounds cannot escape and may
reach lethal levels for wetland biota.
Treatment wetlands are often subjected to waters with higher oxygen demands
exerted by both carbonaceous and nitrogenous compounds. This causes a greater
depletion of electron acceptors such as oxygen, nitrate, sulfate, and iron in both the
water column and the underlying soils. The REDOX potential in treatment wetlands
is therefore typically lower than for natural wetlands, ranging from the denitrifying
regime downward to the methanogenesis regime.
292
6.4.3
pH
Prior to flooding, soils may have widely varying pH conditions ranging from
about 3 to 10 units. Following flooding, pH in wetland soils may initially decline
due to aerobic decomposition liberating carbon dioxide into the interstitial water.
However, this initial pH swing is generally transient and is followed by a typical
trend in both acidic and alkaline soils toward pH neutrality (pH 6.7 to 7.2 units)
over time. This typical trend is considered to be the result of ferric iron reduction
under flooded soil conditions. In some highly organic soils, pH may remain very
low, even following long periods of flooding. This result is likely due to the slow
oxidation of organic sulfur compounds resulting in production of sulfuric acid and
to the presence of humic acids.
6.4.4
Biological Influences on Hydric Soils
Biological, chemical, and physical properties of wetland soils are interdependent.

Microbial wetland fauna make up a significant fraction of the organic carbon occurring in hydric soils. These tiny organisms are competing for sometimes limited and
rapidly shifting supplies of energy containing compounds and nutrients, and their
growth and death have a very significant effect on the fate and transport of the
majority of soil chemical constituents. In addition to the microbial populations,
macrophytic plants diversify soil structure through the growth and death of roots
and creation of decaying plant litter, and wetland animals dig, burrow, scrape, and
otherwise cause bioturbation of wetland sediments on an almost continuous basis.
Some of the major interactions between wetlands biology and sediments are
described below.
6.4.5
Microbial Soil Processes
Soil microbial populations have significant influence on the chemistry of most

wetland soils. Important transformations of nitrogen, iron, sulfur, and carbon result
from microbial processes. These microbial processes are typically affected by the
concentrations of reactants as well as the REDOX potential and pH of the soil.
Organic nitrogen is biologically transformed to ammonia nitrogen through the
process of mineralization, which results as a consequence of organic matter decomposition that results from actions of both aerobic and anaerobic microbes. Ammonia
is in turn converted to nitrite and nitrate nitrogen through an aerobic microbial
process called nitrification. Nitrate nitrogen can be further transformed to nitrous
oxide or nitrogen gas in anaerobic wetland soils by the action of another group of
microbes (denitrifiers). Nitrogen gas can also be transformed to organic nitrogen by
bacterial nitrogen fixation in some aerobic and some anaerobic wetland soils.
Bacteria can transform reduced iron and possibly manganese to oxidized forms.
These chemosynthetic processes utilize oxygen as an electron acceptor and usually
are accelerated by acidic conditions typical of acidic coal mine drainage waters.
Sulfate can be reduced to sulfide by anaerobic bacteria in wetlands. The
sulfate serves as an electron acceptor in the absence of free oxygen at low REDOX
293
potentials. Sulfides can provide a source of energy for chemautotrophic and photosynthetic bacteria in aerobic wetlands, resulting in the formation of elemental sulfur
and sulfate. The formation of sulfide under anaerobic conditions enables the precipitation of dissolved heavy metals in treatment wetlands.
Organic carbon is microbially degraded to carbon dioxide by aerobic respiration
when oxygen is available and by fermentation under anaerobic conditions. Greater
energy is released under aerobic respiration, resulting in more efficient assimilation
of organic matter into microbial cellular material. In fermentation, organic matter
serves as the terminal electron acceptor, forming acids and alcohols. Methane can
be formed in wetlands due to the action of bacteria using carbon dioxide as an
electron acceptor at very low REDOX potentials.
6.4.6
Treatment Wetland Soils
The sediments that form in treatment wetlands are often different from those
that form in natural wetlands, for a number of reasons. First, the enhanced activity
of various microbes, fungi, algae, and soft-bodied invertebrates leads to a greater
proportion of fine detritus compared to leaf, root, and stem fragments. There is
significant formation of low-density biosolids (sludge). Second, there may be a
precipitation of metal hydroxides, carbonates, or sulfides, which add mineral flocs
to the sediments. Finally, there is often a high ionic strength associated with treatment
of effluents reflected in high dissolved salt content. The effect of high ionic strength
is to alter the structure of the highly hydrated organic materials comprising wetland
sediments and soils.
The considerations listed previously show that wetland soils are a vital and
integral link in processes that govern water quality. Therefore, it seems reasonable
to expect consideration of wetland soils to be an important part of treatment wetland
design; however, that is not the case. Antecedent soils are altered and replaced by
new organic soils. The sorption capacity of the antecedent soils is re-equilibrated
with the new water quality of the incoming water, perhaps along a gradient from
inlet to outlet. If there are leachable chemicals, they are depleted and exit the wetland.
Roots and rhizomes of new plantings (constructed wetlands) or replacement species
(natural wetlands) repopulate the top 30 cm of the wetland and set up a new
biogeochemical cycle.
The long hydroperiods of treatment wetlands are conducive to the buildup of
organics: first litter and microdetritus, then the sediments formed from their decomposition, and, finally, the organic soils generated from those sediments and deposited
mineral solids.
In short, the wetland rearranges itself to accommodate the environment created
by the designer. The functioning of the wetland after such adaptation is no longer
dependent upon the previous condition and type of soils, hydrology, and biota; it is
now totally dependent upon the new soils, hydrology, and biota. It is this new
sustainable mode of wetland operation that is the target of most designs.
Available data indicate that the final state of a treatment wetland, and the accompanying suite of water quality functions, are largely independent of the initial
condition of the real estate upon which it is built. During the interim period of
294
adaptation, antecedent conditions are important because they dictate the short-term
performance of the wetland. That period of adaptation appears to extend for up to
2 years for newly constructed wetlands and longer for alteration of natural wetlands
to a treatment function.1,2
If soils are unsatisfactory for plant or microbial growth, the wetland treatment
system is liable to have inadequate plant cover. A knowledge of the physical and
chemical composition of site soils is essential to predict accurately some internal
chemical and biological processes in treatment wetlands. The rate of soil accretion
in wetland treatment systems affects the potential removal of conservative elements
such as phosphorus and heavy metals and also is an important consideration during
design of berm height above the wetland substrate. Some sorbed materials can be
released if exposed to lower concentrations in incoming water. Violent hydrologic
events are capable of resuspending particulate deposits. It is therefore incumbent on
the designer to minimize or prevent such occurrences.
The main environmental factor that influences the nature of wetlands soils is
dissolved oxygen concentration. Vertical oxygen gradients are typically established
in wetland soils due to bacterial respiration and chemical oxidation demand and due
to the greatly reduced rate of oxygen diffusion in saturated soils compared to
unsaturated soils. These oxidation gradients result in a chain of oxidation-reduction
reactions that provide many wetlands with their typical profile of declining REDOX
potentials with depth (Figures 6.10a and b). REDOX, in turn, affects the microbial
processes important in most aspects of wetland use for water quality improvement,
especially including removal of organic carbon and nitrogen.
Wetland soils are as dynamic in character as all other aspects of the wetland
ecosystem. Soils in constructed wetlands built on upland sites undergo gradual
transformation, resulting in accumulations of organic carbon and reduced elements
such as iron and sulfur typical of natural wetland soils. Many of the changes that
occur during wetland development and succession are the result of biological factors
that occur in wetlands such as growth of bacteria and fungi, algae and macrophytic
plants, micro- and macroinvertebrates, and larger animals. While many of these
natural biological processes are not within the control of the wetland treatment
system designer and operator, their effects should be considered when trying to
maximize chances for success with a wetland project.
6.5
6.5.1
CONTAMINANT REMOVAL MECHANISMS
Volatilization
A shallow wetland water body provides the opportunity for air stripping of
volatiles. The efficiency is not as great as for mechanical devices, but the difference
is more than compensated for by the long detention times and large surface areas
in the wetland. Half-lives (time to volatilize one half the substance) range from 24
days for compounds such as benzene, toluene, and naphthalene, and are projected
to be less for more volatile compounds, such as vinyl chloride and chloromethane.9,10
Figure 6.10a
295
Idealized macrophyte root structure in a wetland soil illustrating development of

an oxidized rhizophere (adapted from Kadlec and Knight, 1996).
More soluble, less volatile organics are less likely to volatilize, but then have an
opportunity for enhanced biodegradation to occur. As a result, half-lives for substances such as phenol, tetrahydrofuran, and methanol are also fairly short; these
have been measured to be in the range of 10 to 40 hours in wetlands.11
The half-lives of low molecular weight alkanes (<C8) and mono- and bicyclic
aromatics (including PCBs) have been projected to be less than 12 hours at onemeter water depth.9 Therefore, lighter weight molecules are very likely to be effectively stripped in wetlands designed to remove other constituents with equal or lower
rate constants. Experimental studies verified the strong effect of mixing in the water
phase, and established a diffusion-only half-life of about 8 hours for benzene,
toluene, TCE, and PCE.12
6.5.2
Partitioning and Storage
Many organics are known to sorb strongly to the organic sediments and substrates
in wetlands. In addition, they may be complexed with dissolved organic matter
296
Root
CH 4
N2
Organic C
O2
CH 4
Root
Aerobic
NH4+
NO3
Organic N
NH4+
NO3-
Anaerobic
Figure 6.10b
N2
Pathways of nitrogen transformations in the immediate vicinity of a wetland plant

root (adapted from Reddy and Graetz, 1988).
(DOM). For example, the partition coefficient of hexachlorobenzene (HCB) to wetland sediments has been investigated and it has been determined that the association
of dosed HCB with DOM is a fast reaction that equilibrates in one hour.9
The role of wetland vegetation in buffering air emissions from waste sites
and the role of partitioning between the plantair interface and resulting impact
cycling of contaminants have also been investigated.13 The impact of the quality
of organic matter on the magnitude of desorptionresistance has been studied.
Most studies indicate the presence of a sizeable desorptionresistant-phase in
wetland soils and an increase in the size of the desorptionresistance in older
organic matter.
Volatile substances are gasified. Many materials undergo microbial transformations. These processes all lead to the transformation and transfer of a removed
pollutant either to the atmosphere or to the wetland sediments and soils. The vegetation is extremely important for nutrient transformations and transfers because it
plays a key role in the cycling and temporary storage of many substances.
6.5.3
297
Hydraulic Retention Time
Removals proceed over the time water is held in the wetland. Therefore, detention
time (or the equivalent hydraulic loading rate) becomes the key design variable. The
longer the water is held in the wetland, the better the treatment so long as it is
not at the expense of added depth, which contributes little to the active transfers and
storages. However, wetlands possess irreducible background concentrations of some
substances: about 5 mg/L of BOD and TSS, for instance. Typical detention times
range from one to ten days for existing treatment wetlands, which corresponds to
hydraulic loading rates (rainfall equivalent) of 110 cm/day.
This technology requires land instead of mechanical devices to accomplish
treatment. If the necessary land is available, it typically offers capital savings over
competitive processes. The passive nature of wetlands technology typically offers a
very large advantage in operating costs because operation is simple and maintenance
is very low.
It has been assumed by some people that wetlands are easily conceived and built
and are low technology devices; therefore, they should be easily described in terms
of simple equations. In fact, they are exceedingly complex ecoreactors that require
complex descriptions if they are to meet designed expectations. A design model
must first do an adequate job of predicting wetland hydraulilcs. The basic tool is
the interior water budget. Stream inflows and outflows are typically measurable and
controllable in design. The wetland often will not communicate with groundwater
due to existing or constructed clay seals or liners. The uncontrollable elements of
the water budget are precipitation and evapotranspiration.
The fundamental hydraulics question for treatment wetlands is conveyance
capacity and the related issues of depths and slopes. These issues are answered by
the interior water budget, together with data on the flow resistance of the wetland.
FSF and SSF wetlands are a bit different with respect to frictional characteristics
and should be treated separately. The hydraulic sizing of the wetland is then set so
that operation will occur within the desired parameters of depth and flow.1
Other tools necessary to determine the size of the treatment wetland are the
parameters required to achieve the biogeochemical and physical processes for contaminant mass reduction. These are a description of internal flow paths, the interior
chemical mass balance, and the reaction rate constants. Detailed description of the
designed process of a treatment wetland system is out of the scope of this chapter
and book, but a few lessons from expert practitioners are described below.1,2
A pictorial description of the energy balance in a wetland system is shown in
Figure 6.11. In addition, Figure 6.12 portrays mass balance objectives; meeting this
objective is the primary function of a treatment wetland system. For the sake of
brevity, only parameters of importance for the design are listed below:1
Evapotranspiration, water losses, and gains
Area requirements, number of cells, and cell shape
Overland flow and geohydrology
298
Incoming
Sunlight
(Short Wave)
Clouds Absorb
and Reflect
Surface
Reflects
Evapotranspiration
Evaporation
Transpiration
Radiative
Heat Loss
(Long Wave)
Convective
Transfer
to/from Air
Outgoing Water
Heat Content
Incoming Water
Heat Content
Change in Storage
Conductive Transfer
to/from Ground
Figure 6.11
Components of the wetland energy balance (adapted from Kadlec and Knight,
1996).
Volumetric Flow = Qi
Concentration = Ci
Mass Inflow = Qi Ci
Surface Area = A
Volumetric Outflow = Q e
Concentration = Ce
Mass Outflow = Qe Ce
Mass Removal
Figure 6.12
Components of a chemical budget and associated terminology (adapted from

Kadlec and Knight, 1996).
Water depth, subsurface wetland hydraulics, bed friction, hydraulic conductivity

and changes with deposition, and clogging
Surface water elevation profiles, dynamic responses with precipitation, shadow
and dead zones
Nonideal flow patterns, vertical and transverse
Mixing flow velocity and residence time
Biochemical reaction rates, residence time variations based on flow paths, substrate
additions to achieve desired treatment reactions, plug flow vs. CSTR reactor models
Mass transfer mechanisms
Temperature, dissolved oxygen, and pH profiles
Suspended solids
6.6
299
Nutrients demand and cycling

Flood protection
Earth moving, dikes, berms, and levees
Plant selection and planting, which includes factors such as geographic location,
physiographic features, regional hydrology, climatic conditions, soil characteristics, water treatment objectives, type and intensity of adjacent land use impacts,
wildlife, and aesthetic preferences
TREATMENT WETLANDS FOR GROUNDWATER REMEDIATION
Utilization of wetlands for the purpose of remediating contaminated groundwaters is a relatively new concept. The evolution of ideas has been from an independent
point of view, not based upon other pre-existing aspects of the technology. Constructed wetlands in this context could be a subset of options under the general
heading of phytoremediation in the previous chapter. Several processes are envisioned as effective in pollutant reduction: phytoextraction, phytostabilization, transpiration, stripping, and rhizofiltration.
Phytoextraction refers to plant uptake of toxicants, which is known to occur and
has been studied in the stormwater and mine water treatment wetland context.
However, in many cases the contaminant is selectively bound up in below ground
tissues, roots, and rhizomes, and is not readily harvested. Phytostabilization refers
to the use of plants as a physical means of holding soils and treated matrices in
place. This process is also one of the chief underpinnings of treatment wetlands as
it relates to sediment trapping and erosion prevention in those systems. Wetland
plants possess the ability to transfer significant quantities of gases to and from their
root zone and the atmosphere (Figure 6.10). This ability is part of their adaptation
required for survival in flooded environments. Stems and leaves of wetland plants
contain airways (aerenchyma) that transport oxygen to the roots, and vent water
vapor, methane, and carbon dioxide to the atmosphere. There may also be transport
of other gaseous constituents, such as dinitrogen and nitrogen oxides, and volatile
hydrocarbons. The dominant gas outflow is water vapor, creating a transpiration flux
upward through the plant.
Rhizofiltration refers to a set of processes that occur in the root zone, resulting
in the transformation and immobilization of some contaminants. Wetlands are vertically stratified with respect to REDOX potential and other important chemical
attributes (Figure 6.9). These vertical gradients provide for interzonal processes with
both oxic and anoxic character. The microenvironments in the root zone of wetland
plants also have a great deal of structure, leading to extremely different biogeochemical conditions in zones in close proximity. Typically, oxidized conditions are found
adjacent to roots, while anaerobic conditions may exist only millimeters away. This
varied environment makes possible diffusional transfers between chemically different regions. A prime example is the precipitation of dissolved heavy metal ions as
sulfides in the anaerobic zones of wetlands.
Despite this wealth of scientific knowledge about individual contaminant removal
processes, there have been few attempts to implement wetlands for groundwater
300
remediation. Therefore, the potential of the technology must currently be assessed

from other applications. The next sections briefly address the state of knowledge in
closely related applications.
6.6.1
Metals-Laden Water Treatment
A very large application area for constructed wetlands is the treatment of acid
coal mine drainage. Hundreds of wetlands are now in operation serving this function.
The contaminants of interest are typically pH, iron, and manganese. Despite the
large number of such wetlands, there is not yet a clearly stated design methodology
available for acid mine drainage treatment.
Individual metals have been targeted at mining sites that involve them. For
example, a good deal is known about wetland treatment of copper,14 aluminum,15
and zinc. There are other reports on removal efficiencies of a number of wetlands
receiving a variety of mine effluents. Moderately high efficiencies, usually in the
6090% range are reported from full and pilot scale projects.16,17
Many treatment wetland field studies have investigated removal efficiencies for
multimetal wastewaters, mostly at low to moderate concentrations in domestic/industrial combinations and urban stormwaters.18-21 Moderately high efficiencies, usually in
the 6090% range are also reported in these studies. Laboratory and mesocosm scale
studies bear out these results under more controlled, but less realistic conditions; for
example, fast and high reductions in copper and chromium (VI) in mesocosms.11
Metals in wastewater and contaminated groundwater must be removed prior to
final discharge to protect the environment form toxic effects, but the use of wetlands
to accomplish this goal must be examined cautiously. The potential for economical
treatment is nevertheless quite attractive, and the concept of metal removal in
wetlands has undergone considerable investigation.
Metals are removed by cation exchange to wetland sediments, precipitation as
sulfides, carbonates, and other insoluble salts, and plant uptake. The anaerobic
sediments provide sulfate reduction to sulfide and facilitate chemical precipitation.
As a result, good removals of metals are reported for operating wetland facilities.
Removal of heavy metals such as Ni, Nz, Cu, Fe, Mn, Co, and other metals has
been reported at varying removal efficiencies. Under optimum operating conditions,
some of these metals have been removed at efficiencies of up to 9698%. At most
of these treatment wetland systems designed for heavy metal removal, a majority
of the mass reduction has taken place at deeper depth, indicating that anaerobic
conditions are a must for the precipitation mechanisms. Researchers have shown
that spent mushroom or other organic substrates enhance the formation of anaerobic
conditions in both SSF and FWS systems.1,2
A pretreatment system with limestone and peat mixture beds has been used at
a few treatment wetland systems for the treatment of acid mine drainage or coal
stockpile drainage waters. Limestone is used to neutralize the pH of the input
drainage water and provide for increased alkalinity and precipitations as metal
hydroxides. It has been shown that these drainage waters (with a pH of 23) enter
the actual treatment zone with a pH greater than 6.0 from the limestone pretreatment
beds (Figures 6.13 and 6.14).
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Limestone Bed
Flow Control Culvert
Peat Mixture
Open Water Pool
Open Water Pool
Open Water Pool
Water Flow Direction

Limestone Bed
Peat Mixture Treatment
Open Water Pool
Intermittent Creek
Present Extent of Wetland
Control Culvert
Berm
Figure 6.13
Typical peat/wetland treatment system, designed for heavy metal removal from
stockpile drainage (adapted from Moshiri, 1993).
Limestone
Drain
Deep
Pond
Aeration
+Alkalinity
Fe Removal
Mn Coprecipitation
TSS Removal
Figure 6.14
Deep
Marsh
Fe Removal
Shallow
Marsh
Mn Removal
Rock
Filter
Mn Removal
Alkaline Polishing
Cell
Discharge
pH Increase
Stormwater Control
Chemicals
TSS Removal
Compliance
General schematic of staged aerobic constructed wetlands.
The peat mixture beds are placed downstream of the limestone, with the flow
dispersed laterally to increase the contact area and encourage subsurface flow (SSF).
The subsurface flow through the peat mixture encourages the development of anaerobic conditions for sulfate reduction activities. In addition, the dynamics of the
physical/chemical and biological components of peat/wetland systems utilize other
metal removal mechanisms such as adsorption, cation exchange, and complexation
of soil organic matter (SOM). Some practitioners have added spent mushrooms with
peat to increase the SOM. Removal efficiencies of around 9598% have been
reported for similar systems. It is important to pay attention to the selection of the
302
right type of peat for these systems. The most important factors are high hydraulic
conductivity and available organic content.
Similar removals are obtained for other metals; for instance, chromium is reduced
by more than 70% in about 70 hours in surface flow wetlands.1,2 The area design
approach selects the wetland area required to remove a given amount of metal.
Recommended areas for iron and manganese reduction are in the range of 100500
square meters per kilogram of metal removed per day. Longer detention times
produce even greater reductions. Less is known about some elements and compounds, such as boron, arsenic, cyanide, and selenium. However, enough is known
that the correct conditions for removal may be intentionally designed into the
wetland.22
In summary, metal removal in wetlands stems from a variety of biogeochemical
processes, including aerobic and anaerobic processes in the water column, on the
surface of living and decaying plants, and in sediments. The most significant mechanisms include:
Sorption and/or exchange onto organic matter (detritus)

Filtration of solids and colloids
Formation of insoluble metal sulfides
Formation of carbonates
Association with iron and manganese oxides
Metal hydrolysis (catalyzed by bacteria under acidic conditions)
Reduction to nonsoluble, nonmobile forms (also catalyzed by bacteria)
These processes are involved to various degrees depending on specific circumstances, and it is critical to identify their relative importance in specific treatment
wetlands. Identifying and quantifying these processes provides a basis for the rational
design of treatment wetlands and informs on the stability and biological availability
of the contaminants they retain.
6.6.1.1 A Case Study for Metals Removal*
The site is a former fibers manufacturing site located in the coastal plain of
Virginia. A technical solution was needed to reduce zinc loadings to meet NPDES
or Publicly Owned Treatment Works (POTW) zinc limits for discharge from the
impacted area. After a feasibility study and pilot test, a constructed treatment wetlands was retrofitted into an impoundment area holding zinc containing sediments.
The area also receives a discharge of zinc and iron laden landfill leachate from an
adjacent industrial 36-acre landfill. A passive treatment system was preferred to a
mechanical treatment system as a cost-effective and long-term solution to rehabilitate
the impacted area and provide treatment of the water in the impounded area.
At the start of the restoration project, the wetlands contained no vegetation as a
result of the acidic water. Early efforts included pH adjustment by adding limestone
gravel and slurry to raise pH. Attempts were made to replant the area with several
* Courtesy of Joseph McKeon, BASF Corporation, Remediation Manager, Ecology and Safety
Department.
303
species to determine which would survive. Phragmites australis volunteered and

populated the entire wetlands, crowding out most of the replanted species. The
Phragmites community continues to thrive and has spread to areas with hospitable
moisture conditions, as well as repopulating areas where vegetation was removed
for construction.
The wetlands was designed as a two stage aerobic/anaerobic treatment system
to remove the iron in an oxic environment and the zinc as sulfide in an anaerobic
environment. A partitioning dike was built across the wetlands to separate the aerobic
one third of the 16.2-acre wetlands. The characteristics of the leachate coming from
the adjacent landfill approximates high strength acid mine drainage with an acidic
pH and high iron concentrations. The leachate is passively intercepted in a series of
anoxic limestone drains (ALDs), which are mitigation chambers installed below the
water table. Each ALD contains a specified volume of high calcium carbonate
limestone that dissolves upon contact with the acidic leachate, thus raising the pH
and increasing the alkalinity. At the point of ALD discharge into the wetlands, the
pH is about 7.0 and contains both iron (II) and zinc. The iron oxidizes to Iron (III)
Oxide and precipitates to the substrate of the wetlands. Some zinc coprecipitates
with the iron and some is transported in solution to the anaerobic treatment component of the wetlands. Sulfate naturally occurring in the leachate and supplementally added in the compost cell is reduced to hydrogen sulfide and forms a relatively
insoluble and nonbiologically available precipitate of zinc sulfide.
Spent mushroom compost is used to drive the wetlands anaerobic at the aerobic/anaerobic boundary and to add alkalinity and sulfate to the water. One of the
principle components of the compost is manure which serves as a carbon (food)
source for the biologically mediated reduction process. Limestone in the compost
adds alkalinity, providing additional buffering capacity to stabilize pH. Other nutrients in the compost contribute to the health of the vegetation in the wetlands. A
compost cell is also installed in the area receiving the largest amount of leachate
and zinc loadings to further condition the water before it enters the anaerobic
treatment area.
Attenuation of zinc is dependent on the reduction of sulfate to produce hydrogen
sulfide. The rhizosphere of the Phragmites provides the substrate to support the
sulfate reducing bacteria. Phragmites also transpires large volumes of water during
the warm months to control water levels in the impounded wetlands area. This
species of plant is not an important part of the food chain so uptake of metals is not
an issue for managing the passive treatment system. Phragmites does provide habitat
for insects, reptiles, and amphibians and is used by deer as a bedding area.
Zinc concentrations as high as 400 mg/l are introduced into the wetlands in the
landfill leachate and are reduced to as low as 0.3 mg/l enabling discharge to the
local POTW without further treatment. Treatment efficiency is higher in the warmer
months when biological activity is at maximum and lower during the cold months.
Water level management helps to minimize discharge during the colder months, thus
enabling more contact time with the treatment area and thus assisting zinc attenuation. The treatment system was designed with excess treatment capacity to manage
other zinc containing streams, if necessary. Various sections of the treatment wetland
system is shown in Figures 6.15a-d.
304
Figure 6.15a
Headwaters of the wetlands. (Photo courtesy of Joseph McKeon.)
Figure 6.15b
The aerobic or oxic area. (Photo courtesy of Joseph McKeon.)
Figure 6.15c
Spent mushroom compost at the beginning of the anoxic or anaerobic

area. (Photo courtesy of Joseph McKeon.)
Figure 6.15d
Vegetation in the anaerobic area. (Photo courtesy of Joseph McKeon.)
305
306
6.6.2
Removal of Toxic Organics
Organic contaminants partition strongly to solid organic substrates. Wetland

sediments are therefore excellent sinks for organics. Subsequent to such partitioning,
the organic chemical may diffuse downward, or undergo biodegradation. The wetland environment is complicated by the existence of biofilms on submerged plant
parts and litter. Although small in terms of mass per unit volume, these biofilms are
very active in biodegradation, and consequently serve as important sinks for organics.23 In this aspect, wetlands resemble conventional attached growth bio-treatment
processes. The number of toxic organics that can potentially create environmental
problems is very large. Not all of these have been studied with respect to wetland
technology. Those that have been investigated show removals due to volatilization,
storage, and biological degradation in the wetland environment.
6.6.2.1 Biodegradation
Anthropogenic organic chemical additions to wetlands for treatments are modifications to an exceedingly complex background array of hydrocarbons and organic
chemical reactions. Hydrocarbon molecules are susceptible to fragmentation and
chemical conversion in the wetland environment, predominantly via microbially
mediated pathways. Partial conversion may occur via hydrolysis, dealkylation and
ring cleavage, or the removal of amino, nitro, chlorine, hydroxyl, acid, or thio groups
from the parent molecule. Oxidative processes ultimately produce carbon dioxide
and water, while anaerobic processes will enhance reductive dechlorination and may
terminally result in the evolution of methane. It is therefore important to identify
the byproducts of degradation.
Trichloroethene (TCE) and 1,1,2,2-Tetrachloroethane (PCA), at concentration
ranges of 100 to 1000 ppb, were naturally attenuated when contaminated groundwater from an aerobic, sandy aquifer discharged through anaerobic sediments in a
freshwater wetland at a U.S. army base in Maryland.24 Microcosm experiments
confirmed field observations that Cis 1,2-DCE, and VC are the dominant daughter
products from anaerobic biodegradation of both TCE and PCA in the wetland
sediments. Cis 1,2-DCE was produced by reductive dechlorination of TCE and
dihaloelimination of PCA. VC was produced by reductive dechlorination of Cis 1,2DCE and dihalaelimination of the 1,1,2-TCA that was produced through reductive
dechlorination of PCA. Parent and daughter concentrations in the microcosms
decreased to less than 5 ppb in less than 35 days, showing extremely rapid degradation rates in these organic rich sediments.
Wetlands have all the basic elements needed for the attenuation of chlorinated
alkenes and alkanes, which include high organic carbon content in the sediments to
bind the contaminants; high microbial density and diversity in the sediments to
biodegrade contaminants; and both anaerobic and aerobic conditions to ensure that
contaminants can be fully degraded without the accumulation of potentially toxic
intermediates such as VC. Treatment wetlands can be designed and constructed
specifically to enhance the natural physical and biochemical processes to degrade
chlorinated organic compounds (Figure 6.16). Some basic steps to be taken into
307
Biofilm formation
Figure 6.16
Biofilms dominate the sedimentwater interface and the surfaces of litter and
standing dead material.
consideration on such a project include site suitability assessment, risk management,

modeling and conceptual design;,permitting, design, construction, and operation and
maintenance.
Though anaerobic environments, such as high organic carbon wetland sediments,
are often sufficiently reducing to make reductive dechlorination reactions thermodynamically favorable, the transfer of electrons from reduced species to a chlorinated
solvent is often kinetically constrained. The reduction rate may be enhanced in the
presence of compounds capable of facilitating transfer of electrons from the bulk
reductant to the chlorinated solvent of interest. Nickel and copper complexes with
Aldrich humic acid have recently been shown to be effective electron mediators for
the reductive dechlorination of TCE.25 Porewaters from the high organic carbon
sediment zone of the West Branch Canal Creek Wetland at Aberdeen Proving
Grounds, Maryland, were used. Using titanium (III) citrate as the bulk reductant,
Ni and Cu complexes (of DOC) present at the site sediments rapidly reduced TCE.
The reaction was pseudo-first order with a half-life of approximately one hour for
both DOC-metal complexes. Reaction rates were comparable to the Aldrich humic
acid-transition metal systems. Dechlorination was complete with the dominant products being ethene and ethane, the mass balance was near 100%, and chlorinated
intermediates were either absent or at extremely low concentrations.
The partitioning of compounds from the aqueous phase into biota is not the only
significant process that occurs after the initial discharge of xenobiotics into wetland
systems. Partitioning of xenobiotics from the aqueous phase into the sediment phase
may be of equal significance, attested to by the structural range of organic compounds
(PAHs, PCBs, PCDDs, Chloro Phenols, etc.) recovered from contaminated sediments.
It is well established that many heavy molecular weight and high Kd compounds
after introduction into the wetlands environment are not readily accessible to chemical recovery. This does not necessarily imply, however, that they are of no environmental significance: the degree to which they are desorbed and therefore become
accessible to biota is a central issue that has implicaitons both for toxicity of
308
xenobiotics and for their resistance to microbial attack. Results that indicate decreasing recoverability and irreversible sorption from the sediment phase with increasing
time from deposition may be accommodated under the general description of aging.26
Details of the mechanisms by which xenobiotics are bound to components of the
sediment phase have not been fully established, although several plausible hypotheses have been put forward. Proposed mechanisms of interaction include ionic and
covalent binding, long range (Van der Waals) forces, or sorption by undefined
mechanisms. A recent study27 indicated 3062% of chlorobenzene and 4783% of
phenathrene of the adsorbed mass residing in the desorption-resistant fraction.
In another recent study partitioning of hexachlorobenzene (HCB), lower chlorinated benzenes, and hexachlorbutadiene (HCBD) between the plantair interface
was measured in field and laboratory studies using bark, leaf, and leaf litter of bald
cypress (Taxodium distichum) and black willow (Salix nigra).28 A first order kinetic
model was applied to the experimental results to determine a plantair partition
coefficient (KPA). The role of wetland vegetation in buffering air emissions from
waste sites was established.
With high microbial populations compared to terrestial environments, wetland
soils are highly effective at consuming and processing labile, complex organics. The
supply of low molecular weight organic substrates from decomposition of organic
matter for dechlorination in organic rich wetland sediments is important to understanding the potential of using sediment microorganisms for natural degradation of
chlorinated organic compounds. A recent study29 indicated that 2,3,5,6-Tetrachloro
Phenol can be dechlorinated in wetland sediments and that 2,4,5-Trichloro Phenol,
and 2,5-and 3,4-dichlorophenols are major intermediates before the eventual dechlorination to 3-chlorophenol is achieved.
In another study30 intrinsic biodegradation of PAHs was evaluated using two
microbiological analyses: heterotrophic bacterial production using 3H-Leucine incorporation to estimate the growth rate of the entire community and PAH mineralization
rates using degradation of 14C-naphthalene, phenanthrene, and fluoranthene to 14CO2.
Bacterial growth was generally reduced at locations that had PAH concentrations
above 100 ppm. However, PAH mineralization rates were significant across the site
and PAH mineralization accounted for up to 15% of the heterotrophic bacterial
growth substrate demand.
Additional investigations revealed that complete mineralization of hexachlorobenzene (HCB) is possible in heavily anaerobic, methanogenic wetland sediment
environments.31 HCB was reductively dechlorinated to isomes of dichlorobenzene
(DCB) and monochlorobenzene. After further reductive dechlorination of DCB, all
the monochlorobenzene was degraded to CO2 under methangenic conditions. This
study also found that uncomplexed Cd and Pb in the sediment porewater was
inhibitory to the reductive dechlorination reactions.
Research focused on the transformations of alachlor and atrazine (members of
the chloroacetamide and chloro-s-triazine herbicide classes, respectively)32 revealed
that degradation is promoted by naturally occurring inorganic sulfur nucleophiles in
anoxic salt marsh porewaters. Bisulfide (HS) and polysulfides (Sn2 ) have been
reported in salt marsh porewaters as high as 5.5 mm and 0.43 mm, respectively. The
rates of sulfhydrolysis in these environments may greatly exceed rates of other
309
removal processes (biotic or aerobiotic) for the above compounds and may represent
an important sink for these herbicides in salt marsh environments.
Studies have examined the relationship between irreversible sorption (aging)
and bioavailability in the vegetated wetland environment using plant uptake as an
endpoint. In a recent study using black willow (Salix nigra), and Scirpus olney, it
was found that plant uptake of about 46% of the phenanthrene was observed in
sediment with phenanthrene in a fully desorption resistant state.33 Both plants
appeared to access the desorption resistant phase to some extent. Two mechanisms
appear to be important: the direct uptake of the porewater in equilibrium with the
desorption resistant phase, and the sorption of the organic onto the root followed
by uptake.
Other studies have reported that phenolic compounds at high concentrations can
be remediated in treatment wetlands using plants such as Schoenoplectus and Phragmites. Trinitrotoluene (TNT), cyclotrimethaylenetrinitramine (RDX), and cyclotetramethylenetetranitramine (HMX) at concentrations of 4, 4, and 0.10 ppm, respectively, were treated in a treatment wetland planted with canary grass, woolgrass,
sweet flag, parrot feather, sago pond weed, water stargrass, and elodea. The treatment
efficiencies were greater than 95%.34
6.6.3
Removal of Inorganics
Reduction of phosphorus and nitrogen compounds requires the longest detention

of any pollutants. Approximately 90% of the incoming inorganic load can be eliminated by 14 days detention in a surface flow wetland.1 These substances are required,
at low loading rates, to sustain a healthy wetland. Nitrogen removal may require
active or passive reaeration to promote nitrification; denitrification requires a carbon
source to fuel the denitrifer population.
In a recent study using native wetland plants such as bulrushes (Scirus spp.),
cattails (Typha spp.), and sedges (Carex spp.), an influent water containing 62 mg/L
of NO3 was treated to consistently nondetectable levels of effluent quality.7 This
test is continuing to see whether perchlorate also can be treated by the same system.
It is not possible to forecast the types of substances that will be contained in
leachates over the entire history or anticipated discharge. Treatment wetlands have
capabilities for removing a wide variety of substances, and hence operate as broad
spectrum treatment technology. They have the further property of pulse averaging
because of long detention times. A brief spike of a given substance will, at a
minimum, be diluted by the relatively large volume of water in the wetland. Averaging is approximately over the detention time of the wetland.
6.6.4
Wetland Morphology, Hydrology, and Landscape Position
Wetlands are often constructed to remove pollutants from ground or surface

waters. The intention is that constructed wetlands will degrade or sequester pollutants
so they do not pose a risk to humans and wildlife downstream of pollutant sources.
Pollutants retained in constructed wetlands may be converted to less toxic forms or
sequestered in the sediments or biota of wetlands. Ultimately, pollutants may be
310
removed from wetlands by harvesting soils and biota and transferring them to longterm storage sites such as landfills.
While wetlands may remove pollutants from ground and surface waters, pollutants may leave wetlands through aquatic-terrestrial food chain links. Many birds
and mammals feed on larger aquatic invertebrates and vertebrates that may accumulate significant amounts of pollutants. Thus, factors that promote the accumulation
of pollutants in larger aquatic organisms can lead to risks to wildlife and, ultimately,
human health. By managing the factors that promote accumulation of pollutants in
organisms inhabiting constructed wetlands, a manager can reduce the ecological risk
these prey items represent to terrestrial organisms.
The relationships among wetland landscape position, hydrology, morphology,
and toxic accumulation in fish in natural depression wetlands can be manipulated
in constructed wetlands to reduce risk to wildlife from accumulated pollutants. The
distribution of wetlands in the landscape and the amount of time they hold water
during the annual hydrological cycle determines the amount of time fish will be
present; wetlands close to other aquatic habitats and holding water for much of the
year are more likely to have fish populations. Fish in wetlands with shallow maximum depth and greater water level fluctuations accumulate significantly more toxins.
These relationships suggest: 1) constructed wetlands should be located in the landscape such that the chance of colonization by fish is minimized; 2) when possible,
stable water levels should be maintained in constructed wetlands; and 3) wetlands
should be constructed with steep sides and flat bottoms.
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18. Crites, R. W., R. C. Watson, and C. R. Williams, Removal of metals in constructed
wetlands, conference preprint, Water Environ., 68th Ann. Conf., Miami, FL, 1995.
19. Delgado, M., M. Biggeriego and E. Guardiola, Uptake of Zn, Cr, and Cd by Water
Hyacinths, Water Res., 27, No. 2, 269272, 1993.
20. Strecker, E. W., R. R. Horner, and T. E. Davenport, The Use of Wetlands for Controlling Stormwater Pollution, The Terrene Institute, Washington, D.C., 1992, 66.
21. Zhang, T., J. B. Ellis, D. M. Revitt, and R. B. E. Shutes, Metal uptake and associated
pollution control by Typha latifolia in urban wetlands, in Constructed Wetlands in
Water Pollution Control, P. F. Cooper and B. C. Findlater, Eds., Pergamon Press,
Oxford, UK, 1990, 451-459.
22. Masscheleyn, P. H., R. D. Delaune, and W. H. Patrick, Jr., Arsenic and selenium
chemistry as affected by sediment redox potential and pH, J. Environ. Qual., 20,
522527, 1991.
23. Alvord, H. H. and R. H. Kadlec, The interaction of atrazine with wetland sorbents,
Ecol. Eng., 5, No. 4, 469479, 1995.
24. Lorah, M.M. and L. D. Olsen, Natural attenuation of chlorinated volatile organic
compounds in a freshwater tidal wetland, Wetlands Remed.: Int. Conf., Salt Lake
City, November, 1999.
25. Burris, D. R. and E. J. OLoughlin, Reductive dehalogenation of trichloroethene
mediated by wetland DOC-transition metal complexes, Wetlands Remed.: Int. Conf.,
Salt Lake City, November, 1999.
26. Neilson, A. H., Organic Chemicals: An Environmental Perspective, CRC/Lewis Publishers, Boca Raton, Florida, 1999.
27. Pardue, J. H. and W. S. Shin, Desorption resistance of organic compounds in wetland
sould, Wetlands Remed.: Int. Conf., Salt Lake City, November, 1999.
28. Leppich, J., J. H. Pardue, and W. A. Jackson, Plant Air partitioning of chlorobenzenes in wetland vegetation at a superfund site, Wetlands Remed.: Int. Conf., Salt
Lake City, November, 1999.
29. Chiang, S. V. and F. M. Saunders, Intrinsic microbial dechlorination of 2,3,4,6tetrachloro phenol in anaerobic wetland sediment slurry, Wetlands Remed.: Int. Conf.,
Salt Lake City, November, 1999.
312
30. Montgomery, M. T. et al., Measuring intrinsic bacterial degradation of PAHs in a salt

marsh, Wetlands Remed.: Int. Conf., Salt Lake City, November, 1999.
31. Jackson, W. A. and J. H. Pardue, Natural attenuation case study for chlorogenzenes
in a forrested wetland, Wetlands Remed.: Int. Conf., Salt Lake City, November, 1999.
32. Roberts, A. L. and K. A. Lippa, Reactions of herbicides with reduced sulfur species
in salt marshes, Wetlands Remed.: Int. Conf., Salt Lake City, November, 1999.
33. Gomez-Hermosillo, C., Bioavailability of desorption resistant phenanthrene to wetland plants, Wetlands Remed.: Int. Conf., Salt Lake City, November, 1999.
34. L. L. Behrends et al., Phytoremediation of explosives contaminated groundwater
using constructed wetlands, Wetlands Remed.: Int. Conf., Salt Lake City, November,
1999.
CHAPTER
Engineered Vegetative Landfill Covers

CONTENTS
7.1
7.2
7.3
7.4
7.5
7.6
Historical Perspective on Landfill Practices................................................314

The Role of Caps in the Containment of Wastes........................................315
Conventional Landfill Covers ......................................................................316
Landfill Dynamics........................................................................................317
Alternative Landfill Cover Technology .......................................................321
Phyto-Cover Technology..............................................................................321
7.6.1 Benefits of Phyto-Covers over Traditional RCRA Caps.................326
7.6.2 Enhancing In Situ Biodegradation...................................................326
7.6.3 Gas Permeability ......................................................................327
7.6.4 Ecological and Aesthetic Advantages .........................................327
7.6.5 Maintenance, Economic, and Public Safety Advantages ..............329
7.7 Phyto-Cover Design .....................................................................................329
7.7.1 Vegetative Cover Soils .....................................................................330
7.7.2 Nonsoil Amendment ........................................................................331
7.7.3 Plants and Trees ...............................................................................331
7.8 Cover System Performance..........................................................................332
7.8.1 Hydrologic Water Balance ...............................................................332
7.8.2 Precipitation .....................................................................................335
7.8.3 Runoff...............................................................................................335
7.8.4 Potential Evapotranspiration Measured Data .............................337
7.8.5 Potential Evapotranspiration Empirical Data .............................339
7.8.6 Effective Evapotranspiration ......................................................340
7.8.7 Water Balance Model ................................................................343
7.9 Example Application....................................................................................344
7.10 Summary of Phyto-Cover Water Balance....................................................347
7.11 General Phyto-Cover Maintenance Activities .............................................348
7.11.1 Site Inspections ................................................................................348
7.11.2 Soil Moisture Monitoring ................................................................349
313
314
7.11.2.1 Drainage Measurement.....................................................350

7.11.3 General Irrigation Guidelines ..........................................................352
7.11.4 Tree Evaluation ................................................................................356
7.11.4.1 Stem ..................................................................................356
7.11.4.2 Leaves ...............................................................................357
7.11.5 Agronomic Chemistry Sampling .....................................................358
7.11.6 Safety and Preventative Maintenance..............................................359
7.11.7 Repairs and Maintenance.................................................................359
7.12 Operation and Maintenance (O&M) Schedule............................................359
7.12.1 Year 1 Establishment ..................................................................360
7.12.2 Years 2 and 3 Active Maintenance.............................................360
7.12.3 Year 4 Passive Maintenance .......................................................361
7.13 Specific Operational Issues..........................................................................362
7.13.1 Irrigation System Requirements ......................................................362
7.13.2 Tree Replacement.............................................................................362
References..............................................................................................................362
Maintaining and enhancing the closed landfill as a bioreactor requires modification of design and operational criteria normally associated with traditional
landfill closure
7.1
HISTORICAL PERSPECTIVE ON LANDFILL PRACTICES
The practice of using shallow earth excavations, or landfills, for disposal of liquid
and solid waste has a very long history. Landfill practices basically followed the
design philosophy of out of sight, out of mind in that a pit or trench was excavated
into the ground, waste was placed into the excavation, and, when it was full, the
excavation was covered with soil and abandoned. If thought was ever given to the
matter, it was likely assumed that the soil surrounding the waste effectively prevented
contaminant migration from the burial zone.
It was not until 1976, with the passage of the Resource Conservation and
Recovery Act (RCRA), and 1980, with the passage of Comprehensive Environmental
Response, Compensation, and Liability Act (CERCLA) that federal and state regulations mandated much improved methods for disposal of waste in landfills. Today
there are a plethora of federal and state regulations controlling all aspects of landfill
disposal of municipal, radioactive, and hazardous waste. The problem in the U.S.,
however, is that hundreds of thousands of landfills were operated and then decommissioned prior to the requirements of current regulations. Many of these old landfills
now come under the closure requirements of RCRA or CERCLA, depending on the
agreements between the responsible parties. In 1989, U.S. Environmental Protection
Agency (USEPA) stated that there are 226,000 sanitary landfills in the U.S. requiring
evaluation for potential risks to human and environmental receptors.1
Regardless of the corrective action imposed on these old sites, almost all of them
will require installation of a new cover as a final step in the closure process. The
ENGINEERED VEGETATIVE LANDFILL COVERS
315
design of most landfill covers in the U.S. has been based on criteria developed by
EPA for use in closing either RCRA subtitle C (hazardous waste) or subtitle D
(municipal solid waste) landfills. Two major themes emerge in reviewing recent
work in landfill cover design:2 1) there has been an overemphasis on regulatory
compliance, thus inhibiting innovative and creative design that looks at the entire
landfill system as a holistic biogeochemical environment, and 2) there are few
published data on field performance of constructed cover systems and their impacts
on the biogeochemistry of the groundwater within the footprint of the landfill.
7.2
THE ROLE OF CAPS IN THE CONTAINMENT OF WASTES
Because of the expense and risk associated with treating or removing large
volumes of landfill wastes, remediation usually relies upon containment, which
requires the construction of a suitable cover. Both regulators and the public usually
accept covers as part of the presumptive remedy for final landfill remediation;
therefore, covers are likely to be included in the optimal remedial actions for closure
of most landfills.
The intent of landfill remediation is to protect the public health and the environment. In keeping with this intent, a modern philosophy has evolved requiring contaminants in the waste to be isolated from receptors and contained within the landfill.
As a result, landfills have become warehouses in which wastes are stored for an
indefinite time, possibly centuries.
There are fundamental scientific and technical reasons for placing a cover on
landfill sites. Although regulations are often the most apparent influence governing
the selection and design of landfill covers today, these regulations were drafted
because of specific environmental concerns and were based upon scientific and
technical understandings. The three primary requirements for landfill covers are to:
Minimize infiltration: water that percolates through the waste may dissolve
contaminants and form leachate, which can pollute both soil and groundwater as
it travels from the site.
Isolate wastes: a cover over the wastes prevents direct contact with potential
receptors at the surface and prevents movement by wind or water.
Control landfill gas: landfills may produce explosive or toxic gases, which, if
allowed to accumulate or to escape without control, can be hazardous.
Landfills have been covered by barriers for years, usually built with little regard
for the monetary and environmental costs associated with constructing and maintaining them. A typical landfill cover design consists of a sequence of layered
materials to control landfill gas infiltration and promote internal lateral drainage.
The uppermost layer of a landfill cover consists of a vegetative soil layer to prevent
erosion, promote runoff, and insulate deeper layers from temperature changes. The
landfill cover is not a single element but a series of components functioning
together.3
316
Landfill covers are designed to minimize infiltration of rainfall and melting snow
into the landfill in order to minimize postclosure leachate production. This objective
is achieved by converting rainfall into surface runoff and infiltration into evapotranspiration and lateral drainage without compromising cover integrity. Secondary performance objectives of landfill cover design include the following:3 minimize postclosure maintenance; return the site to beneficial use as soon as possible; make the
site aesthetically acceptable to adjacent property owners; accommodate post-closure
settlement of the waste; address gas and vapor issues; provide stability against
slumping, cracking, and slope failure; provide resistance to disruption by animals
and plants; and comply with landfill closure regulations.
The design features of a landfill cover are varied to affect changes in the overall
water balance within the landfill to meet primary landfill cover objectives. The design
adopted must take into account numerous other considerations, including costs, long
term maintenance implications, and construction risks. The relatively large areas
that landfill covers protect, and the thickness and number of individual layers within
them, make covers a cost-intensive component of landfill facility design.
7.3
CONVENTIONAL LANDFILL COVERS
Nearly all conventional landfill covers in current use incorporate a barrier within
the cover. The impermeable barrier layer is intended to prevent water from moving
downward in response to the force of gravity. In effect, these covers are designed
to oppose the forces of nature. Barrier-type covers commonly include five layers
above the waste (Figure 7.1).1 The top layer consists of cover soil typically two feet
thick and supports a grass cover that provides erosion control. The barrier layer
consists of either a single low-permeability barrier or two or more barriers in
combination. The fourth layer is designed to remove landfill gases as they accumulate
underneath the barrier layer. The bottom layer is a foundation layer of variable
thickness and material; its purpose is to separate the waste from the cover and to
establish sufficient gradient to promote rapid and complete surface drainage from
the finished cover.
The barrier layer is the defining characteristic of conventional landfill covers. It
may be composed of compacted clay, a geomembrane, a clay blanket, or two or
more layers of materials in combination. A compacted clay layer is frequently
specified to have a maximum saturated hydraulic conductivity (K) 1 107 cm/sec.
In contrast, both the drainage and gas collection layers are constructed to enhance
flow and commonly contain washed and selectively sieved sand, gravel, or specially
designed synthetic materials.
The soil in the top layer of barrier-type covers is usually too thin or has inadequate
water holding capacity to store infiltrating precipitation during a large storm. These
covers rely on barrier layers and rapid drainage through lateral drainage layers to
prevent precipitation from reaching the waste. Barrier-type covers must accommodate specific site conditions, and supplemental components are sometimes added.
For example, gravel may be added to the surface soil in desert regions to control
317
Vegetation
Topsoil
0'-6"
Vegetative Layer
Common Borrow Material
1'-18"
Protective
Cover Layer
Geocomposite
(Textile-Net-Textile)
40-mil LLDPE
2'-30"
(min.)
Foundation Layer
Waste
Figure 7.1
Typical single barrier cover system.
wind erosion, or a layer of cobbles may be used with the cover to discourage animal
burrowing into the waste.
7.4
LANDFILL DYNAMICS
Landfills that contain a large amount of organic, putrescible materials (such as

municipal solid waste) literally function as bioreactors. Most landfill bioreacters in
general contain anaerobic and/or facultative microorganisms. Landfill leachate is generated as a result of the percolation of water or other liquids through the waste and
also due to the accumulation of moisture generated as a result of microbial degradation
of waste. Leachate is a concentrated fluid containing a number of dissolved and
suspended materials, specifically, high concentrations of organic compounds (organic
acids, hydrocarbons, etc.) and certain inorganic compounds (ammonia, sulfates, dissolved metals, etc. characteristic of the parent waste materials) from which it is derived.
In addition, natural microbial activity in landfills also results in the generation of gases
such as methane, carbon dioxide, ammonia, and hydrogen sulfide, a fraction of which
will be dissolved in the leachate and may be introduced into the groundwater.
Numerous landfill investigation studies4 have suggested that the stabilization of
waste proceeds in sequential and distinct phases. The rate and characteristics of
leachate produced and biogas generated from a landfill vary from one phase to
another and reflect the processes taking place inside the landfill. These changes are
depicted in Figure 7.2.
318
Figure 7.2
Description of leachate and gas concentration changes during landfill lifecycle.
The initial phase is associated with initial placement of waste and accumulation
of moisture within landfills. Favorable biochemical conditions are created for the
decomposition of waste. During the next phase, transformation from an aerobic to
anaerobic environment occurs, as evidenced by the depletion of oxygen trapped
within and introduced to landfill media and continuous consumption of nitrates and
sulfates. Subsequent phases involve the formation of organic acids and methane gas.
During maturation phase, the final state of landfill stabilization, available organic
carbon and nutrients become limiting, and microbial activity shifts to very low levels
of activity. Gas production dramatically drops and leachate strength remains constant
at much lower concentrations than in earlier phases.
Biochemical decomposition of putrescible solid waste is shown below by an
example (Equation 7.1). Typical landfill gas composition during peak activity as a
bioreactor is: 60% methane, 40% carbon dioxide, 510% other gases, and 0.31.0%
VOCs and non-monitored organic compounds. Gas generation rates during peak
activity typically fall within the ranges of 515 ft3 per pound of refuse per year.9
C 6 H10 O 5 H 2 O
Anaerobic
3CH 4 + 3CO 2
Bacteria
(7.1)
Due to very high gas pressures generated at the source areas within the landfill
(up to 4 atmospheres), migration of dissolved contaminants into the gaseous phase
could be a serious concern. Contaminants transferred into the gas phase could be
readsorbed in the waste above the water table, or dissolve in the moisture, condense
in the waste zone, or migrate away from the landfill. The potential for contaminant
migration from the dissolved phase into the landfill gas can be evaluated as shown
in Equation 7.2, and Figure 7.3.
Figure 7.3
319
Equilibrium mass transfer conditions of contaminants into landfill gas.
Under non-equilibrium conditions:
dm
= K C g HC w A
dt
(7.2)
where
dm
dt
K
H
Cg
Cw
A
= transfer rate from gas to water

=
=
=
=
=
phase transfer coefficient

Henrys Law Constant of VOC
gas phase concentration of VOC
water phase concentration of VOC
gas/liquid contact area
The progress toward final stabilization of any landfill and the organic waste in
it is subject to physical, chemical, and biological factors within the landfill environment, age and characteristics of the waste, operation and management controls
applied, as well as site-specific external conditions.
Although barrier layers are sometimes referred to as impermeable layers, in
practice this is seldom true. An extensive review of failures and failure mechanisms
for compacted soil covers in landfills was performed and emphasized that natural
physical and biological processes can be expected to cause [clay] barriers to fail in
the long term.5 Another study discussed a field test conducted in Germany in which,
320
Precipitation
Runoff
0.15 m
Topsoil
0.47 m
Soil Barrier
K 1 x 10-5 cm/sec
Foundation Gravel
Waste
Figure 7.4
Subtitle D cover for municipal solid waste landfills.
seven years after construction, percolation through the compacted clay was almost
200 mm/yr and increasing. Geomembrane barriers are also prone to leak.6 Others
have traced most leaks in geomembranes to holes left by construction.7,8
A modification of the typical barrier cover is the subtitle D cover (Figure 7.4)
that relies on compaction to create a layer of soil with reduced K value. Used
primarily for municipal landfills in dry regions, its use and components are specified
in subtitle D of RCRA (40 CFR, Part 258.60), hence the name. From the surface
downward, the cover includes an erosion control layer and a layer of compacted
soil. A major advantage of the subtitle D cover is that its construction cost is lower
than for an RCRA subtitle C cover. Even though it has gained regulatory and public
acceptance, the subtitle D cover cannot ensure long-term protections against infiltration of water into the waste, even in dry regions, because 1) the topsoil layer has
limited water holding capacity, 2) there is no drainage layer, 3) few roots can grow
in the barrier layer to remove water, and 4) soil freezing and root activity are likely
to increase the K value of the barrier soil layer over time.
7.5
321
ALTERNATIVE LANDFILL COVER TECHNOLOGY
Alternative covers to the RCRA subtitle C or D design include evapotranspiration

(ET) covers and capillary barriers. The ET cover uses no barrier or horizontal
drainage layers; it is designed to work with the forces of nature rather than attempting
to control them. An ET cover in its simplest form is a vegetated soil cover with a
sufficiently deep soil profile so that infiltrated water is stored until removal by
evaporative losses from the soil surface and by plant roots at depth in the profile. A
capillary barrier also relies on water removal by ET, but is designed such that water
storage near the surface is enhanced to promote the efficient removal of infiltrated
water by the ET process. Optimization of material types and thicknesses for capillary
barriers is critical to their effective performance. The use of sands or clays as the
fine-soil component in the capillary barrier has proven to be less effective in storing
water than silt loams. Capillary barriers can be thought of as enhanced ET covers
alternative cover systems that work best in semi- and/or arid environments where
high ET rates and low precipitation make it possible to remove all infiltrated water
by ET. However, even in arid environments there are situations where ET covers
and capillary barriers can allow excessive percolation, particularly where the soil
used in the cover design has insufficient storage capacity to accommodate winter
snow melt events.
7.6
PHYTO-COVER TECHNOLOGY
The phyto-cover is the most popular application of the ET cover and is an

engineered agronomic system that harnesses the natural transpiration process of
plants to limit percolation to the groundwater. A phyto-cover relies on shallow- and
deep-rooted plants to create a thick root zone from which the plants can extract
available moisture. In effect, the plants serve as natural, solar-powered pumps to
withdraw soil moisture and either convert it into biomass or evaporate it through
their leaves. The withdrawal rate of the botanical pumps is limited by the available
energy (sunlight), rate of growth, and available soil moisture; withdrawal virtually
ceases during winter dormancy. Accordingly, the depth and composition of the root
zone must be sufficient to store accumulated water like a sponge and hold it until
the plants remove it. Properly designed, this sponge and pump water removal
system (Figure 7.5) can limit water from percolating below the root zone and can
be equally protective of groundwater as a RCRA cap. Thus, a phyto-cover serves
as a functional alternative to natural clay, geocomposite, or geosynthetic membrane
cap, yet offers several advantages over those technologies.
The effectiveness of poplars in maintaining low soil moisture levels was first
documented by data collected from a phyto-cover application in Iowa.10 The phytocover consistently maintained soil moisture levels substantially below the soils field
capacity (i.e., the amount of water that soil can retain without allowing percolation)
of 4045%. Soil dryness was maintained by the trees prodigious water extracting
ability. The capacity of certain trees such as hybrid poplar and willow trees to extract
soil moisture has been demonstrated by monitoring data from landfill at many sites.
322
Precipitation
Poplars
Evapo-transpiration
Evaporation
Infiltration
Surface Runoff
10'-0"
Root
Depth
Topsoil Storage
Native Soil Storage
Daily Cover
Waste
Figure 7.5
Conceptual phyto-cover diagram.
The poplars are employed at this site not as a cover, but to treat collected landfill
leachate, which is applied to the poplars during the growing season. The total amount
of water extracted from the soil in one growing season by these two- and three-yearold poplars was equivalent to about 62 inches of precipitation.10
One of the most important design considerations for a phyto-cover is choosing
appropriate tree species and varieties. Selected trees must be capable of achieving the
desired treatment objective and adapt to the irrigation water, soils, and climate of the
site. Typically, achieving the highest possible rate of evapotranspiration is an important
goal. Critical site conditions for plant selection include soil chemistry, irrigation water
or groundwater chemistry, and adaptation to pests and diseases of the area. Any factor
that compromises tree health and growth will reduce performance. For example, hybrid
poplar clones that include either trichocarpa or maximowiczii parents are quite susceptible to Septoria canker if used in the U.S. midwest.10
Especially for the commonly used Salicaceae, a number of different types of
plant materials may be used. These include stem cuttings, whips or poles, and bare
root or potted material. Use of larger or rooted plant material will result in more
rapid establishment and reduced weed competition, but plant material and planting
costs are much higher than for smaller material. Whips and poles are commonly
used for deep planting applications. Economics, especially planting costs, drive most
larger installations (>5 ha) toward short stem cuttings.
Certain varieties may result in a more valuable final wood product because of
straighter stems or better paper processing properties. Significant differences in
damage from voles has been observed among hybrid poplar trees at phytoremediation
sites. Salt tolerance is a very important selection criterion, as differences between
species and varieties can be significant. Only limited data for Salicaceae are currently
available to guide design, but a number of relevant research programs are ongoing.
For an increasing number of sites, use of non-native species is unacceptable for
local community groups and sometimes for regulators. Use of native material will
generally ensure resistance to local pests and disease, but may not afford the greatest
efficiency.
323
Once the tree system forms a complete canopy, spacing has little effect on
evapotranspiration or nutrient requirements. The impact of spacing on hydraulic and
nutrient loading is primarily an early establishment phase concern. Establishing
dense initial plantings with the intention of thinning may provide small increases in
early capacity, but thinning operations are often neglected and the resulting mature
tree stands are excessively dense. Enough space must be left between tree rows to
allow planned maintenance activities such as mowing or spraying.
The engineered phyto-cover system consists of densely planted, deep-rooted
trees and understory vegetation (perennial rye grass and clover). Photographs of
hybrid poplar tree stands of varying ages are shown in Figure 7.6. The water-holding
root zone (sponge) includes the existing topsoil and fill at the site (including
intermediate and daily cover soil) supplemented with additional soil or soil amendments as dictated by design calculations. A phyto-cover will provide a protective,
living skin for a landfill that permanently heals the wound to the landscape
originally created by anthropogenic activities. This skin can equal the percolationblocking performance of a rain coat RCRA cap while being substantially more
cost effective and providing additional benefits. The final design of a phyto-cover
often includes provisions for monitoring soil moisture levels to ensure that performance criteria are met.
Two-year Old Stand of Poplars
Four-year Old Poplar Trees
Figure 7.6
Phyto-covers: comparison of two-year-old and four-year-old growth of a phytocover (courtesy of Licht, 1998).
Engineered phyto-cover systems have been applied to contain spilled petrochemicals and cover landfills, as well as buffers to remove nitrogen from industrial and
municipal wastewater. Sites where phyto-covers have been installed and recent
research and demonstration sites for phyto-cover systems include the following:2,10-13
A 15-acre construction debris landfill in Beaverton, OR was covered with trees
in 1990 as an alternative to excavation of the fill, the installation of a liner, and
then recovering with a geomembrane. The phyto-cover is serving to protect
groundwater cost-effectively. The owner has continued to expand the cover as new
areas are closed.
324
From 1992 to 1993, the Riverbend Landfill in McMinneville, OR planted a 17acre phyto-cover to manage landfill leachate water and soluble compounds. All
nutrient and water cycling results indicate the cap is achieving all regulatory
requirements for ammonia treatment and ground protection.
From 1993 to 1995, a 15-acre perimeter buffer was planted to reduce infiltration
from upgradient runoff, grow a visual and sound barrier, and intercept downgradient leachate seepage. Data collected at the site indicate the cap has been successful in stopping all leachate.
At the Grundy county Landfill in Grundy Center, IA, a two-acre cap and perimeter
buffer was planted from 1993 to 1994 to reduce leachate formation by installing
a phyto-cap over a completed subtitle D cap. The cap also provides a visual and
sound barrier, and intercepts downgradient leachate drainage.
A three-acre poplar cap was planted in 1994 at the Bluestem 1 Landfill in Cedar
Rapids, IA over a pre-subtitle D cap. The cap serves to reduce leachate formation
vertically and intercepts downgradient leachate drainage. The data collected at
this site have been used in writing specifications for soil and compost cover
requirements and use of MSW waste as a planting media.
A five-acre cap and perimeter boundary were planted in 1994 over a pre-subtitle
D cap at the Bluestem 2 Landfill in Marion, IA to reduce leachate formation.
Moisture management data from this cap have been used in subtitle D equivalence
comparison between a soil/clay cover and the sponge and pump concept for
deep rooted trees in four feet of rootable soil.
In 1995, a ten-acre area was planted with poplar trees and a clover/grass understory
over a subtitle D cell filled with MSW and industrial waste. The Department of
Environment Quality and governors office were interested in future phytoclosures
for many funded pre-RCRA landfills in Virginia that have been abandoned and
are creating potential environmental risk. The trees are growing well and are being
maintained by the owner. A soil moisture measurement system using time domain
reflectometry (TDR) is used to monitor the impact of tree roots on vadose zone
water content. A drip irrigation system using collected storm water can control
the water stress during periods when moisture in the root zone has been exhausted.
At a railroad RCRA site in Oneida, TN, a one-acre area impacted by coal and
creosote from past manufacturing activities was covered with poplar trees and
grass in 1997. The site soils were amended with compost and mineral fertilizer,
then trenched in the root zone. The trees and grass managed to accelerate biomass
growth with resulting water uptake and in situ constituent removal. The site
groundwater is monitored by a university research grant to measure groundwater
elevation and the containment of constituents. The concept is similar to landfill
capping where the phytosystem pumps water at high rates during the growing
season and minimizes groundwater movement during the dormant season.
The Woodburn WasteWater Treatment Plant in Woodburn, OR has been a demonstration site since 1995; a full-scale installation took place in 1998. This site is
the first full-scale tertiary treatment of secondary municipal wastewater effluent
and is being designed for no leakage through the root zone in the summer months.
The Mid-Lakes Co-op site in Bonduel, WI used an aesthetically pleasing poplar
cover over a spill plume to contain pollutant migration, make use of all available
precipitation, protect public exposure, and remove constituents from the groundwater . Closure requirements for this site included planting trees, monitoring the
depth to groundwater, and monitoring groundwater quality over a three-yearperiod.
325
In Staten Island, NY a phyto-cover consisting of poplars, willows, paulowia, and

grasses is being used to prevent constituent migration and formation of leachate.
Enhancement of existing vegetation is expected to establish hydraulic control of
groundwater by reducing water infiltration through the landfill materials.
Evidence collected at a closed landfill in Elmore, OH indicates naturally occurring
trees have created a treatment barrier for leachate seeps. An evaluation of on-site
box elder and osage orange trees yielded evidence of TCE uptake. An evaluation
of the existing cover for supplemental enhancement for additional groundwater
remediation and restoration was then conducted.
A poplar tree phyto-cover was installed in 1996 at a landfill in Acme, NC. The
trees were planted in the most downgradient area of the landfill to stop leachate
migration. Groundwater constituent concentrations have dropped substantially in
the area of the poplar trees but not in areas where trees were not planted.
From 1992 to 1993, over 2000 poplar trees were planted at a site in Anderson,
SC to be used for processing waste from mining ore material. The waste was used
to fill low areas over six acres of the site. Data collected at the site indicate
infilitration and leachate formation is being controlled.
In 1991, a succession of trees (willow and black locust), legumes, and grasses
were planted to dewater slurry waste at a site in Baton Rouge, LA. The waste
material was in a slurry state from a depth of 6 inches to 30 feet below ground
surface. The planted vegetation reduced the hydrated state of the waste and the
occurrence of leachate through the impoundment.
A process waste was placed as a slurry into an impoundment at a site in Texas
City, TX. Naturally occurring trees (osage, orange, and mulberry) and vegetation
have reduced the hydrated state of the top ten feet of the waste. Research on the
site has found that dewatering and net water removal are directly correlated to the
size of the trees.
Ongoing research, funded by the USEPA Great Plain and Rocky Mountain Hazardous Substance Research Center involves planting trees at CERCLA sites to
control erosion and leaching of zinc, arsenic, lead, and cadmium.
A grass/soil cover system is one of five alternative covers being evaluated by
Sandia National Labs in NM as part of an alternative landfill cover demonstration
study. Similar phyto-cover systems are being considered as potential demonstration sites by USEPA ORD at sites in Tulsa, OK; Beatty, NV; and Hill Air Force
Base in CA.
A phyto-cover system has been proposed and designed at the 95% completion
level for the F.E. Warren Air Force Base Superfund Site in Cheyenne, WY. This
site is currently being considered as a technology demonstration candidate by
USEPA-Region VIII.
Pfitzer junipers have been used in a landfill cover field demonstration at Beltsville,
MD. The juniper phyto-cover was installed over a clay layer to add to the robust
cover development, but not as a replacement of the low-permeability layer. The
objective of the demonstration study was to document the influence of junipers
as water scavengers, yet maintain the water runoff performance of the lowpermeability cap. Compared to a reference soil, the bioengineered juniper cover
reduced infiltration; it was demonstrated that the mature plant system improved
the systems resilience to failure.
Research regarding the establishment of sufficient vegetation to provide adequate
biomass growth with resultant evapotranspiration is being conducted at Idaho
National Engineering Lab, Idaho Falls, ID. This research focuses on four plant
326
species to deplete soil moisture, and the configuration of a capillary barrier and root
zone to prevent deep percolation during wet periods. The use of such phyto-covers
has been demonstrated to be applicable to landfill sites in the semi-arid west.
In Ljubljana, Slovenia, a ten-acre cover was planted with poplar trees in
19931994 with the primary goal of protecting groundwater by reducing leachate
formation through municipal and industrial wastes. Installation of the cover has
greatly improved the aesthetics of the area and increased the value of the wildlife
habitat. The design concept is being considered as a model that will become
national policy.
The author also knows of many other phyto-cover applications in MA, OH, MD,
NC, MI, PA, NY, NJ, and IL.
In 1998, USEPA began an effort to establish a design database and improve numerical prediction methods for alternative landfill covers. The initial task of the Alternative
Cover Assessment Project (ACAP) was to catalog past and existing research efforts
into measurement of cover performance and to describe the current state of numerical
prediction methods. The primary criterion was to measure percolation directly. Several
research sites operated by branches of the federal government were included in this
study. These sites include the national laboratories at Hanford, Sandia, Los Alamos,
Savannah River, and Idaho Falls, and DOE locations at Monticello, UT, Nevada Test
Site, DoD locations at California, Hawaii, Colorado, Utah, and others.
7.6.1
Benefits of Phyto-Covers over Traditional RCRA Caps
In addition to satisfying the critical antileaching requirement, phyto-covers provide a number of significant pollution control, ecological, and economic benefits
when compared to traditional RCRA caps:
A phyto-cover actually enhances natural biodegradation processes, instead of
interfering with them, as a RCRA cap would.
A gas-permeable phyto-cover allows for passive venting of gaseous byproducts
of biodegradation and allows oxygen to move into the fill to facilitate additional
biodegradation.
A phyto-cover provides a forest ecosystem and an attractive alternative to an
RCRA cap.
A phyto-cover can be installed with less cost and less risk to public safety than
a RCRA cap and, once the cover is established, the system has a natural stability
that minimizes long-term maintenance requirements.
7.6.2
Enhancing In Situ Biodegradation
Installing a phyto-cover at a site has the potential to enhance biodegradation of

waste materials, including organic waste and contaminants, in the root zone. In
natural ecosystems, high concentrations of indigenous soil microorganisms are found
in association with plant roots, because the roots exude a wide variety of compounds
such as sugars, amino/acids, carbohydrates, and essential vitamins. These compounds not only sustain the microbial consortia, which can degrade many organic
compounds directly, but also enhance and accelerate cometabolic degradation of
327
other pollutants resistant to direct degradation. In addition, the plants themselves

will take up and metabolize or volatilize some of the organic contaminants in the
fill. Finally, exuded organic acids also help in sequestering and immobilizing any
metals present in the root zone. By contrast, a RCRA cap provides no stimulation
to natural biodegradation and would be expected to substantially change biogeochemical conditions in the fill by trapping the gaseous byproducts of biodegradation (e.g., methane, carbon dioxide, and ammonia), thereby affecting factors
critical to natural attenuation mechanisms, such as pH and REDOX potential.
The main reason for the enhanced in situ biodegradation in landfills with phytocovers is the ability of the atmospheric oxygen to transfer into the landfill. The
primary mechanism transferring oxygen into the landfill is diffusion into the soil
from the atmosphere, based on an excellent summary shown below:14
The exchange of gases between the soil and the atmosphere is facilitated by two
mechanisms: mass flow and diffusion. Mass flow of air, which is due to pressure
differences between the atmosphere and the soil air, is less important than diffusion
in determining the total exchange that occurs. It is enhanced, however, by fluctuations
in soil moisture content. As water moves into the soil during a rain air will be
forced out. Likewise, when soil water is lost by evaporation from the surface or is
taken up by plants, air is drawn into the soil. Mass flow is also modified slightly by
other factors such as temperature, barometric pressure, and wind movement. Most
of the gaseous interchange in soils occurs by diffusion.
The minimum rate of oxygen diffusion at the bottom of the root zone was
estimated to be 5 108 grams per centimeter, squared per minute, or 2340 pounds
per year per acre.14 The maximum rate could be up to 9200 pounds per year per
acre. Over the surface of a 30-acre landfill, this translates into at least 70,000 pounds
of oxygen per year into the landfill, which facilitates stabilization of the waste. By
contrast, the single-barrier cap would admit only an estimated 75 pounds of oxygen
or about one tenth of one percent of the influx that could support the aerobic natural
attenuation mechanisms (Figures 7.7a and b).15
7.6.3
Gas Permeability
Unlike RCRA caps, which are essentially impermeable to gases and therefore
require elaborate gas venting systems to deal with gases and vapors generated by
biodegradation of the fill, a phyto-cover is porous and permeable to gas. A phytocover can thus eliminate the need for a gas collection system at many sites. Equally
important, a phyto-cover will allow oxygen to migrate into the fill, which will help
to support additional aerobic biodegradation and thereby hasten the completion of
the waste life cycle.
7.6.4
Ecological and Aesthetic Advantages
Both a phyto-cover and an RCRA cap are designed to be vegetated on the surface,
but vegetation on a phyto-cover has the appearance of a tree farm and, eventually,
328
Figure 7.7a
Biogeochemical conditions and mass balance for a presumptive remedy.
Figure 7.7b
Biogeochemical conditions and mass balance for a holistic remedy.
a forest, and serves the same ecological function as a forest while the RCRA cap is
covered with grass and, in order to protect the impermeable liner, must be prevented
from functioning like local natural ecosystems. Specifically, maintenance of the
integrity of the RCRA caps impermeable layer dictates that deep-rooted plant
species, such as trees and shrubs, not be allowed to colonize the site through natural
succession. Moreover, protection of the impermeable liner also requires that small
burrowing mammals, such as those normally associated with a meadow, must be
perpetually monitored for and eliminated when found. By contrast, the trees of a
phyto-cover provide nest sites for birds and other arboreal species and readily accept
in-fill by shrubs and native tree species, as deemed appropriate under site management criteria. Because no animal is likely to excavate below the deep root zone, it
is not necessary to prevent native fauna from inhabiting the phyto-cover. Besides
offering a preferred natural ambiance, the phyto-cover forest would also serve the
community as a noise pollution buffer and assist incrementally with global climate
issues by fixing substantially more carbon dioxide from the atmosphere than a grass
RCRA cap.
7.6.5
329
Maintenance, Economic, and Public Safety Advantages
The ongoing maintenance requirements for an established phyto-cover are minimal. Although relatively intensive monitoring for disease and pests is needed during
the three growing seasons that the trees need to become fully established, maintenance activities thereafter are expected to be minimal because of the self-healing
nature of the phyto-cover. Like a natural forest, the phyto-cover is expected to be
resistant to wind and water erosion. Unlike a RCRA cap, which can suffer cracks,
rips, and tears due to factors such as differential settling or physical intrusion, the
phyto-cover maintains its integrity and actually heals itself with new root growth in
response to physical disturbances. Thinning of trees may be undertaken in the future
to avoid crowding as the trees reach their mature size. However, the trees cut in a
thinning operation represent a valuable forestry crop, so revenue from their sale
should compensate for the operations costs.
The lower economic cost of the phyto-cover compared to the RCRA cap is accompanied by lower noneconomic social costs in the form of safety risks. Studies have
shown that remedy implementation imposes risks of injury and death to site workers,
neighbors, and the public using transportation routes. These risks are more certain and
typically substantially greater in magnitude than risks to the public from exposure to
site contaminants. For example, assuming that bulk construction materials can be found
at an average distance of 15 miles (i.e., 30 miles round trip) and using the U.S. truck
fatality rate of 4.7 108/mile, construction of RCRA C cap at a 30-acre landfill
site could lead to an estimate of transportation fatalities risk of 0.033.16 This estimate
will be further increased if the nontruck driver fatalities estimate is combined with
this. Since phyto-covers require less site work and fewer truckloads of imported
material, such as borrow soil and gas collection layer sand, constructing a phyto-cover
instead of an RCRA cap would involve less risk of an accidental injury or fatality to
a construction worker and lower risks of traffic incidents associated with truckloads
of construction materials carried over local roads
Finally, unlike a RCRA cap, which locks the site into an impermeable barrier
strategy, the phyto-cover system can be operated in a flexible way to take into account
the results of ongoing performance monitoring data. For example, if performance
data show that native species perform as well as hybrid poplars in preventing
infiltration, then the natural transition to native species can be accelerated, to enhance
the ecological service provided by the area. By the same token, in the unlikely event
that performance data show that a part of the cover is not performing to expectation,
then a supplementary measure such as additional sponge or denser planting would
be available to improve performance.
7.7
PHYTO-COVER DESIGN
The typical components of an engineered phyto-cover system consist of vegetative cover soils (existing and supplementary), soil amendments, nonsoil amendments, understory grasses and plants, and trees. An irrigation system is an optional
component to ensure sufficient water for tree growth in case of drought. Irrigated
330
trees grow more rapidly, thus meeting closure objectives in less time; however, there
is often lack of a convenient water source or on-site operation and maintenance
personnel to make an irrigation system feasible at a site. The need for on-site
irrigation should be based upon the expected water consumption of the trees.
7.7.1
Vegetative Cover Soils
The existing cover soil at many sites is sufficient to support an adequate root
system for healthy tree growth. This is evidenced by the vigorous growth of trees
often seen at abandoned landfills (Figure 7.8); however, the ability to grow trees is
not evidence that percolation and leachate production are controlled. Typically,
natural stands of vegetation are not effective at controlling percolation. Therefore,
sufficient soil and nonsoil amendments may need to be added to meet the requirements for tree growth, and to achieve minimum land surface slopes to promote
surface drainage and to provide sufficient soil water holding capacity for storage to
function as an adequate sponge. The amount of soil and nonsoil amendments
necessary must be determined by site-specific information, often collected in the
later stages of design.
Figure 7.8
Existing root penetration of a tree at a landfill site.
Any supplemental cover soil added to achieve the required grades, as well as
sufficient water storage capacity, will comprise common borrow soils. Supplemental
soil should be placed in 6-inch thick and loose lifts, and be lightly compacted to
achieve the minimum slope and thickness. This material is typically available from
several sources in the vicinity of most sites; the specific local source usually depends
upon availability during the construction period. The surficial lift of supplemental
soil and existing cover, depending upon which is exposed at the final grade surface,
331
must be ripped in two directions following final grading to assure noncompaction

and to prepare the surface to receive the nonsoil amendments.
7.7.2
Nonsoil Amendment
The addition of nonsoil amendments will increase the water-holding capacity

and nutrient transfer properties of the common borrow soils. Typical nonsoil amendments include compost, chipped wood, digested sewage biosolids, lime-stabilized
sludge, manure, and other organic biomass. The incorporation of this type of organic
matter into the existing and supplemented soils will greatly increase the tilth, fertility,
and water-holding capacity of the soil, and further reduce percolation through the
cover. Biosolids compost and lime-stabilized sludge are readily available through a
compost contractor. Typically a minimum 6-inch thick layer of organic amendments
needs to be applied to the soil surface after achieving final grade. This material is
spread evenly in a six-inch thick layer on the area to be planted with the engineered
phyto-cover system and is ripped into the surficial soils to a depth of 14 to 18 inches.
Ripping is performed in both an east-west and north-south orientation in order to
achieve a uniform mixing within the soil profile. Finally, the site is tilled in preparation for planting.
If the organic materials used for the nonsoil amendment have a high carbon to
nitrogen ratio, fertilizer is added along with organic amendments to aid in stabilizing
these amendments and to provide sufficient nutrients to the rooting plants. This
organic amendment is expected to supply all micronutrients required by the plants.
A mineral fertilizer is also added as needed, based on nutrient analyses of the applied
compost, to supplement the macronutrient reserves of nitrogen, phosphorous, and
potassium. All amendment addition, ripping, and tilling is completed prior to understory planting in the fall and before the trees are installed in the following
early spring.
7.7.3
Plants and Trees
The area to be planted will generally exhibit a minimum 2% or greater grade;

therefore, stabilization of the site cover material remains necessary to prevent erosion. Understory planting will be established for early erosion control and water
uptake during the first year. Understory establishment is a combination of annual
and perennial grasses, such as varieties of rye, oats, wheat, barley, and fescue, applied
at a rate of 20 to 40 pounds per acre. This mixture of seed is designed to meet the
short- and long-term objectives of the understory. Annual species will be fast growing
to control near-term erosion; perennial grasses will be deep-rooted species selected
as the primary long-term understory for the site. The long-term effectiveness of the
overstory is dependent upon establishment and long-term maintenance of the understory, which understory depletes shallow soil moisture, turn causing tree roots to
grow deeper to meet water requirements. As discussed earlier, the success of a phytocover is dependent upon establishment of deep-rooted trees to create a sufficient
sponge to store soil moisture in the dormant season.
332
The trees normally selected for construction of a phyto-cover are hybrid poplars
of the variety Deltoides x nigra.10,13 The candidate varieties, DN-21, DN-34, OP 367
and others, are planted based on demonstrated growth ability and hardiness in the
environment. The poplars are installed as either rooted plants or whips at a density
of approximately 1200 trees per acre.15 The rows are located by measurement and
flagged, and the trees installed by a tractor and mechanical planter. These trees are
typically planted with an in-row spacing of 3 feet and a row spacing of 10 to 13
feet. They are planted in rows positioned along the land elevation contours, perpendicular to slopes to aid in reducing sheet flow velocities and surface erosion.
7.8
COVER SYSTEM PERFORMANCE
The engineered phyto-cover system should be designed to meet the post-closure

and remediation objectives established for any landfill site as specified below:
Minimize infiltration of precipitation through the cover system into the waste to
protect groundwater quality at the site.
Resist surface soil erosion by wind and precipitation.
Minimize long-term maintenance.
Protect human health and the environment.
Offer post-closure and future beneficial use.
The achievement of these objectives is outlined in this and subsequent sections.

7.8.1
Hydrologic Water Balance
The engineered phyto-cover system is designed to mature into a remedial system

that exceeds the hydrologic performance of more conventional cover systems. However, instead of acting as a constructed barrier layer, which diverts precipitation from
the cover area as surface runoff or internal drainage, this system intercepts and uses
the water for plant growth. In other words, the engineered phyto-cover functions as
a sponge and pump system, with the root zone acting as the sponge, and trees acting
as the solar-driven pumps. In contrast to restrictive permeability barrier design, the
engineered phyto-cover design involves the storage of free water in soil pores and
the extraction of stored water by the tree roots.
The effectiveness of engineered phyto-cover systems as landfill closure systems
has been demonstrated at sites in the U.S. At sites in various climates with engineered
and agronomically optimized growing conditions, rapidly growing poplar trees are
capable of transpiring all natural precipitation that infiltrates into a site. While the
performance of engineered phyto-cover systems has been demonstrated, a proven
tool to design phyto-covers is not available. Therefore, to support the design and
demonstrate the effective performance of phyto-cover systems, this section discusses
some fundamental scientific methods of water balance analysis.
As discussed previously, the phyto-cover system utilizes specially selected trees
with a grass understory to optimize evapotranspiration and achieve the equivalent
333
performance of a conventional barrier cover system. This alternative landfill cover

system has been designed to minimize percolation to the waste by incorporating a
landfill soil cover with sufficient evapotranspirative and water holding capacity to
store precipitation temporarily in the nongrowing season for subsequent evapotranspiration by vegetation in the growing season. The two key design elements in
engineering a phyto-cover system are 1) determining the thickness and material
composition of the soil cover system required to provide sufficient water storage
capacity; and 2) incorporating a supportive phyto-cover system to access water stored
in the soil cover system for evapotranspiration to the atmosphere.
Moisture flow and moisture content in a landfill are extremely important to the
dynamic processes of decomposition and potential leachate generation. The fundamental means to assess the moisture conditions is through an evaluation of various
processes comprising a water mass balance. A water mass balance analysis is an
accounting procedure for tracking the moisture inputs to storage and the moisture
outputs that influence the potential flux of water through the cover into the waste.
The primary elements of a water mass balance include precipitation, surface runoff
(R/O), potential evapotranspiration (PET), infiltration (I), soil moisture storage (ST),
actual evapotranspiration (AET), and flux (or percolation) of water through the
system. The water shedding efficiency of a cap is then derived by calculating the
percentage of flux relative to total precipitation. The phyto-cover system design
concept involves maximizing efficiency by optimizing ET, runoff, and soil moisture
storage to minimize infiltration, flux, and potential leachate generation. The water
balance accounting for a phyto-cover can be summarized by the following equation
and Figure 7.9:
Percolation = Precipitation Runoff Evapotranspiration Moisture Storage
(7.3)
The water mass balance processes within a landfill are typically evaluated using
the hydrologic evaluation of landfill performance (HELP) model, developed by the
Waterways Experiment Station.17 The applicability of this model to design and
evaluation of an engineered phyto-cover system has been reviewed, and it has been
determined that the HELP model is inappropriate for this analysis because of several
computational deficiencies.18,19 The HELP model was developed based on assumptions pertaining to water management through low permeability soil covers with
vegetative covers comprising short-rooted grasses. No opportunity exists for user
input of higher ET values more representative of plant species with significantly
higher potential water uptake than the short grasses assumed by the HELP model.
Therefore, the model significantly underestimates evapotranspiration from trees and
other deeply rooted vegetation that are key elements of a phyto-cover system. This
application limitation of the HELP model results in an overestimation of infiltration
and coincident underestimation of efficiency (overestimation of drainage) if the
model were to be applied to an evaluation of a phyto-cover system.
A detailed assessment of various computer models used for landfill cover designs
during the early phases of the alternative cover assessment program (ACAP) came
to similar conclusions.11,12 Of the four codes tested, HELP was the most widely used
334
Precipitation
Leaf Transpiration
Canopy
Interception
Surface Evaporation
Soil Evaporation
Surface Evaporation
Surface Cover
Interception
1) Surface Litter or
Compost
Infiltration
Storage
Root
Depth
2) Soil and Nonsoil

Amendments
3) Waste Rootable Upper

Layer (Contributes toward
Storage)
Potential
Infiltration
Depth of
Capillary
Zone Draw
Thickness of the Arrow is

Proportional to the Volume of Water
Figure 7.9
Diagram of a phyto-cover (modified from Licht, 1998).
for landfill design, and the most user-friendly and highly dependable. HELP predictions consistently provided the highest estimates of drainage. Three concerns with
HELP were 1) a nonrealistic response of increased drainage as available water
capacity increased, 2) insensitivity of drainage to thickness of the cover surface
layer, and 3) consistent overprediction of drainage. EPIC was also relatively easy
to use, but consistently underpredicted drainage in comparison to other codes. The
study suggested that Richards equation-based codes (HYDRUS2D, UNSATH)
were better able to capture the behavior of alternative landfill covers than simple
water balance codes such as HELP and EPIC.
Although the HELP model itself cannot accurately simulate the hydraulic effects
of an engineered phyto-cover system, the water balance method that is the fundamental principle applied within the HELP model has been employed to evaluate the
performance of vegetative cover systems.20 These same scientific principles are
employed to design and evaluate the performance of an engineered phyto-cover
system with a new software tool called PHYTOSOLV.15,21 In using the water balance
method, the first step is to acquire accurate precipitation records applicable to the
site and encompassing various extreme wet and dry periods. The second step is to
determine the quantity of surface water runoff and infiltration (which are functions
335
of the site soils, slope, and surface texture). Infiltration is computed as the difference
between precipitation rates for the site and surface-water runoff from the soil cover.
The third step is to apply PHYTOSOLV, assuming a variety of soil cover depths, to
generate a range of annual hydrologic water balances using daily precipitation data.
Finally, a supporting phyto-cover system is designed that would access infiltrated
soil water throughout the entire extent of root growth (the sponge), and the
necessary evapotranspiration rate (the pump) required to deplete soil moisture
during the growing season is computed. This iterative water balance analysis is used
to select the appropriate soil cover design to best achieve desired hydraulic performance, thereby minimizing generation of leachate. The measure of performance
for the designed phyto-cover is compared to the water-shedding efficiency of traditional barrier cover systems. Presented below is a discussion of each of these steps
and the basis for the general engineered phyto-cover system design.
7.8.2
Precipitation
Long-term precipitation data need to be assembled from the closest weather

station to evaluate local hydrologic conditions. There are no established regulatorily
approved procedures or protocols to evaluate the hydrologic performance of a phytocover design. Therefore, long-term data are needed in order to characterize the longterm precipitation trends and extremes. Typically, precipitation can vary widely from
site to site for a given year, season, or month. To demonstrate this variability, data
should be assembled summarizing average monthly and annual precipitation for
decades at weather stations near any given site. For example, during a long period
at a site in Maryland, the average annual precipitation varied from a minimum of
26.29 inches in 1965 to a maximum of 62.36 inches in 1996. Similar variability can
also be observed in monthly precipitation totals. To the extent practical, these
dynamics must be accounted for in the design of the phyto-cover system to demonstrate adequate performance under extreme weather conditions. The application of
these data to evaluate the phyto-cover design assumes that daily precipitation totals
are the result of individual storm events.
7.8.3
Runoff
Runoff from the designed phyto-cover is computed using the USDA Soil Conservation Service (SCS) curve number model.22 The model computes direct runoff
from an individual storm event as a portion of total precipitation (Figure 7.10). The
method was developed from field studies by measuring runoff from various soil
cover, land slope, and soil type combinations. Curve numbers were developed based
upon each of the combined hydrologic effects of these factors and enable the model
to be applied to any area within the U.S. The curve number model is widely used
and is incorporated into the HELP model and other agronomic models to compute
rainfall runoff and other elements comprising a water balance. The major deficiency
in this model is that it underestimates runoff from small precipitation events. This
discrepancy results in overestimates of infiltration and the amount of water that must
be managed by the cover system.3 Consequently, the resultant engineered
336
Direct Runoff (Q), inches
7
6
Curves on this sheet are for

the case Is = 0.2S, so that
(P - 0.2s)2
Q=
P + 0.8S
r
be
10
90
m
Nu
ve
80
r
Cu
70
60
50
40
1
0
0
10
11
12
Rainfall (P), inches
Figure 7.10
Runoff SCS Method.
phyto-cover is overdesigned and conservative: the engineered phyto-cover has the

ability to control more infiltration than it is designed to manage.15
(P I a )
Q=
(P I a ) + S
2
(7.4)
where
Q
P
S
Ia
=
=
=
=
runoff (in)
precipitation (in)
potential maximum retention after runoff begins (in)
initial abstraction (in)
The initial abstraction is all water loss before runoff begins. It includes water
detained in surface depressions, as well as water intercepted by vegetation, evaporation,
and infiltration. The initial abstraction is highly variable but from data collected from
small agricultural watersheds, Ia was approximated using the following equation:
Ia = 0.2 S
(7.5)
By eliminating Ia as an independent parameter, this approximation allows use of

a combination of retention storage (S) and precipitation (P) to predict a unique runoff
amount. Substituting Equation 7.5 into Equation 7.4 gives
2
P 0.2 S)
(
Q=
P + 0.8 S
(7.6)
337
where S is related to the soil and cover conditions of the watershed through the
curve number CN. CN has a range from 30 to 100, and is related to S by the following
equation:
S=
1000
10
CN
(7.7)
The use of the SCS runoff equation for this analysis assumes that the difference
between precipitation and runoff is infiltration.15
The curve number can be estimated by either using the HELP model or other
computations. The HELP model computes a curve number based upon final grade,
soil type, and vegetative cover. Using this model is recommended because it objectively estimates a curve number based upon the final design. In addition, the methods
in the HELP model were developed and approved by the USEPA. When using the
model, the minimum final grade should be specified for the land surface slope and
a good vegetative cover be assumed for the understory. These two assumptions
ensure that the selected curve number is conservative (minimize runoff/maximize
infiltration).
7.8.4
Potential Evapotranspiration Measured Data
Potential evapotranspiration (PET) is a measure of the maximum rate at which

evapotranspiration can occur when adequate soil moisture is available for utilization
by vegetation. These data are measured in the field utilizing lysimeters planted with
single species covers (usually perennial grasses). Soil moisture levels are maintained
at optimum levels and evapotranspiration is measured by weighing the lysimeter.
Data collected through these methods are the most reliable and most defendable
estimates of potential evapotranspiration; however, measured site-specific data are
not readily available for most sites.
The monthly potential evapotranspiration rates measured for grasses are adjusted
to best represent the supplemental evapotranspiration available from the trees. This
step is performed by incorporating a consumptive-use coefficient (Kc) applicable to
the trees utilized in the phyto-cover design. A consumptive-use coefficient of 1.35
was measured for areas with cottonwood trees, willows, and grass.15,23 This value is
near the low end of the range for consumptive-use coefficient values derived for
densely planted trees in other parts of the U.S.; it has been reported that consumptiveuse coefficient values for densely planted trees vary from 1.3 to 1.6.24 The cottonwood is one species used to develop the hybrid poplar trees selected for the phytocover system. Hybrid poplar trees have been developed specifically to achieve a high
consumptive use coefficient, in addition to disease resistance and high growth rates;
therefore, the selection of a consumptive-use coefficient of 1.35 is conservative for
this engineered phyto-cover system.
The consumptive-use coefficient is used to adjust the measured potential evapotranspiration for grasses only during the growing season for trees April through
October (Figures 7.11a and b). The growing season begins with approximately 10%
338
Potential Evapotranspiration (inches)
10
9
8
7
6
5
4
3
2
1
0
Jan
Feb
Mar
Apr
May
Jun
Jul
Aug
Sep
Oct
Nov
Dec
Total 46.18 Inches

Figure 7.11a
Measured potential ET for a site with cool wet climatic conditions.
Potential Evapotranspiration (inches)
10
9
8
7
6
5
4
3
2
1
0
Jan
Feb
Mar
Apr
May
Jun
Jul
Aug
Sep
Oct
Nov
Dec
Total 55.62 Inches

Figure 7.11b
Potential ET of phyto-cover at the same site adjusted for consumptive use.
leafing in April, 50% leafing in May, and 100% leafing in June, July, and August.
Thereafter, leaf falloff occurs at a level of 70% in September and 20% in October.15
No leafing is assumed during the dormant season. Factoring these together, a combined consumptive-use coefficient for grasses and trees can be developed and used
to compute the monthly potential evapotranspiration rate for trees and grasses for
the phyto-cover design. It should be noted again, though, that these PET rates cannot
be achieved unless adequate soil moisture is available.
7.8.5
339
Potential Evapotranspiration Empirical Data
Modern equations to compute potential ET normalize estimated PET to a reference crop evapotranspiration rate (Erc; mm/day). The reference crop ET rate is
defined as the rate of ET from an idealized grass crop with a fixed crop height of
0.12 m, albedo of 0.23, and a surface resistance of 69 m/s. The reference crop closely
resembles an extensive surface of short green grass cover of uniform height that is
actively growing, completely shading the ground, and not short of water. The normalization of PET rates facilitates the comparison of computed rates from different
methods and equations. This also extends the application of crop specific consumptive use coefficients for estimating PET between methods.
The potential evapotranspiration from a site can be estimated empirically utilizing a radiation-based equation with the general form
Erc =
(R G)
+ n
(7.8)
where:
Erc
Rn
G
= potential ET [mm/day]
= constant
= gradient of the saturation vapor curve as a function of temperture
(kPa/C)
= psychrometric constant (kPa/C)
= net radiation exchange for the crop cover (mm/day)
= soil heat flux (mm/day)
Each of the constants in Equation 7.5 can be evaluated using average daily
temperature, mean elevation of the site above sea level, and atmospheric constants.
Substantial evidence supports the application of Equation 7.8 for determining PET
for areas with uniform vegetation cover. The following radiation-based equations
for estimation of potential evapotranspiration are recommended:15,25
E r c = 1.74
(R G)
+ n
(7.9)
for arid locations with relative humidity less than 60% in the month having peak
evaporation, and
E r c = 1.76
for all other humid locations.
(R G)
+ n
(7.10)
340
The variables in Equations 7.9 and 7.10 are evaluated using the following
expressions:
=
4098e s
(237.3 + T)2
(7.11)
where
T
es
= temperature (C)
= saturation vapor pressure (kPa)
17.27 T
e s = 0.6108 exp
(237.3 + T)
(7.12)
= atmospheric pressure (kPa) estimated from the site elevation using the
relationship
= 0.0016286
P = 101.0 0.011 5E + 5.44 107 E2

E
(7.13)
= land surface elevation (meters)

= latent heat of evaporation of water (MJ/kg)
= 2.501 0.002361 T
(7.14)
G = 0.38(Tday2 Tday1)
(7.15)
n
n
R n = 0.25 + 0.50 S0 0.9 + 0.1 0.34 0.14 e d T 4
N
N
n
N
S0
ed
7.8.6
(7.16)
=
=
=
=
bright sunshine hours per day

total day length in hours
extraterrestrial radiation (MJ/m2/day)
vapor pressure (kPa) = relative humidity (fraction) times the es
(computed above)
= Stefan-Boltzmann Constant (4.903 109 MJ/m2/K4/day)
Effective Evapotranspiration
The actual or effective ET is calculated by adjusting the PET value to account

for the reduction in the ET rates as soil moisture is depleted. This adjustment is
performed using a standard model of ET as a function of soil moisture.15,26 The
model is shown graphically in Figure 7.12. The effective ET rate occurs at the PET
Figure 7.12
341
Actual vs. potential evapotranspiration.
rate until soil moisture content is at a percentage of field capacity, then declines
linearly at soil moisture levels drier than this value until it is approximately zero at
the wilting point of the plants. Mathematically, the relationship between soil moisture
is expressed as follows:
(t )
= E r
t
(7.17)
where
Er = PET
Er =
( t )
PET
i
when
i s
when w i
(7.18)
(7.19)
342
The application of Equations 7.17 through 7.19 to compute the change in soil
moisture between two time intervals requires the integration of these equations.
Consider the time interval from 0 to a time t. The soil moisture at time t expressed
as a function of the soil moisture at time 0 is as follows:
t
(t ) = (0)
E dt
r
(7.20)
If the soil is wet (moisture content greater than i) the moisture content at time
t (2) is simply the initial moisture content (1) minus the PET rate multiplied by
the time interval.
2 = 1 PET t
(7.21)
If the soil is dry (moisture content less than i) the moisture content at time t
is the initial moisture content minus the integrated ET rate over the time interval.
t
(t ) = (0)
(t )
PET dt
i
(7.22)
Equation 7.22 cannot be solved directly because there is no relationship for soil
moisture as a function of time.
The equation to characterize the change in moisture content when the soil is dry
can be derived by substituting Equation 7.19 into Equation 7.17.
(t )
( t )
=
PET
t
i
(7.23)
Separating variables and integrating Equation 7.23 between limits,

2
d(t )
PET
=
dt
(t )
i
(7.24)
ln 2 ==
1
PET
t
i 0
(7.25)
Substituting and exponentiation of both sides of Equation 7.22 yields

PET
2
= exp
t
1
i
(7.26)
343
The moisture content at time t (2) can therefore be computed from the initial
moisture content (1) using the formula:
PET
2 = 1 exp
t
i
(7.27)
Equations 7.21 and 7.27 describe the change in moisture content with time when
the soil is dry or wet, respectively. A third case that needs to be considered is when
conditions change between wet and dry during the time period being evaluated (one
day for this model). Before Equation 7.21 is evaluated, the time necessary for
conditions to change from wet to dry at current PET rates is computed with the
following equation:
td =
( 1 i )
PET
(7.28)
If the time is greater than one day (the time period), Equation 7.21 is applied.
If the time is less than one day, Equation 7.21 is applied for the computed time (td),
and Equation 7.27 is applied for the remaining portion of the time period (1 td)
7.8.7
Water Balance Model
Water balance models of the soil profile are based upon fundamental principles
of the behavior of water in the soil. During a storm event, surficial soils are saturated
by precipitation. Initially, water percolates vertically in the profile, redistributing
moisture until the remaining water held by surface tension on the soil particles is
in equilibrium with gravitational forces causing drainage. The moisture content at
which this equilibrium occurs is termed field capacity. Water uptake by plants
continues to drive the drying process with little soil moisture restrictions until
moisture contents reach 25 to 80% of field capacity. Transpiration rates decrease as
the soil continues to dry until the wilting point of the plants is reached. Further
declines in soil moisture levels are controlled by the hydraulic conductivity of the
soil and occur as a result of evaporative and diffusion processes.25,27
These principles are used to develop a water balance model of an engineered
phyto-cover system. The water balance for a phyto-cover system begins with precipitation. It is assumed for this analysis that all precipitation is in the form of rain;
this assumption causes conservative design considerations related to cover thickness
and total water storage requirements. The soil surface separates precipitation into
runoff and infiltration. Runoff is estimated using the curve number model discussed
previously. This procedure was selected because it consistently underpredicts runoff
volumes and adds an additional degree of conservatism in that infiltration is overestimated. The runoff analysis for water balance assumes that daily precipitation
totals correspond to individual storms. After precipitation infiltrates the soil, water
is either stored, removed through ET, or, if moisture content is in excess of field
capacity, percolated through root zone and into the waste.
344
7.9
EXAMPLE APPLICATION
An example application was developed for a hypothetical site in Central Maryland. Precipitation data were assembled from the Conowingo Dam weather station
to evaluate local climatic conditions. Average annual precipitation for the 37-year
record evaluated is 45.2 inches. A more detailed look at long-term precipitation
trends and totals indicates that precipitation can vary widely for a given year, season,
or month. From 1960 through 1996 the average annual precipitation varied from a
minimum of 26.29 inches in 1965 to a maximum of 62.36 inches in 1996. Similar
variability can also be observed in the monthly precipitation totals. To the extent
practical, this variability must be accounted for in the design of the phyto-cover
system to demonstrate adequate performance under extreme weather conditions.
Therefore, the available daily precipitation data for the 37-year period between 1960
and 1996 were assembled in order to design the phyto-cover system. Figure 7.13
shows the daily precipitation data for a three-year period of the total years analyzed.
Daily precipitation records for all 37 years are utilized in this analysis in order to
account for rainfall runoff and extreme precipitation conditions.
Daily Precipitation (in)
3.00
2.00
1.00
62
10
/6/
6/1
6/6
/61
4/6
2
2/2
11
/4
7/1
5/6
1
60
3/2
5/6
12
/3/
3/6
0
8/1
3/6
0
4/2
1/1
/
60
0.00
Date
Figure 7.13
Daily precipitation data for a three-year period for the example application; this
analysis was performed for 37 years of data looked at for the site.
9.00
0.90
8.00
0.80
7.00
0.70
0.00
0.50
1.00
1.50
2.00
2.50
3.00
5.00
0.50
4.00
0.40
3.00
0.30
Daily ET
62
Daily Storage
/6/
Legend
10
6/6
6/1
4/6
2/2
11
/4/
5/6
7/1
5/6
3/2
/3/
12
3/6
3/6
8/1
1/1
61
0.00
1
0.00
60
1.00
0.10
2.00
/60
0.20
Soil Water Storage (in)
6.00
0.60
Daily Precipitation
345
1.00
4/2
Daily Evapotranspiration (in)
Date
Figure 7.14
Predicted daily performance of the final engineered phyto-cover design.
Potential ET rates are known for this area of the U.S. from data collected during
a 12-year lysimeter study in Seabrook, NJ.15,28 Actual ET rates are computed based
upon potential ET rates and soil moisture levels. For this example, the actual and
potential ET rates are assumed to be equal until moisture contents fall to less than
25% of soil moisture storage between field capacity and wilting point. At lower
moisture contents, ET is assumed to decline linearly to zero at the wilting point.
Other soil moisture models support the assumption that ET rates begin to decline
when the moisture content is 25% of the difference between field capacity and
wilting point (according to EPIC27 and CREAMS29) developed by the U.S.D.A.
Therefore, the methodology and assumptions of this water balance analysis are
technically defensible and comparable to the EPIC and CREAMS models developed
by the USDA. An example of the expected daily performance of the final design of
the engineered phyto-cover is shown in Figure 7.14. Figures that simulate daily soil
water storage, daily evaportranspiration, and observed precipitation from 1960
through 1996 can be obtained through this analysis. If the total water holding
capacity of the designed phyto-cover is more than the highest daily storage predicted,
then the phyto-cover can be theoretically expected to prevent percolation.
The water mass balance analysis employing the data presented above was used
to determine the site-specific performance of various engineered phyto-cover systems with different water holding capacities. This analysis is summarized in Figure
7.15 and shows that the average annual percolate is a function of the total water
holding capacity of the cover design. The greater the total water holding capacity
of the phyto-cover the less the average annual percolate.
Table 7.1 shows the designed water holding capacity of a phyto-cover utilizing
existing soil cover, supplemental imported soils, and municipal solid waste. The
existing soil cover at the site is assumed to have a thickness of 1.0 foot. The water
346
10.00
Existing Conditions (8.5 in/yr)
Standard Single-Barrier Cover

Compacted Clay (1.09 in/yr)
1.00
0.10
10.00 inches
Phyto-Cover, Total Water

Storage 10 inches (0.24 in/yr)
5.95 inches
Average Annual Flux through Cover (in/yr)
Decreased Leachate Production
100.00
0.01
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20
Total Water Storage Capacity (in)
Increased Cover Thickness
Figure 7.15
Long-term performance as a function of total water holding capacity.
Table 7.1 Analysis of the Water Holding Capacity (WHC) of the Phyto-Cover Sponge
Material
Additional Imported Soil Cover
Existing Landfill Soil Cover
Root Growth in Landfill Matrix
Total
Thickness
Field
Wilting
(feet)
Capacity Point
2.0
1.0
5.0
0.284
0.244
0.292
0.135
0.136
0.077
WHC
(in/foot)
Total WHC
(inches)
1.79
1.30
2.58
3.58
1.30
12.90
17.58
holding capacity (WHC) for the soil type at the site (silt clay loam) is 1.3 inches
per foot.15,17 The supplemental soil cover has been assumed to be a silt loam with
a water holding capacity of 1.8 inches per foot for this water balance analysis. Figure
7.16 shows the water holding capacity of different types of soils.
The water holding capacity of waste in a mature landfill is between 0.5 and 1.7
inches of water per foot depending on the percentage of municipal solid waste.3
Water holding capacity as high as 4.85 inches of water per foot of waste has been
reported. The landfill is assumed to consist primarily of municipal solid waste. The
HELP model reports that this type of waste has a water holding capacity of 2.58
in/foot. Poplar trees grow vigorously over landfills, as evidenced by conditions at
347
Water Content in Inches per Foot of Soil
4
Gravitational Water
ts
cit
lan
a
ap
eld
dily
ble
ssi
Fi
te
Wa
cce
P
to
te
a
Re
Ra
ed
tR
a
nly
d
uce
O
ible
ss
cce
rA
te
Wa
oin
gP
tin
Wil
Limited Availability
Figure 7.16
Clay
Hv. Clay
Loam
Clay
Loam
Silt
Loam
Lt. Clay
Loam
Loam
Fine
Sandy
Loam
Sandy
Loam
Fine
Sand
Sand
Water holding characteristics of soils.
abandoned landfills, and routinely develop roots deeper than 8 feet below the soil
surface. Accordingly, the engineered phyto-cover system is designed to root into the
waste to capture additional water holding capacity.
According to Table 7.1, 17.78 inches is the total water holding capacity with an
additional 2 feet of soil cover, the existing average 1.0 feet of soil cover, and root
growth 5 feet into the landfill matrix. Therefore, the performance efficiency of the
designed phyto-cover is greater than 98%; this level of efficiency favorably compares
with the performance efficiency of the RCRA cap over a long period of time.
7.10
SUMMARY OF PHYTO-COVER WATER BALANCE
After the phyto-cover is in place and functioning, the moisture levels in the waste
and soils below the root zone and above the water table will fall well below field
capacity as gravity and capillary action pull moisture out. These now-drier unsaturated materials will provide a water absorption capacity in addition to that within the
root zone to absorb potential infiltration below the root zone during occasional
extremely wet periods. As the overlying soils again fall below field capacity with
additional evapotranspiration, capillary action will act to remove moisture again
from below the root zone and above the water table. Thus relatively small amounts
of water moving through the root zone during infrequent periods of extreme precipitation will not proceed directly to the water table, but will be held by the waste and
unsaturated soils, and acted on by capillary action and osmotic potential to move
back up and into the atmosphere. In contrast, there is no upward gradient for
movement of potential leakage from a membrane cap.
348
This design for the phyto-cover system incorporates a margin of safety because
the water-balance calculations were based on the following conservative input values:
Underestimation of surface-water runoff by the curve number method (overestimation of infiltration)
Assumption of a consistently short growing season
Consumptive-use coefficient lower than known measured values for the type of
trees in the design
Assumption of root growth depth shallower than that known to occur with the
type of trees in the design
Not accounting for additional storage capacity provided by the very large volume
of landfill matrix which will remain below field capacity most of the time, and
the subsequent capillary removal of moisture which may, on occasion, extend into
this mass
In addition to the use of these conservative design parameter inputs, the engineered phyto-cover system design, unlike the design of RCRA barrier caps, can
include the actual measurement of soil moisture as an element of operations and
maintenance (O&M), thus ensuring continuous evaluation of the systems hydraulic
performance.
This analysis demonstrates that the designed phyto-cover could perform at least
as effectively as a conventional landfill cover over a long period of time. In addition,
once the phyto-cover is installed, the waste below the root zone will continuously
dry up and will encounter a significant loss in moisture content. This continuous
drying will provide additional water holding capacity to handle the flux associated
with an extreme precipitation event. In summary, the analysis effectively demonstrates that the engineered phyto-cover system presented has the ability to achieve
the objectives of conventional landfill covers and to protect human health and the
environment, by protecting groundwater quality through minimizing the generation
of landfill leachate. In addition, if coupled with monitored natural attenuation of
groundwater, the engineered phyto-cover technology provides the optimum balance
for achieving all of the stated goals for landfill closure.
7.11
GENERAL PHYTO-COVER MAINTENANCE ACTIVITIES
7.11.1 Site Inspections

To ensure the continued proper functioning and integrity of the engineered phytocover system, regularly scheduled inspections should be conducted by on-site personnel and the local expert. In addition, during the early part of the growing season
or upon discovery of any unusual operational conditions, inspections by members
of the maintenance team should be completed. The local expert should have general
knowledge of erosion control, irrigation systems, soil moisture monitoring, and
vegetation care. Inspections should be conducted during the growing season on a
weekly schedule during the first year of the O&M period, biweekly during the second
349
year, and monthly or as needed thereafter throughout the O&M period. Detailed
descriptions of the activities specific to each time period are provided in later
sections. During the first three years of the maintenance period, additional inspections of the cover system should be conducted following storm events. Inspection
observations should be recorded on an inspection log and stored on-site in a threering log binder. Photographic documentation of the growth and maturation of phytocover should also be collected and included with the inspection log.30
The log from each inspection should be reviewed by the maintenance team to
evaluate phyto-cover system maturation and recommend any required corrective
action. Expert personnel should be consulted, as necessary, to assist in the identification of diseases and pests that may affect the overall maintenance and health of
the cover system and, in particular, the hybrid popular trees planted at the site.
To determine the condition of the phyto-cover system during routine inspections,
the site operator should walk the perimeter and traverse the cover along a significant
number of randomly selected, noncontiguous tree rows. Different rows should be
selected each week, except when reinspection is necessary. Conditions that the site
operator will inspect include, but are not limited to 1) surface disturbances or rutting;
2) gullies, washouts, or other cover disturbances caused by water erosion; 3) settlement/subsidence; 4) wear, such as burrows due to animals; 5) vegetation condition;
6) evidence of malfunctions within the irrigation system; 7) saturated soils and
precipitation ponding; 8) insects or pests; 9) tensiometer readings; 10) irrigation
totalizer readings; and 11) structural integrity of the perimeter fencing.
Immediate restorative actions are required if any of the following conditions are
observed during a visual inspection:
Evidence of stressed vegetation, or evidence of animal, insect, disease, or other
damage to vegetation
Evidence of saturated soils, ponding water, or excessively dry soils
Erosion that could compromise the integrity of the phyto-cover system
Other conditions that may interfere with the proper performance of the phytocover system
The site operator should document the inspection results and any observed
deficiencies on an inspection log, and corrective action should be undertaken and
documented.
7.11.2 Soil Moisture Monitoring
As the phyto-cover matures, trees will develop roots through the surficial vegetative soil zone and into the underlying waste.30 Initially, the majority of root growth
will be laterally along the surficial soil zone (the upper 24 inches). The cover uses
root uptake to de-water the root zone and underlying waste. By monitoring the
soil-moisture content in this zone, the site operator can qualitatively estimate water
removal by plant uptake and moisture replenishment through irrigation and natural
precipitation. Measurements will be made using two tensiometers placed at selected
locations within the phyto-cover. Tensiometers will be placed at the beginning of
350
the growth season between trees in the rows, in areas of contrasting moisture content
based on visual observation of the site after significant precipitation events.
A tensiometer is a simple device that measures the relative moisture of the soil
by comparing uptake or loss of water through a ceramic membrane and recording
the change in vacuum (Figure 7.17). The tensiometer data will be used along with
site-specific precipitation data to determine the rate and frequency of irrigation
applications as discussed below. Tensiometers must be removed and stored in accordance with the manufacturers instructions prior to the onset of freezing conditions.
Figure 7.17
7.11.2.1
Photograph of a field tensiometer.
Drainage Measurement
While many studies have documented parameters related to phyto-cover performance (soil-moisture content, precipitation, runoff), these measurements by themselves do not address the central issue, namely the actual deep percolation through
the cover. In most cases, the collection of soil moisture, runoff, and precipitation
data has been performed to meet regulatory performance requirements. Methods
utilizing these data to estimate the ability of a cover design to limit the flux of water
have to rely on predictive methods and thus have inherent uncertainties.11,12
Methods of determining deep percolation include those based on fixed fractions
of annual precipitation, groundwater quality and level changes within the footprint
of the landfill, water balance models, environmental tracer models, and lysimetry.11,12
Water-balance lysimetry is the most direct, quantitative method utilized to directly
measure deep percolation through engineered phyto-covers. It has not been used
universally due to the high cost of installation.
351
Water-balance lysimeters are typically soil-filled containers buried flush with the
soil surface that allow for some method of collecting drainage. Often these lysimeters
can also be used to measure water storage either directly through weighing or by
using independent methods (e.g., neutron probe or TDR) to monitor soil water
storage. Lysimeters are semipermanent structures that are often expensive to construct and must be designed to account for soil physical properties and site-specific
environmental variables. Despite these concerns, it was concluded that lysimeters
provide the most reliable means of measuring deep percolation, given adequate
surface area and long-term monitoring, with precision in drainage often better than
1 mm/year.11,12
Measurement of percolation by drainage lysimetry is made possible by the
presence of an impermeable geomembrane forming the bottom boundary. The interruption of downward movement of moisture by the geomembrane causes increased
moisture content in the soil layer immediately above the membrane. Drainage occurs
when the soil above the membrane liner reaches near-saturation point. This requirement presents a design problem if roots from surface vegetation are allowed to
penetrate to the bottom of the lysimeter. When the downward flux of moisture is
impeded by an impermeable membrane and plants are allowed access to the trapped
moisture, percolation is reduced, which can result in false negatives. This factor can
be addressed if the lysimeter is relatively deep and roots are restrained from
approaching the bottom liner of the lysimeter. Of all currently available methods,
only the use of water-balance lysimeters (over several years, combined with climatic
observations, plant community activities, and soil parameters) can provide the data
necessary to quantify the performance of phyto-covers and validate and calibrate
numerical models used for design purposes.19 Many different configurations of
water-balance lysimeters are shown in Figures 7.18a through h.
Surface Flow
Diversion
10 m
Manhole
Cover Materials:
Variable Depth
Electronic Measurement
of Runoff and Drainage
20
tu
Na
pe
Slo
ral
Interim Cover: Variable Depth
Geosynthetic
Root Barrier
3 to 5% Slope
60-mil
HDPE Liner
Geocomposite
Drainage Layer
French Drain,
Sump Pump
Figures 7.18a
Detail of proposed lysimeter test facility design (courtesy of Rock and USEPA,
1999).
352
Access Trench
Berm
Drainage
Measurements
Drainage
Precipitation
Soil Moisture Content
Soil Moisture Potential
Figures 7.18b
Lysimeters: 2 rows of 5 each

Dimensions: 3m wide
3m long
3m deep
Construction: concrete walls and floor
Lysimeter facility at INEEL EBTF (courtesy of Rock and USEPA, 1999).
Lysimeter Dimension: 12 m x 18
Diversion Berms
37% slope
Runoff
Collection
60-mil HDPE Liner

Measurements
Drainage
Soil Moisture
Drainage
Precipitation
Air Temperature
Relative Humidity
Solar Radiation
Wind Speed
Runoff
Dew Point
Figures 7.18c
Live oak (Atlanta) lysimeter (courtesy of Rock and USEPA, 1999).
7.11.3 General Irrigation Guidelines

The phyto-cover system will require intermittent irrigation from approximately
May through September, depending on observed weather conditions and year of
operation. An existing site precipitation gauge should be utilized to measure precipitation received at the site on a weekly basis at a minimum. If precipitation exceeds
353
33% Slope
Cover
Materials
Runoff
Collection
Drainage Grid and

Hypalon Membrane
Sand Bedding
Measurements
Collection Sump
Soil Moisture
Drainage
Precipitation
Soil Temperature
Runoff
Vegetation
Activities
Figures 7.18d
Drainage
Collection
Omega Hills lysimeter facility (courtesy of Rock and USEPA, 1999).
TDR
Cover Soil
40-mil HDPE
Berm
3% Slope
Collection Pipe
Drainage
Collection
Measurements
Soil Moisture
Figures 7.18e
Twentynine Palms lysimeter facility (courtesy of Rock and USEPA, 1999).
0.25 inches in a 24-hour period, or a total of 1 inch in any 1-week period, the
irrigation system should be turned off at the backflow prevention valve to prevent
overwatering of the phyto-cover system and saturation of the soils. The precipitation
gauge information should be augmented by the tensiometer data collected at the
phyto-cover. The tensiometer readings should be used along with the tree indicator
parameters described later to determine if the precipitation events have provided
sufficient soil moisture or if augmentation through irrigation is required. The cover
system soils must also be visually inspected prior to reactivation of the irrigation
system to determine soil moisture conditions. If either saturated soils or standing
water is observed, irrigation of the engineered phyto-cover system should not be
conducted until the affected surface is dry, standing water is absent, and the
tensiometer readings indicate a reduction in soil moisture to less than the assumed
354
3% Slope
Cover
Materials
Drainage Geocomposite
60-mil VFPE Geomembrane

Measurements
Overall Dimensions: 15.2 m long by 9.1 m wide
Drainage
Collection
Drainage
Precipitation
Soil Moisture
Irrigation
Runoff
Figures 7.18f
Rocky Mountain Arsenal lysimeter facility (courtesy of Rock and USEPA, 1999).
Cover Soils
Size: 4.6 m wide x 11.0 m long
Instrument Access
20-mil Reinforced Geomembrane
Fiberglass _______
Drainage
15 cm PVC Pipe
Measurements
Drainage
Precipitation
Soil Moisture
Soil Temperature
Figures 7.18g
Air Temperature
Soil Heat Flux
Net Radiation
Snow Depth
Hill AFB lysimeter facility (courtesy of Rock and USEPA, 1999).
field capacity (+/ 30 centibars). Again, indicator parameters should be the primary
method used to determine when to resume irrigation. The irrigation system zone
capabilities make it possible to irrigate discrete areas of the cover in the event that
significant areal variability in soil moisture is observed. An example of an irrigation
system is shown in Figure 7.19.
Minirhizotron
Access Tube
355
Datalogger
Cover
Materials
Interim Cover
Soil Water Content

Figures 7.18h
Figure 7.19
Soil Water Pressure
Soil Temperature
Detail of a vadose zone monitoring station (courtesy of Rock and USEPA,

1999).
An example of an irrigation system for a phyto-cover.
For the first 3 years, hybrid polar trees planted at the site will require approximately 1 inch of water per week to promote rapid growth and development of a
healthy root system. This water can be from natural precipitation or through irrigation. The ideal distribution of any required irrigation water would be in daily events,
irrigating at night to reduce evaporative losses. The drip irrigation system will be
adjusted by the site operator to assure that trees receive the appropriate amount of
water. This is very important because insufficient water will cause trees to wilt and
excess watering will stunt growth and possibly cause trees to die from lack of oxygen
at the root zone.
Should natural precipitation occur coincident with irrigation, the irrigation should
continue until either 1 inch of precipitation is received within 7 days, or if any single
356
daily precipitation event exceeds 0.25 inches.30 In the event that irrigation is stopped
due to the 0.25-inch standard being met, then irrigation should continue again within
2 days of the event, unless soils are visually saturated or tensiometer readings indicate
less than 30 centibars vacuum.
The irrigation system must be turned off and winterized during the dormant
season for trees; generally, this occurs in mid- to late September. Soil-moisture
monitoring and inspection of the engineering phyto-cover system should be
conducted at the beginning of the next growing year to verify soil moisture content
before the drip irrigation system is reactivated.
7.11.4 Tree Evaluation
The most important and effective indication of maturation and health of the tree
population is the presence of abundant, large leaves and an increase in both stem
height and girth. Most woody plants grow intermittently, and it is not unusual to see
growth in what are known as flushes when environmental factors are favorable,
and slower growth when unfavorable conditions exist. The following field evaluation
techniques will assist in the evaluation of tree performance.
7.11.4.1
Stem
The woody stems of one-year-old rooted stock poplar trees at planting have an
average diameter of less than one half inch at planting. During the first year of
growth, it is not unusual for the diameter to double; This increase in girth is referred
to as secondary growth. In addition to the increase in girth, the height of the tree
may increase by an average of 25% or more. The increase in length is known as
primary growth (Figure 7.20).
In addition to increases in primary and secondary growth, the stem will form
branches to expose as many leaves as possible for the production of energy. It is not
unusual for poplar species present at the site to form branches all along the stem during
the first year of growth. As primary growth increases in later years, these branches are
generally lost through the process of abscission, and replaced by branches higher up
the stem at the tree crown. Abscission is a change in plant hormonal conditions that
causes the plant to shed leaves and small limbs, while at the same time generating
protective materials (cork) to cover the wound or abscission site.
A few simple field tests can be completed during the early years to assess stem
condition. The simplest method involves bending the top of the stem, which should
be supple and flexible and not crack or break. A second test involves scratching bark
from the stem to reveal the cambium. This test should be performed if the bending
test indicates problems with the meristematic tissue. If the cambium is green, then
the meristematic tissue is healthy, and the stem is healthy. To assess the cambium,
the stem should be scratched beginning at the top and working down to the base of
the tree, as die-back in the stem generally occurs from the extremities back to
the roots.
Figure 7.20
7.11.4.2
357
Healthy stem of a growing poplar tree.
Leaves
The leaves of trees serve to convert raw materials (sunlight, water, CO2, etc.)
into sugars and control the loss of water by evapotranspiration. The leaves are
composed of several different cell types, but the most important structures affecting
performance of the phyto-cover system are the cuticle-covered epidermis and the
stomata located on the underside of the leaves. The cuticle is a waxy coating that
limits secondary or cuticle transpiration. The stomata are the primary means of
transpiration, and account for more than 90% of transpirative losses. Indicators to
check include uniformity in leaf color and growth.
Poplar tree leaves form from buds on the stem and branches. Healthy poplar
leaves form large delta-shaped leaves with a diameter that can grow in excess of six
inches at the widest part, with lengths in excess of six inches as well (Figure 7.21a).
The leaves are a brilliant green color with variations of darker green also present;
They should not contain black or brown areas of discoloration. The leaves are
attached to the stem by a flat-shaped petiole.
Leaves are the primary indication of stress or disease (Figure 7.21b). They
indicate stress from a variety of environmental conditions including drought, overwatering, lack of oxygen or excessive CO2 at the roots, and animal foraging and
infestation. Drought conditions are evidenced by withering and, if severe enough,
by early abscission, whereas other stresses can cause the leaves to change color and
wither on the stem without falling. Infestation and foraging are more readily diagnosed by physical evidence associated with discoloration or the loss of part of an
otherwise healthy leaf. Visible evidence of leaf stress must be immediately addressed,
as certain conditions can cause rapid declines in health and survivability of the tree.
358
Figure 7.21
(a) Healthy and (b) diseased leaves of a poplar tree.
7.11.5 Agronomic Chemistry Sampling

Soil and foliage samples must be collected in August during the first 3 years of
operations, and in subsequent years as the need may arise to diagnose growth
problems or apparent disease. Nutrient analyses of soils and leaves must be used to
determine the fertilizer addition necessary, including organic content analyses
(American Society for Testing and Materials [ASTM] D-2974) and pH (ASTM D4972), among others (e.g., nitrogen, phosphorous, etc.). Additional testing must be
performed as necessary to diagnose performance problems identified during inspections, and assess the results of any corrective action taken.
359
The phyto-cover system must be divided into representative sections by assigning

transects perpendicular to the tree rows. A reasonable number of soil subsamples
across each transect must be collected and combined into one sample. Soils can be
collected within 18 inches of trees, and must be collected from a depth of approximately 12 inches below grade. The samples must be analyzed for pH and essential
micronutrients as discussed above. Results should be reviewed and compared to
suggested concentrations provided in the environmental soil analysis report supplied
by the agronomic testing laboratory to determine necessary fertilizer addition or pH
adjustments at the site. Laboratory recommendations for fertilizing deciduous trees
should be used to determine the appropriate fertilization rate.
In addition to soil samples, samples of leaf tissue must be collected from the
same transects. For each transect, a total of 20 leaves (or the minimum number
required by the laboratory, if higher) must be collected from 20 trees. It is suggested
that samples be collected from healthy, recently matured leaves. These samples must
be composited and analyzed for 13 nutrient elements.
7.11.6 Safety and Preventative Maintenance
During maintenance, all fertilizers, herbicides, and insecticides must be brought
on-site in ready-to-apply concentrations. No mixing of undiluted applications should
be permitted, and all chemicals brought on-site must be approved by the site operator
and accompanied by appropriate material safety data sheets. All chemicals brought
on-site must be documented to have no deleterious effect on the trees. If required by
local statute, all herbicides and insecticides must be applied by a licensed contractor.
7.11.7 Repairs and Maintenance
Based upon the outcome of the visual observations, the inspection logs must
address, as needed, repair and maintenance of security control devices, vegetation,
erosion of the phyto-cover system, surficial settlement, and irrigation system. If a
problem is identified during the course of site inspections, the situation should be
evaluated by the site operator and necessary responses must be initiated in a time
frame appropriate to the condition. After the repair, a reinspection must be made
and documented on an inspection log. If, upon reinspection, it is determined that
additional corrective maintenance is necessary, prompt attention must be given to
the deficiency.
7.12
OPERATION AND MAINTENANCE (O&M) SCHEDULE
The O&M associated with the phyto-cover is divided into three distinct phases:
year 1 establishment; years 2 and 3 active maintenance; and year 4 and
succeeding years passive maintenance. The site operator or assignee must perform
maintenance activities, and record observations on the inspection log form. Each
maintenance period is discussed in detail in the following sections.
360
7.12.1 Year 1 Establishment

Management tasks for year 1 Establishment include the following activities:
1. The inspector(s) will conduct weekly site inspections of the entire cover system
during the growing season and after major storm events. Biweekly inspections
will be conducted during the dormant season.
2. Periodic mowing will be conducted to maintain the understory health and reduce
understory competition with the trees. It is anticipated that monthly mowing between
the tree rows during the growing season will be sufficient. Care must be exercised
so that irrigation drip lines are not damaged during mowing. Mowing between trees
within the rows is not necessary and will result in damage to the drip piping.
3. Herbicides will be applied by an appropriate contractor, as required, to prevent
the propagation of undesirable species. The selected herbicide must not have any
effect on the poplar trees.
4. Insecticide will be applied by an appropriate contractor, as required, based on inspections for infestations of cottonwood beetles, eastern tent caterpillars, or other pests
that pose potential problems. The selected herbicide will have no effect on the trees.
5. Monitoring will include foliar and soil sampling during August of the first year;
results will be analyzed for year 2 fertilization requirements. Foliar and soil
sampling will be conducted in accordance with the methods of the Agricultural
Research Service, USDA, to determine soil fertility status as it affects foliation
and plant rooting patterns.
6. Repair or replacement of erosion control and security features will be implemented, as required, by an appropriate contractor. This will include surface application of compost mulch, straw, or shredded yard debris.
7. Irrigation system inspection and maintenance will be conducted, including:
inspecting and maintaining the backflow prevention valve, supply manifold,
zone valves, and drip lines; and,
winterization of the drip system, including turning off water supply valving,
blowing out the lines with air, and removal of batteries from the zone valves
at the end of the irrigation season.
7.12.2
Years 2 and 3 Active Maintenance
The following tasks will be performed for years 2 and 3 Active Maintenance
for the phyto-cover system:
1. The inspector will conduct biweekly site inspections of the entire cover system,
year round and after major storm events.
2. The inspector will contract to apply fertilizer in April, as recommended by agronomic analyses from the year 1 August foliar and soil sampling.
3. The inspector will supply weed control on an as-needed basis. Less emphasis
should be required in year 2, and weed control should only be applied if specific
stress indicators that can be attributed to weeds are present on the trees.
4. Mowing will take place as required to maintain the understory health.
5. Dead or diseased trees must be removed and replaced with a healthy tree.
6. Insecticides may be required. Spraying leaf surfaces is especially important for
an infestation of cottonwood beetle or eastern tent caterpillar, should it occur.
361
Such insect infestations are normally a more significant problem during the first
2 years of establishment.
7. Monitoring will include August foliar and soil sampling as in year 1 for nutrient
content. Results will be analyzed to determine the following years spring fertilization requirements.
8. Repair or replacement of erosion control structures will be implemented as
required.
9. Irrigation system inspection and maintenance will be conducted, including:
inspecting and maintaining the backflow prevention valve, supply manifold,
zone valves, and drip lines; and,
winterization of the drip system, including turning off water supply valving,
blowing out the lines with air, and removal of batteries from the zone valves
at the end of the irrigation season.
7.12.3 Year 4 Passive Maintenance

Passive maintenance of the phyto-cover system will be conducted beginning in
year 4 and continuing for succeeding years. These tasks will include the following
activities:
1. Monthly site inspections will be conducted. More frequent inspections will be
completed during the spring leafing and fall bud setting to evaluate the tree growth,
at the discretion of the site operator.
2. Fertilization will be applied, as required, based on the previous years agronomic
analyses.
3. Weed control will not be required unless undesirable species present a threat to
the trees.
4. Dead or diseased trees must be removed and replaced with a healthy tree.
5. Insecticides will be applied only if necessary.
6. August foliar and soil sampling may not be required, but nutrients may be applied
periodically in following years to maintain the best growth at the discretion of
the site operator.
7. Repair or replacement of erosion control features will be implemented as required.
8. Irrigation system operations should only be required during periods of unusually
dry weather, when precipitation amounts are lower than normal. Inspection and
maintenance of the irrigation system will be conducted on an annual basis, and
before the system is used after a long period of inactivity, including:
clearing of potential sediment buildup in the drip lines; and,
maintaining the connection of the backflow prevention valve, manifold, zone
valves, and drip lines.
Over the life of the phyto-cover, indigenous species will be allowed to invade
in several stages of forest community succession, leading to climax culture of a
mature forest predominant in the region. This is inherent in the design of the system,
leading to a self-sustaining biotic community and providing an alternative to harvesting and replanting. Furthermore, it allows the slower growing, longer lived trees
already populating the perimeter of the site to colonize into the poplar stand as the
poplar trees reach the end of their life expectancy of 50 or more years.
362
The protection of human health and the environment provided by the phytocover system, as designed, will be equivalent in performance to that of a singlebarrier cover system. If it is determined that the invasion of indigenous species does
not maintain the performance at an equal or better level of protection, these other
species will not be allowed to establish themselves and supplant the design species
(poplars).
7.13
SPECIFIC OPERATIONAL ISSUES
7.13.1 Irrigation System Requirements

The irrigation system comprises several components that require routine evaluation and maintenance. The backflow prevention valve will require seasonal frost
proofing. Prior to operating the valve in the spring, the bleed valves must be closed,
and the unit checked for leaks. The irrigation manifold piping will also require
seasonal frost proofing. After closing and frost proofing the backflow prevention
valve, the manifold should be evacuated using compressed air.
In addition to frost-proofing requirements, the zone control valves require routine
maintenance. The valves should be monitored during weekly inspections to ensure
proper operation. This can be accomplished by opening and closing the valves with
the programmable controller. The valves can be operated by nine-volt batteries. More
frequent battery changeouts may be required depending upon the programmed irrigation cycle frequency.
7.13.2 Tree Replacement
Should the replacement of trees be required, the optimal planting time would be
the end of March or beginning of April. Trees can also be planted in the fall; however,
this is not recommended for bare-root stock. One-year-old rooted stock of the same
species and preferably from the same supplier should be obtained and planted
immediately upon receipt. Trees should be planted in the same location as the tree
being replaced. To plant the trees, dig or drill a 6-inch diameter or larger, 18- to 24inch-deep hole and place the root mass directly into the hole. Carefully backfill the
hole with the soils removed during excavation or with a good quality organic humus.
Compact the soils around the tree carefully by hand, and water each tree with at
least ten gallons of water. Place a bamboo stake and protective cover around the
tree, and replace the drip irrigation pipe so that the drip emitter is within 6 inches
of the tree stem.
REFERENCES
1. USEPA, Final Covers on Hazardous Waste Landfills and Surface Impoundments,
Technical Guidance Document, Office of Solid Waste and Emergency Response,
Washington, D.C., 1989.
363
2. Rock, S. A. and P. G. Soyre, Phytoremediation of hazardous wastes: potential regulatory acceptability, Remed. J., Autumn, 1998.
3. McBean, E. A., F. A. Rovers, and G. J. Farquhar, Solid Waste Landfill Engineering
and Design, Prentice Hall, Englewood Cliffs, NJ, 1995.
4. Reinhart, D. R. and T. G. Townsend, Landfill Bioreactor Design and Operation, Lewis
5. Suter, G. W., R. J. Luxmoore, and E. D. Smith, Compacted soil barriers at abandoned
landfill sites are likely to fail in the long term, J. Environ. Qual., 22, 217226, 1993.
6. Koerner, R. M. and D. E. Daniel, Final Covers for Solid Waste Landfills and Abandoned Dumps, ASCE Press, Reston, VA, 1997.
7. Board, M. and D. Laine, Corralling liner nightmares, MSW Manage., 5, 4851, 1995.
8. Crozier, F. and T. Walker, How much does your liner leak?, Wastes Manage., 2426,
1995.
9. Finn, S., Golder Associates, personal communication, 1998.
10. Licht, L., Ecolotree, Inc., personal communications, 1996, 1997, 1998.
11. USEPA, Alternative Cover Assessment Project (ACAP), Phase I Report, prepared by
Water Resources Center, Desert Research Institute, August, 1999.
12. Rock, S., personal communications, 1997, 1998, 1999, 2000.
13. Gatliff, E., personal communication, 2000.
14. Brady, N. C., The Nature and Properties of Soils, MacMillan Publishing Company,
New York, 1992.
15. Potter, S., ARCADIS G & M, Inc., personal communications, 1997, 1998, 1999, 2000.
16. Bent, Tim, Bridgestone-Firestone, Inc., personal communication, 1997.
17. Schroeder, D. R. et al., The Hydrologic Evaluation of Landfill Performance (HELP)
Model: Users Guide for Version 3, EPA/600/9-94/1689, USEPA Risk Reduction
Engineering Laboratory, Cincinnati, OH, 1994.
18. Ecolotree, Inc. and CH2H-Hill, Inc., Ecolotree Cap System; Focused Feasibility Study
for Selected Virginia Landfills, April 22, 1996.
19. Khire, M. V., C. H. Benson, and P. J. Bosschur, Water balance modeling of earthen
final covers, J. Geotech. Geoenviron. Eng., 123, 744754, 1997.
20. Anderson, J. E., Soil Plant Cover Systems for Final Closure of Solid Waste Landfills
in Arid Regions, in Landfill Capping in the Semi-Arid West: Problems, Perspectives,
and Solutions, Environmental Science and Research Foundation, Idaho Falls, ID,
1997, 2738.
21. ARCADIS G & M, Inc., Proprietary Software PHYTOSOLVE for Phyto Cover Evaluation, 1998.
22. Soil Conservation Service, Urban Hydrology for Small Watersheds, Technical Release
55, 1986.
23. Schultz, E. F., Problems in Applied Hydrology, Water Resource Publications, Fort
Collins, CO, 1973.
24. Stewart, B. A. and D. R. Nielson, Irrigation of Agricultural Crops, Agronomy No.
30, American Society of Agronomy and Soul Science Society of America, Madison,
WI, 1990.
25. Maidment, D. R., Ed., Handbook of Hydrology, McGraw-Hill, Inc., New York, 1993.
26. Fedder, R. A., P. J. Kowalrik, and H. Zaradyn, Simulation of Field Water Use and
Crop Yield, Centre for Agricultural Publishing and Documentation, Wageningen,
Netherlands, 1978.
27. Sharpley, A. N. and J. R. Williams, Eds., Erosion/Productivity Impact Calculator: 1.
Model Documentation, Technical Bulletin, 1768, U.S. Dept. Agric., Washington,
D.C., 1990.
364
28. American Society of Civil Engineers (ASCE), Evapotranspiration and Irrigation

Water Requirements, ASCE Press, New York, 1990.
29. Knisel, W. G. Ed., CREAMS: A Field Scale Model for Chemicals Runoff and Erosion
from Agricultural Management Systems, U.S. Dept. Agric., Conservation Research
Report, No. 26, 345, 1980.
30. Hannum, E., ARCADIS G & M, Inc., personal communications, 1999, 2000.
L1282/Appendix A/frame Page 365 Monday, June 18, 2001 9:16 AM
APPENDIX
Physical Properties of Some Common

Environmental Contaminants
365
Compound
154.21
152.20
58.08
56.06
53.06
364.92
178.24
44.05
60.05
102.09
41.05
223.27
71.08
58.08
76.53
114.14
169.23
94.12
17.04
130.19
130.19
93.13
123.15
23.15
202.27
Molecular
Weight
7.92 105 (25C)

2.8 104
3.97 105 (25C)
4.4 106 (25C)
1.10 104 (25C)
4.96 104
6.51 105 (25C)
6.61 105 (25C)
1.23 103 (25C)
3.92 106 (20C)
3.46 106 (25C)
3.03 103 (20C)

5.00 106 (25C)
1.08 102 (25C)
3.83 106 (20C)
3.89 1010 (25C)
2.91 104 (20C)

3.88 104 (25C)
4.87 104 (20C)
0.136 (25C)
1.25 106 (25C)
Henrys Law Constant

atmm3/mol
Physical Properties of Some Common Environmental Contaminants
0.00155 (25C)
0.0290 (20C)
266 (25C)
265 (25C)
110-115 (25C)
6 106 (25C)
1.95 x 104 (25C)
760 (20.2C)
11.4 (20C)
5 (25C)
73 (20)
7 103 (20C)
20 (20C)
360 (25C)
3.6 (20C)
6 x 105 (2030C)
Low
10 atm (25.7C)
4.1 (25C)
10 (35.2C)
0.6 (20C)
0.1 (30C)
0 (20C)
Vapor Pressure
mm Hg.
3.47 (25C)
3.93 (25C)
Miscible
200,000 (25C)
80,000 (25C)
0.011 (25C)
0.075 (25C)
Miscible
Miscible
12% by wt. (20C)
Miscible
2.155 g/L (30C)

Miscible
141 g/L
842 (2030C)
100 wt. % at (20C)
531g/L (20C)
1.8 g/L (20C)
0.2 wt. % (20C
1.3 wt. % (20C)

3.3 (Room Temp)
600 (20C)
Solubility mg/L
1.25
3.68
0.43
0.28
1.13
2.61
4.41
Unavailable
Unavailable
Unavailable
0.34
3.20
Unavailable
0.51
1.68
Unavailable
2.03
Unavailable
0.49
Unavailable
Unavailable
1.41
Unavailable
Unavailable
Log Koc
366
Acenaphthene
Acenaphthylene
Acetone
Acrolein
Acrylonitrile
Aldrin
Anthracene
Acetaldehyde
Acetic Acid
Acetic Anhydride
Acetonitrile
2-Acetylaminofluorene
Acrylamide
Allyl Alcohol
Allyl Chloride
Allyl Glycidyl Ethe
4-Aminobiphenyl
2-Aminopyridine
Ammonia
n-Amyl Acetate
sec-Amyl Acetate
Aniline
o-Anisidine
p-Anisidine
Antu
Table A1
78.11
84.24
228.30
252.32
252.32
122.12
276.34
252.32
108.14
312.37
290.83
290.83
290.83
173.04
143.01
171.07
390.57
163.83
252.73
249.20
72.11
252.32
126.59
154.21
157.01
129.39
148.91
54.09
58.12
Benzene
Benzidine
Benzo[a]anthracene
Benzo[b]fluoranthene
Benzo[k]fluoranthene
Benzoic Acid
Benzo[ghi]perlene
Benzo[a]pyrene
Benzyl Alcohol
Benzyl Butyl Phthalate

-Bhc
-Bhc
-Bhc
Bis(2-chloroethoxy) Methane
Bis(2-chloroethyl) Ether
Bis(2-chloroisopropyl) Ether
Bis(2-Ethylhexyl) Phthalate
Bromodichloromethane
Bromoform
4-Bromophenyl Phenyl Ether
2-Butanone
Benzo[e]pyrene
Benzyl Chloride
Biphenyl
Bromobenzene
Bromochloromethane
Bromotrifluoromethane
1, 3-Butadiene
n-Butane
B
0.00548 (25C)
3.88 1011 (25C)
8.0 106
1.2 105 (20-25C)
0.00104
7.02 108
1.4 107 (25C)
< 2.4 106
Insufficient vapor
pressure data for
calculation at 25C
1.3 106 (25C)
5.3 106 (20C)
2.3 107 (20C)
2.5 107 (20-25C)
3.78 107
1.3 105
1.1 104
1.1 105 (25C)
2.12 104
5.6 104
1.0 104
4.66 105 (25C)
4.84 107 (25C)
3.04 104 (20C)
4.15 104 (25C)
2.4 103 (25C)
1.44 103 (2425C)
5.00 101 (25C)
6.3 102 (25C)
9.30 101 (25C)
1800 (25C)
500 (25C)
0.014 (25C)
0.0012 (25C)
0.00055 (25C)
3400 (25C)
0.00026 (25C)
0.0038 (25C)
42,900 (25C)
42.2 (25C)
2.0 (25C)
0.24 (25C)
31.4 (25C)
81,000 (25C)
10,200 (25C)
1700 (20C)
0.4 (25C)
4500 (0C)
3.130 (25C)
No data found
25.57 wt. % (25C)
0.0038 (25C)
493 (20C)
7.5 (25C)
409 (25C)
0.129 M (25.0C)
0.03 wt. % (20C)
735 (20C)
61 (20C)
95.2 (25C)
0.83 (20C)
1.1 107 (25C)
5 107 (20C)
9.59 1011 (25C)
0.0045 (25C)
1.01 1010 (25C)
5.6 109 (25C)
1 (58C)
8.6 106 (20C)
2.5 105 (20C)
2.8 107 (20C)
.7 105 (20C)
1 (53C)
1.55 (25C)
0.85 (20C)
6.2 108 (25C)
50 (20C)
5.6 (25C)
0.0015 (20C)
100 (25.0C)
5.54 109 (25C)
1 (22.0C)
102 (25C)
4.14 (25C)
141.07 (24.05C)
149 (20C)
2105 (25C)
1820 (25C)
.832.54
3.279
3.553
3.279
2.06
1.15
1.79
5.0
1.79
2.45
4.94
0.09
5.6
2.28
3.71
2.33
1.43
2.44
2.08
Unavailable
1.92
.60
6.14
5.74
6.64
1.482.70
6.89
5.606.29
1.98
PHYSICAL PROPERTIES OF SOME COMMON ENVIRONMENTAL CONTAMINANTS

367
Compound
76.13
153.82
409.78
409.78
409.78
127.57
112.56
142.59
64.52
106.55
119.38
Carbon Dissulfide
Carbon Tetrachloride
Chlordane
cis-Chlordane
trans-Chlordane
4-Chloroaniline
Chlorobenzene
p-Chloro-m-cresol
Chloroethane
2-Chloroethyl Vinyl Ether
Chloroform
0.0133
0.024 (20C)
4.8 105
Insufficient vapor
pressure data for
calculation at 25C
Insufficient vapor
pressure data for
calculation at 25C
1.07 105 (25C)
0.00445 (25C)
1.78 106
0.0085 (25C)
2.5 104
0.0032 (25C)
2.5 10 (25C)
2.36 106
3.3 104 (25C)
1.91 104 (20C)
8.81 106 (25C)

1.02 105 (25C)
1.20 105 (25C)
1.25 102 (25C)
1.14 102 (25C)
1.17 102 (25C)
7.04 103 (2022C)
Henrys Law Constant

atmm3/mol
0.025(25C)
11.8 (25C)
No data found
1064 (20C)
26.75 (20C)
198 (25C)
No data found
360 (25C)
113 (25C)
1 105 (25C)
No data found
2230 (25C)
0.76 (20C)
15 (25C)
10 (20C)
7.0 (25C)
13 (20C)
42 (25C)
1.03 (25C)
1.81 (25C)
2.14 (25C)
55.5 (25C)
Vapor Pressure
mm Hg.
3.9 g/L (2025C)

502 (25C)
3850 (25C)
5,740 (20C)
15,000 (20C)
9300 (25C)
No data found
2300 (22C)
1.160 (25C)
1.85 (25C)
0.051 (2025C)
222 (25C)
Miscible
5000 (25C)
0.8 wt. % (20C)
74,700 (25C)
201,000 (20C)
Miscible
1.26 (25.0C)
309 (25.0C)
34 (25.0C)
590 (22C)
Solubility mg/L
2.42
1.68
2.89
0.51
0.82
1.64
6.0
2.382.55
2.35
5.57
6.0
Unavailable
Unavailable
Unavailable
Unavailable
Unavailable
Unavailable
Unavailable
Unavailable
3.40
2.95
2.83
Unavailable
Log Koc
368
56.11
118.18
116.16
116.16
116.16
74.12
74.12
74.12
134.22
134.22
134.22
90.18
Molecular
Weight
Physical Properties of Some Common Environmental Contaminants (Continued)
1-Butene
Butoxyethano
n-butyl Acetate
sec-Butyl Acetate
tert-Butyl Acetate
n-Butyl Alcohol
sec-Butyl Alcohol
tert-Butyl Alcohol
n-Butylbenzene
sec-Butylbenzene
tert-Butylbenzene
n-Butyl Mercaptan
Table A1
p, p DDD
p, p DDE
p, p DDT
157.56
123.54
164.38
88.54
350.59
70.09
98.19
84.16
100.16
98.14
82.15
66.10
p-Chloronitrobenzene
l-Chloro-1-nitropropane
Chloropicrin
Chloroprene
Chloropyrifos
Crotonaldehyde
Cycloheptane
Cyclohexane
Cyclohexanol
Cyclohexanone
Cyclohexene
Cyclopentadiene
320.05
319.03
354.49
70.13
68.12
154.60
188.61
-Chloroacetophenone
o-Chlorobenzylidenemalonitrile
Cyclopentane
Cyclopentene
162.62
128.56
204.66
228.30
152.24
201.22
221.26
78.50
2-Chloronaphthalene
2-Chlorophenol
4-Chlorophenyl Phenyl Ether
Chrysene
Camphor
Carbaryl
Carbofuran
Chloroacetaldehyde
400 (31.0C)
1.86 101 (25C)

6.3 102 (25C)
1.02 106 (30C)

6.49 106 (30C)
1.9 x 107 (25C)
<1 (20C)
5.8 (25C)
23.8 (25C)
200 (20C)
1.87 105 (25C)
30 (20C)
95 (20C)
1 (20C)
4 (20C)
67 (20C)
<6.91 103 (20C)

1.57 101 (2025C)
8.4 102
3.20 102
4.16 106 (25C)
1.96 105
1.94 101 (25C)

5.74 106 (25C)
1.2 105 (25C)
4.6 102 (25C)
2.16 105
2.34 105
5.2 105
0.012 (20C)
3.4 x 105 (20C)
0.017 (25C)
1.42 (25C)
0.0027 (25C)
6.3 x 10-9 (25C)
0.18 (20C)
6.578 106 (25C)
2 105 (33C)
100 (20C)
Not applicable reacts with

water
6.12 104
5.6 107 (25C)
2.2 104
7.26 1020
3.00 105 (20C)
1.27 105 (20C)
3.88 108 (3033C)
0.160 (24C)
0.0013 (25C)
0.0004 (25C)
0.003 wt. % (20C)

<0.8 wt. % (20C)
1.621 g/L (25C)
2 (25C)
18.1 wt. % (20C)
30 (25C)
58.4 (25C)
36,000 (20C)
23,000 (20C)
213 (25C)
0.0103 mol/L at room
temperature
164 (25C)
535 (25C)
6.74 (25C)
28,000 (25C)
3.3 (25C)
0.006 (25C)
0.12% (20C)
0.4105 (25C)
700 (25C)
about 50 wt. %, forms a
hemihydrate
Miscible
water
4.64
6
6.26
Unavailable
Unavailable
Unavailable
Not applicable
reacts with
water
2.68
3.34
0.82
3.86
Unavailable
Unavailable
Unavailable
Unavailable
Unavailable
Unavailable
Unavailable
3.93
2.56
3.6
5.39
Unavailable
2.42
2.2
Unavailable

369
208.28
278.35
147.00
147.00
147.00
253.13
120.91
98.96
98.96
96.94
96.94
163.00
112.99
110.97
110.97
380.91
222.24
122.17
194.19
198.14
184.11
182.14
182.14
390.57
Dibromochloromethane
Di-n-butyl Phthalate
1, 2-Dichlorobenzene
1, 3-Dichlorobenzene
1, 4-Dichclorobenzene
3, 3-Dichlorobenzidine
Dichlorodifluoromethane
1, 1-Dichloroethane
1, 2-Dichloroethane
1, 1-Dichloroethylene
trans-1, 2-Dichloroethylene
2, 4-Dichloropheno
1, 2-Dichlorophenol
cis-1, 3-Dichloropropylene
trans-1, 3-Dichloropropylene
Dieldrin
Diethyl Phthalate
2, 4-Dimethylphenol
Dimethyl Phthalate
4, 6-Dinitro-o-cresol
2, 4-Dinitrophenol
2, 4-Dinitrotoluene
2, 6-Dinitrotoluene
Di-n-octyl Phthalate
Molecular
Weight
278.36
168.20
Compound
76 (20C)
1.4 10-5 (25C)
1.5 (25C)
2.3 (25C)
0.4 (25C)
1 105 m/L (22C)
4.887 (25C)
234 (25C)
87 (25C)
591 (25C)
410 (30C)
0.089 (25C)
50 (25C)
43 (25C)
34 (25C)
1.8 107 (25C)
0.22 (0.7) Pa
(25C)
0.098 (25C)
0.22 0.7 Pa (25C)
5.2 105 (25C)
0.00039 (20C)
1.1 104 (20C)
3.5 104 (20C)
0.0014 mm (25C)
10 (20C)
No data found
10
Vapor Pressure
mm Hg.
7868 (25C)
4320 (25C)
250 (25C)
6000 (25C)
270 (22C)
300
3 (25C)
4000 (20C)
400 (25C)
145 (25C)
143 (25C)
74 (25C)
3.11 (25C)
280 (25C)
5060 (25C)
8300 (25C)
5000 (25C)
6300 (25C)
4500 (25C)
2800 (25C)
2700 (25C)
2800 (25C)
0.20 (25C)
1000 (25C)
0.00249 (25C)
10 (25C)
Solubility mg/L
2.07
1.63
2.64
1.25
1.79
1.79
8.99
1.92
3.14
3.23
3.23
2.2
3.3
2.56
1.48
1.15
1.81
1.77
2.94
1.71
1.68
1.68
4.55
1.84
6.22
3.914.10
Log Koc
370
6.55 106 (25C)

4.2 107
1.4 106
1.57 108 (1820C)
8.67 107
2.17 107
1.41 1012 (25C)
7.33 10
Insufficient vapor
pressure data for
calculation at (25C)
9.9 104
6.3 105
0.0024 (25C)
0.0047 (25C)
0.00445 (25C)
4.5 108 (25C)
0.425 (25C)
0.00587 (25C)
9.8 104 (25C)
0.021
0.00674 (25C)
6.66 106
0.00294 (25C)
0.00355
0.00355
2 107
8.46 107
Henrys Law Constant

atmm3/mol
Dibenz[a,h]anthracene
Dibenzofuran
Table A1
184.24
221.04
138.25
142.28
116.16
235.91
236.36
209.82
197.03
120.91
114.96
220.98
73.14
117.19
203.83
203.83
142.24
101.19
115.18
45.08
225.30
121.18
86.18
86.18
112.22
112.22
73.09
60.10
1, 2-Diphenylhydrazine
2, 4-D
Decahydronaphthalene
n-Decane
Diacetone Alcohol
1, 4-Dibromobenzene
1, 2-Dibromo-3-chloropropane
Dibromodifluoromethane
1-3-Dichloro-5, 5
Dimethylhydantoin
Dichlorofluoromethane
sym-Dichloromethyl Ether
Dichlorvos
Diethylamine
2-Diethylaminoethanol
1, 1-Difluorotetrachloroethane
1, 2-Difluorotetrachloroethane
Diisobutyl Ketone
Diisopropylamine
N, N-Dimethylacetamide
Dimethylamine
p-Dimethylaminoazobenzene
Dimethylaniline
2, 2-Dimethylbutane
2, 3 -Dimethylbutane
cis-1, 2-Dimethylcyclohexane
trans-1, 4-Dimethylcyclohexane
Dimethylformamide
1, 1-Dimethylhydrazine
688 (20C)
760 (8.9C)
0.0527 (25C)
195 (20C)
1 (20C)
40 (19.8C)
40 (19.8C)
1.7 (20C)
60 (20C)
1.3 (25C)
1520 (10C)
1 (29.5C)
319.1 (25C)
234.6 (25C)
14.5 (25C)
22.65 (25C)
3.7 mm (25C)
157 (25C)
2.42 102 (2030C)

water
5.0 103
2.56 105 (25C)
1.07 101 (20C)

6.36 104 (20C)
1.77 105 (25C)
4.98 106 (20C)

1.943 (25C)
1.18 (25C)
3.54 101 (25C)
8.70 101 (25C)
2.45 109 (25C)
1.35 (25C)
1 (22.0C)
0.161 (25C)
0.8 (21C)
1.87 101 (25C)
5.0 104 (25C)

2.49 104 (20C)

water
2.6 105 (25C)

0.0047 (20C)
1 (22.5C)
4.11 1011 (25C)

1.95 102 (20C)
39.2 (25C)
1 wt. % (20C)
815,000 (14C)
Miscible
0.01 wt. % (20C)

0.05 wt. % (20C)
Miscible
Miscible
Miscible
13.6 (2030C)
1105.2 (25C)
21.2 (25C)
19.1 (25C)
6.0 (25C)
3.84 ppm (25C)
Miscible
Miscible
1 wt. % (20C)
Decomposes
0.022 (25C)
Miscible
16.5 (25C)
1000 at room
temperature
0.21 wt. % (25C)
221 (25C)
890 ppm (25C)
0.889 ppm (25C)
Not applicable
reacts with
water
1.57
Not applicable
reacts with
water
9.57
Unavailable
Unavailable
2.78
Unavailable
Unavailable
Unavailable
Unavailable
3
Unavailable
Unavailable
Unavailable
Unavailable
Unavailable
Unavailable
0.7
Unavailable
Unavailable
3.2
2.11
2.82
1.68
Unavailable

371
Compound
406.92
406.92
422.92
380.92
380.92
06.17
92.53
323.31
61.08
90.12
132.18
88.11
100.12
-Endosulfan
-Endosulfan
Endosulfan Sulfate
Endrin
Endrin Aldehyde
Ethylbenzene
Epichlorohydrin
EPN
Ethanolamine
2-Ethoxyethanol
2-Ethoxyethyl Acetate
Ethyl Acetate
Ethyl Acrylate
100.20
100.20
100.20
72.15
157.22
126.13
168.11
168.11
168.11
88.11
233.11
174.34
Molecular
Weight
1.01 104 (25C)

1.91 105 (25C)
Insufficient vapor
pressure data for
calculation
5.0 107
3.86 107 (25C)
0.00868 (25C)
2.382.54 105 (20C)
9.07 107 (20C)

1.34 104 (25C)
1.942.59 103 (20C)
1.73 (25C)
3.152 (25C)
1.84 (25C)
2.18 (25C)
2.96 106 (20C)

<1.47 103 (20C)
2.75 107 (35C)
4.79 107 (35C)
4.88 106 (25C)
1.46 109 (2530C)
24.2 (25C)
Henrys Law Constant

atmm3/mol
0.530 (25C)
0.280 (25C)
0.117
0.26 (25C)
0.26 (25C)
152 (25C)
60,000 (20C)
Miscible
Miscible
23 wt. % (20C)
100 ml/L (25C)
.5 wt. % (20C)
7 107 (25C)
2 107 (25C)
10 (25.9C)
13 (20C)
0.0003 (100C)
<1 (20C)
4 (20C)
2 (20C)
94.5 (25C)
29.5 (20C)
5.25 (25C)
5.50 (25C)
5.94 (25C)
33.2 (25C)
1.795 (25C)
2.8 wt. % (20C)
0.015 wt. % (20C)
0.05 wt. % (20C)
0.01 wt. % (20C)
Miscible
42 (25C)
0.008 (25C)
Solubility mg/L
105 (25C)
105 (25C)
No data found
100 (33.3C)
98.4 (25C)
82.8 (25C)
1.287 (25C)
0.5 (20C)
<1 (20C)
8.15 104 (35C)
2.25 104 (35C)
37 (25C)
2 107 (30C)
0.057 (25C)
Vapor Pressure
mm Hg.
3.92
4.43
1.98
1
3.12
Unavailable
Unavailable
Unavailable
Unavailable
Unavailable
3.31
3.37
3.37
Unavailable
Unavailable
Unavailable
Unavailable
0.61
Unavailable
2.18
Unavailable
0.54
2.51
Unavailable
Log Koc
372
2, 3-Dimethylpentane
2, 4 Dimethylpentane
3, 3-Dimethylpentane
2, 2-Dimethylpropane
2, 7-Dimethylquinoline
Dimethyl Sulfate
1, 2-Dinitrobenzene
1, 3-Dinitrobenzene
1, 4-Dinitrobenzene
Dioxane
Diuron
n-Dodecane
Table A1
Heptachlor
Heptachlor Epoxide
Hexachlorobenzene
Hexachchlorobutadiene
Hexachlorocyclopentadiene
Hexachloroethane
2-Hexanone
Glycidol
Fluoranthene
Fluorene
Formaldehyde
Formic Acid
Furfural
Furfuryl Alcohol
Ethylamine
Ethyl Bromide
Ethylcyclopentane
Ethylene Chlorohydrin
Ethylenediamine
Ethylene Dibromide
Ethylenimine
Ethyl Ether
Ethyl Formate
Ethyl Mecaptan
4-Ethylmorpholine
2-Ethylthiophene
373.32
389.32
284.78
260.76
272.77
236.74
100.16
74.08
202.26
166.22
30.03
46.03
96.09
98.10
45.08
108.97
98.19
80.51
60.10
187.86
43.07
74.12
74.08
62.13
115.18
112.19
0.0023
3.2 105
0.0017
0.026
0.016
0.0025
0.00175 (25C)
0.0169 (25C)
2.1 104
3.27 107
1.67 107 at pH 4
1.523.05 106 (20C)
1.07 105 25C)

7.56 103 (25C)
2.10 102 (25C)
1.73 109 (25C)

7.06 104 (25C)
1.33 107 (25C)
1.28 103 (25C)
2.23 104 (25C)
2.74 103 (25C)
4 104 (25C)
2.6 106 (20C)
1.089 105 (20C)
0.15 (20C)
0.081 (25C)
0.8 (30C)
3.8 (25C)
0.9 (25C)
5.0 10-6 (25C)

10 (146C)
400 (33C)
35 (20C)
2 (20C)
0.4 (20C)
400 (2.0C)
386 (20C)
40 (25.0C)
8 (25C)
10 (21.5C)
11 (25C)
250 (30C)
442 (20C)
194 (20C)
527.2 (25C)
6.1 (20C)
60.9 (60.3C)
180 ppb (25C)

0.350 (25C)
0.006 (25C)
3.23 (25C)
1.8 (25C)
27.2 (25C)
35,000 (25C)
Miscible
0.265 (25C)
1.98 (25C)
Miscible
Miscible
8.3 wt. % (20C)
Miscible
Miscible
0.9 wt. % (20C)
245 (25C)
Miscible
Miscible
3370
Miscible
6.05 wt. % (25C)
118,000 (25C)
1.3 wt. % (20C)
Miscible
292 (25C)
4.34
4.32
3.59
3.67
3.63
3.34
2.13
Unavailable
4.62
3.7
0.56
Unavailable
Unavailable
Unavailable
Unavailable
2.67
Unavailable
Unavailable
Unavailable
1.64
0.11
Unavailable
Unavailable
Unavailable
Unavailable
Unavailable

373
Compound
Indeno[1, 2, 3-cd]pyrene
Isophorone
Indan
Indole
Indoline
1-Iodopropane
Isoamyl Acetate
Isoamyl Alcohol
Isobutyl Acetate
Isobutyl Alcohol
Isobutyl Benzene
Isopropyl Acetate
Isopropylamine
Isopropylbenzene
Isopropyl Ether
276.34
138.21
118.18
117.15
169.99
130.19
88.15
116.16
74.12
134.22
102.13
59.11
120.19
102.18
2.96 1020 (25C)

5.8 106
9.09 103
5.87 102 (25C)
8.89 106 (20C)
4.85 104 (25C)
9.25 106 (20C)
1.09 102 (25C)
2.81 104 (25C)
1.47 102 (25C)

9.97 103 (25C)
2.035 (25C)
1.44 104 (25C)
4.20 105 (20C)
4.13 101 (20C)
4.22 101 (25C)
1.184 (25C)
4.35 101 (25C)
4.38-5.84 103 (20C)
<2.07 109 (2025C)
Henrys Law Constant

atmm3/mol
010 (25C)
0.38 (20C)
43.1 (25C)
4 (20C)
2.3 (20C)
20 (25C)
10.0 (20C)
2.06 (25C)
73 (25C)
478 (20C)
4.6 (25C)
150 (25C)
45.85 (25C)
2.6 (20C)
1.4 (25C)
48 (25C)
49 (25C)
151.5 (25C)
186.0 (25C)
4 (20C)
1 (132.4)
Vapor Pressure
mm Hg.
0.062
12,000 (25C)
88.9 (25C)
3558 (25C)
10,800 (25C)
0.1065 wt. % (23.5C)
0.2 wt. % (20C)
26,720 (22C)
6300 (25C)
8.7 wt. % (20C)
33.71 (25C)
18,000 (20C)
Miscible
48.3 (25C)
0.65 wt. % (25C)
2.24 (25C)
0.43 wt. % (25C)
14,300 (20C)
15 (25C)
15 (25C)
9.47 (25C)
50 (25C)
0.013 wt. % (20C)
70,000 (25C)
Solubility mg/L
7.49
1.49
2.48
1.69
1.42
2.16
1.95
Unavailable
Unavailable
Unavailable
3.9
Unavailable
Unavailable
3.45
Unavailable
Unavailable
Unavailable
Unavailable
Unavailable
Unavailable
Unavailable
Unavailable
Unavailable
0.98
Log Koc
374
100.20
114.19
114.19
98.19
98.19
86.18
84.16
144.21
110.11
Molecular
Weight
n-Heptane
2-Heptanone
3-Heptanone
cis-2-Heptene
trans-2-Heptene
n-Hexane
l-Hexene
sec-Hexyl Acetate
Hydroguinone
Table A1
94.94
50.48
84.93
142.20
100.16
108.14
108.14
330.36
98.06
98.14
74.08
86.09
76.10
32.04
31.06
107.16
192.96
Methyl Bromide
Methyl Chloride
Methylene Chloride
2-Methylnaphthalene
4-Methyl-2-Pentanone
2-Methylphenol
4-Methylphenol
Malathion
Maleic Anhydride
Mesityl Oxide
Methyl Acetate
Methyl Acrylate
Methylal
Methyl Alcohol
Methylamine
Methylaniline
2-Methylanthracene
290.83
345.66
490.68
Methoxychlor
Lindane
Kepone
4.01 106 (20C)

9.09 105 (25C)
1.231.44 104 (20C)
1.73 x 104 (25C)
4.66 106 (25C)
1.81 102 (25C)
1.19 105 (25C)
Insufficient vapor
pressure data for
calculation at (25C)
0.2
0.010 (25C)
0.00269 (25C)
Insufficient vapor
pressure data for
calculation
1.49 105 (25C)
1.23 106 (25C)
7.92 107 (25C)
4.89 x 109 (25C)
water
4.8 107
3.11 102 (25C)
8.7 (20C)
235 (25C)
70 (20C)
400 (25C)
127.2 (25C)
3.1 atm (20C)
<1.0 (20C)
15 (20C)
0.24 (25C)
0.108 (25C)
7.95 106 (25C)
5 105 (20C)
1633 (25C)
3789 (20C)
455 (25C)
No data found
No data found
6.7 105 (25C)
2.25 (25C)
3 wt. % (20C)
240,000 (20C)
52,000
33 wt. % (20C)
Miscible
9.590 (25C)
5.624 g/L (25C)
0.039 (25C)
1.91 wt. % (25C)

25,000 (25C)
23,000 (25C)
330 (30C)
13,000 (25C)
7400 (25C)
13,000 (25C)
25.4 (25C)
0.1 (25C)
7.52 (25C)
2.7 (2025C)
0.79
1.34
1.69
2.46
Not applicable
reacts with
water
Unavailable
Unavailable
Unavailable
Unavailable
Unavailable
Unavailable
Unavailable
5.12
1.92
1.4
0.94
3.93
4.9
3.03
4.74
L1282/Appendix A/frame Page 375 Tuesday, June 19, 2001 1:13 PM

375
Compound
68.12
72.15
70.13
76.10
118.13
98.19
112.17
96.17
84.16
60.05
114.23
128.21
100.20
100.20
46.07
141.94
57.05
48.10
100.12
128.26
86.18
86.18
84.16
84.16
192.26
58.12
56.11
118.18
Molecular
Weight
2
7.7 10 (25C)
1.35 (25C)
5.35 101 (25C)
4.35 101 (25C)
3.62 101 (25C)

2.23 104 (25C)
3.70 (25C)
1.30 104 (20C)
3.42 (25C)
1.551.64 (25C)
5.87 103 (25C)

3.89 104 (20C)
3.01 103 (25C)
2.46 104 (20C)
10.27 (25C)
1.732 (25C)
1.693 (25C)
2.77 101 (25C)
6.15 101 (25C)
1.171 (25C)
2.1 101 (25C)
Henrys Law Constant

atmm3/mol
550.1 (25C)
687.4 (25C)
902.1 (25C)
6 (20C)
7 (20C)
46.3 (25C)
1 (20C)
137.5 (25C)
625 (25C)
19.5 (25C)
2 (25C)
65.9 (25C)
61.6 (25C)
49.6 (25C)
405 (25C)
348 (20C)
1516 (25C)
40 (26C)
7 (25C)
211.8 (25C)
189.8 (25C)
195.4 (25C)
270.8 (25C)
10 atm (66.8C)
2.270 (25C)
1.9 (20C)
Vapor Pressure
mm Hg.
2-Methyl-1, 3-Butadiene
2-Methylbutane
3-Methyl-1-Butene
Methyl Cellosolve
Methyl Cellosolve Acetate
Methylcyclohexane
o-Methylcyclohexanone
l-Methylcyclohexene
Methylcyclopentane
Methyl Formate
3-Methylheptane
5-Methyl-3-Heptanone
2-Methylhexane
3-Methylhexane
Methylhydrazine
Methyl Iodide
Methyl Isocyanate
Methyl Mercaptan
Methyl Methacrylate
4-Methyloctane
2-Methylpentane
3-Methylpentane
2-Methyl-1-Pentene
4-Methyl-1-Pentene
1-Methylphenanthrene
2-Methylpropane
2-Methylpropene
-Methylstyrene
Table A1
642 (25C)
49.6 (25C)
130 (25C)
Miscible
Miscible
16.0 (25C)
52 (2C)
41.8 (25C)
30 wt. % (20C)
0.792 (25C)
0.26 wt. % (20C)
2.54 (25C)
4.95 (25C)
Miscible
2 wt. % (20C)
6.7 wt. % (20C)
23.30 g/L (20C)
1.5 wt. % (20C)
0.115 (25C)
13.8 (25C)
17.9 (25C)
78 (25C)
48 (25C)
269 ppb (25C)
48.9 (25C)
263 (25C)
Solubility mg/L
Unavailable
Unavailable
Unavailable
Unavailable
Unavailable
Unavailable
Unavailable
Unavailable
Unavailable
Unavailable
Unavailable
Unavailable
Unavailable
Unavailable
1.36
Unavailable
Unavailable
Unavailable
Unavailable
Unavailable
Unavailable
Unavailable
Unavailable
4.56
Unavailable
Unavailable
Log Koc
376
128.18
138.13
138.13
138.13
123.11
139.11
139.11
74.09
198.22
130.19
380.79
143.19
143.19
230.90
199.21
75.07
61.04
89.09
89.09
137.14
137.14
4-Nitroaniline
Nitrobenzene
2-Nitrophenol
4-Nitrophenol
N-Nitrosodimethylamine
N-Nitrosodiphenylamine
N-Nitrosodi-n-Propylamine
Naled
1-Naphthylamine
2-Naphthylamine
Nitrapyrin
4-Nitrobiphenyl
Nitroethane
Nitromethane
1-Nitropropane
2-Nitropropane
2-Nitrotoluene
3-Nitrotoluene
224.16
87.12
Naphthalene
2-Nitroaniline
3-Nitroaniline
Mevinphos
Morpholine
4.66
2.86
8.68
1.23
4.51
5.41
105 (25C)
105
105 (25C)
104 (25C)
105 (20C)
105 (20C)
2.13 103
2.01 109 (25C)
1.27 1010 (25C)
4.6 104
9.72 105 (25C)
Insufficient vapor
pressure data for
calculation
1.14 108 (25C)
2.45 105
3.5 106
3.0 105 (20C)
0.143 (25C)
2.33 108 (25C)
Insufficient vapor
pressure data to
calculate
45 ml/L (20C)
22 ml/L (20C)
1.4 wt. % (20C)
1.7 wt. % (20C)
0.06 wt. % (20C)
0.05 wt. % (20C)
40
586 (2030C)
1700
2 104 (20C)
6.5 105
(2030C)
2.56 104
(2030C)
0.0028 (20C)
15.6 (20C)
27.8 (20C)
7.5 (20C)
12.9 (20C)
0.15 (20C)
0.25 (25C)
800 (18.5C)
2,000 (25C)
2,000 (25C)
16,000 (25C)
Miscible
35.1 (25C)
9900 (25C)
30 (25C)
1260 (25C)
890 (25C)
Miscible
Miscible
0.0015 (20C)
0.28 (25C)
0.20 (25C)
10-4 (20C)
8.1 (25C)
No data found
No data found
0.23 (25C)
8.1 (25C)
1 (119.3C)
0.003 (20C)
13.4 (25C)
2.64
Unavailable
Unavailable
Unavailable
Unavailable
Unavailable
Unavailable
2.11
Not applicable
reacts with
water
3.51
1.08
2.36
1.57
2.33
1.41
2.76
1.01
2.74
1.231.62
1.26
Unavailable
Unavailable

377
Pentachlorophenol
Phenanthrene
Phenol
Pyrene
Parathion
Pentachlorobenzene
PCB-1254
PCB-1260
PCB-1248
P
257.90
192.00
221.00
154358 with an
average value of
261
222358 with an
average value of
288
327 (average)
324460 370
(average)
266.34
178.24
94.11
202.26
291.27
250.34
403.73
114.23
112.22
90.04
137.14
128.26
Molecular
Weight
0.012 (25C)
0.080 (24C)
7.71 105 (25C)

4.05 105 (25C)
1.7 104 (20C)
6.80 104 (25C)
0.34 (25C)
6.85 107 (25C)
9.8 106 (25C)
6.0 103
(2030C)
0.0027
0.0071
3.4 106
2.56 105 (25C)
3.97 107 (25C)
1.87 105
8.56 108 (25C)
0.0071 (20C)
2025 (25C)
1.18(25C)
93,000 (25C)
0.148 (25C)
24 (25C)
2.24 106 M (25C)
0.054
0.0035
4.94 104 (25C)
0.431 (25C)
2.7 (25C)
9.81 wt. % (25C)
0.005 wt. % (20C)

0.122 (25C)
Solubility mg/L
0.220.25
1.5 (25C)
1.45 (25C)
0.24 (25C)
<1 (20C)
14.14 (25C)
17.4 (25C)
<0.001 (20C)
5.484 (26.0C)
4.3 (25C)
Vapor Pressure
mm Hg.
4 104 (25C)
0.0067 (25C)
0.0046 (25C)
4.06 104 (25C)
750
3.24 104
8.64 104
5.6 104
3.225 (25C
9.52 101 (25C)
1.43 1010 (pH 4)
5.0 10 (25C)
5.95 (25C)
Henrys Law Constant

atmm3/mol
2.96
3.72
1.43
4.66
3.68
6.3
5.61
6.42
5.64
4.7
2.44
2.83
3.71
Unavailable
Unavailable
0.89
Unavailable
Unavailable
Log Koc
378
PCB-1016
PCB-1221
PCB-1232
PCB-1242
Octachloronaphthalene
n-Octane
l-Octene
Oxalic Acid
Compound
4-Nitrotoluene
n-Nonane
Table A1
108.10
105.09
40.06
79.10
n-Propyl Nitrate
Propyne
Pyridine
p-Quinone
68.12
72.15
86.13
70.13
70.13
70.13
140.28
108.14
170.21
108.14
148.12
229.11
230.25
44.10
72.06
102.12
60.10
120.19
112.22
58.08
l, 4-Pentadiene
n-Pentane
2-Pentanone
l-Pentene
cis-2-Pentene
trans-2-Pentene
Pentycyclopentane
p-Phenylenediamine
Phenyl Ether
Phenylhydrazine
Phthalic Anhydride
Picric Acid
Pindone
Propane
-Propiolactone
n-Propyl Acetate
n-Propyl Alcohol
n-Propylbenzene
Propylcyclopentane
Propylene Oxide
202.28
Pentachloroethane
9.48 107 (20C)
0.1 (20C)
18 (20C)
4310 (25C)
20 (25C)
734.6 (25C)
512.8 (25C)
16 (25C)
637.7 (25C)
494.6 (25C)
505.5 (25C)
0.12 (30C)
<0.1 (20C)
2 104 (20C)
<1 (20C)
8.6 atm (20C)

3.4 (25C)
35 (25C)
20.8 (25C)
3.43 (25C)
12.3 (25C)
445 (20C)
1.20 101 (25C)

1.255 (25C)
6.44 105 (25C)
4.06 101 (25C)
2.25 101 (25C)
2.34 101 (25C)
2.13 104 (20C)
6.29 109 (20C)

<2.15 105 (20C)
7.06 101 (25C)

7.63 107 (25C)
1.99 104 (25C)
6.74 106 (25C)
1.0 102 (25C)
8.90 101 (25C)
8.34 105 (20C)
1.1 101 (25C)

8.88 106 (25C)
4.5 (25C)
2.45 103 (25C)
1.5 wt. % (20C)
3640 (20C)
Miscible
7.69 and 500 were

reported at 25C and
20C
558 (25C)
39.5 (25C)
5.51 wt. % (25C)
148 (25C)
203 (25C)
203 (25C)
0.115 (25C)
38,000 (24C)
21 (25C)
0.62 wt. % (20C)

1.4 wt. % (20C)
18 (25C)
62.4 (25C)
37 vol. % (25C)
18,900 (20C)
Miscible
55 (25C)
2.04 (25C)
41 wt. % (20C)
Unavailable
Unavailable
Unavailable
Unavailable
Unavailable
Unavailable
Unavailable
Unavailable
Unavailable
Unavailable
Unavailable
1.9
2.95
Unavailable
Unavailable
Unavailable
Unavailable
2.87
Unavailable
Not applicable
reacts with
water
Unavailable
Unavailable
Unavailable
3.28

379
215.89
1, 2, 3, 5-Tetrachlorobenzene
104.15
334.42
322.30
321.57
Molecular
Weight
321.98
167.85
165.83
92.14
413.82
181.45
133.40
133.40
131.39
137.37
197.45
197.45
255.48
393.70
345.65
215.89
Compound
7.2 1010 (25C)

6 (25C)
20 (25C)
22 (20C)
0.20.4 (25C)
0.29 (25C)
124 (25C)
19 (20C)
72.6 (25C)
792 (25C)
0.022 (25C)
0.017 (25C)
6.46 106 (25C)
0.1 (20C)
2.6 102 (25C)
1 (58.2C)
1.58 103 (25C)
6.45 (25C)
0.00017 (20C)
8 104 (25C)
Vapor Pressure
mm Hg.
5.40 1023 (1822C)

4.56 104 (25C)
0.0153
0.00674 (25C)
0.063
0.00232
0.0162 (25C)
9.09 104 (25C)
0.0091
1.73 (25C)
1.76 107 (25C)
9.07 108 (25C)
4.87 108 (25C)
6.40 105 (20C)

6.9 103 (20C)
2.88 106 (20C)
0.00261
8.46 106 (25C)
Henrys Law Constant

atmm3/mol
5.19 (25C)
0.0193 ppb (22C)

2970 (25C)
150 (25C)
490 (25C)
0.20.4 (25C)
31.3 (25C)
950 (25C)
4,500 (20C)
1100 (25C)
1240 (25C)
1.2 g/L (25C)
800 (25C)
278 (25C)
0.040
0.07 wt. % (20C)
5.92 (25C)
0.031 wt. % (25C)

0.02 wt. % (20C)
25
40 (25C)
Solubility mg/L
6.66
2.07
2.42
2.06
3.18
2.7
2.18
1.75
1.81
2.2
2.85
3.03
1.72
4.82
2.45
5.4 average
value
6.0 average
2.87
2.45
2.87
2.76
Log Koc
380
TCDD
1, 1, 2, 2-Tetrachloroethane
Tetrachloroethylene
Toluene
Toxaphene
1, 2, 4-Trichlorobenzene
1, 1, 1-Trichloroethane
1, 1, 2-Trichloroethane
Trichloroethylene
Trichlorofluoromethane
2, 4, 5-Trichlorophenol
2, 4, 6-Trichloropheno
2, 4, 5-T
1, 2, 4, 5-Tetrabromobenzene
1, 1, 2, 2-Tetrabromoethane
Styrene
Strychnine
Sulfotepp
Ronnel
Table A1
215.89
290.20
72.11
134.22
196.03
287.15
84.14
269.35
174.15
107.16
314.80
266.32
181.45
181.45
147.43
187.38
368.37
101.19
335.29
120.19
120.19
120.19
126.24
112.22
128.26
114.23
114.23
227.13
326.29
Tetraethyl Pyrophosphate
Tetrahydrofuran
1, 2, 4, 5-Tetramethylbenzene
Tetranitromethane
Tetryl
Thiophene
Thiram
2, 4-Toluene Disocyanate
o-Toluidine
1, 3, 5-Tribromobenzene
Tributyl Phosphate
1, 2, 3-Trichlorobenzene
1, 3, 5 Trichlorobenzene
1, 2, 3-Trichloropropane
1, 1, 2-Trichlorotrifluoroethane
Tri-o-Cresyl Phosphate
Triethylamine
Trifluralin
1, 2, 3-Trimethylbenzene
1, 1, 3-Trimethylcyclohexane
1, 1, 3-Trimethylcyclopentane
2, 2, 5-Trimethylhexane
2, 2, 4-Trimethylpentane
2, 3, 4-Trimethylpentane
2, 4, 6-Trinitrotoluene
Triphenyl Phosphate
<0.1 (25C)
1.55 104 (20C)
145 (20C)
0.49 (25C)
13 (25C)
<1 (20C)
79.7 (25C)
0.01 (20C)
0.1 (20C)
1 (40C)
0.58 (25C)
3.4 (20C)
270 (20C)
54 (20C)
1.1 104 (25C)
.51 (25C)
2.03 (25C)
2.42 (25C)
39.7 (25C)
16.5 (25C)
49.3 (25C)
27.0 (25C)
4.26 103 (54.8C)
<0.1 (20C)
1.0 102 (20C)
7.06 105 (25C)

2.49 102 (25C)
<1.89 103 (20C)

2.93 103 (25C)
1.88 106 (25C)
8.9 103 (20C)

1.9 103 (20C)
3.18 104 (25C)
3.33 101 (20C)
4.79 104 (20C)

4.84 x 105 (23C)
3.18 x 103 (25C)
5.7 103 (25C)
3.93 103 (25C)
1.57 (25C)
2.42 (25C)
3.01 (25C)
2.98 (25C)
5.88 102 (2025C)
15,0000 (25C)
2.51 106 (25C)
0.1 wt. % (20C)
18.0 (25C)
6.01 (25C)
0.02 wt. % (20C)

3.1 (25C)
15,000 (20C)
240
75.2 (25C)
51.9 (25C)
48.2 (25C)
1.77 (25C)
3.73 (25C)
1.15 (25C)
2.05 (25C)
1.36 (25C)
0.013 wt. % (20C)
0.001 wt. % (20C)
Miscible
3.48 (25C)
0.02 wt. % (20C)

3015 (25C)
30
water
0.465 (25C)
Miscible
6.1 average
Not applicable
reacts with
water
Unavailable
3.79
2.37
1.73
Not applicable
reacts with
water
2.61
4.05
2.29
3.87
5.7 (average)
2.59
3.37
Unavailable
3.73
3.34
3.57
3.21
Unavailable
Unavailable
Unavailable
Unavailable
Unavailable
2.48
3.72

381
106.17
106.17
106.17
308.33
0.00535 (25C)
0.0063 (25C)
0.0063 (25C)
4.81 104
2.78
Henrys Law Constant

atmm3/mol
6.6 (25C)
8.287 (25C)
8.763 (25C)
115 (25C)
2660 (25C)
Vapor Pressure
mm Hg.
213 (25C)
173 (25C)
200 (25C)
17 (20C)
25,000 (25C)
1100 (25C)
Solubility mg/L
Sources: Montgomery, J. H. and L. M. Welkom, 1990, Groundwater Chemicals Desk Reference, Lewis Publishers, Chelsea, MI.
Montgomery, J. H., 1991, Groundwater Chemicals Desk Reference, Vol. 2, Lewis Publishers, Chelsea, MI.
86.09
62.50
Molecular
Weight
2.11
3.2
2.31
2.96
0.45
0.39
Log Koc
382
o-Xylene
m-Xylene
p-Xylene
Warfarin
Compound
Vinyl Acetate
Vinyl Chloride
Table A1
L1282/Appendix B/frame Page 383 Monday, June 18, 2001 11:29 AM
APPENDIX
Useful Information for

Biogeochemical Sampling
Table B1
Factors Used to Correct Atmospheric Pressures

Adjusted to Sea Level
Elevation of Weather Station

(feet above sea level)
Value to Subtract
(millimeters of mercury)
0
1000
2000
3000
4000
5000
6000
0
27
53
79
104
128
151
Source: USGS Groundwater Sampling Field Manual (Chapter 6).
383
795
15.3
15.1
14.8
14.6
14.4
14.2
14.1
13.9
13.7
13.5
13.3
13.2
13.0
12.8
12.7
12.5
12.4
12.2
12.1
11.9
0.0
0.5
1.0
1.5
2.0
2.5
3.0
3.5
4.0
4.5
5.0
5.5
6.0
6.5
7.0
7.5
8.0
8.5
9.0
9.5
12.4
12.3
12.1
12.0
11.9
13.3
13.1
12.9
12.8
12.6
12.4
12.2
12.1
11.9
11.8
13.2
13.0
12.8
12.7
12.5
14.1
13.9
13.7
13.5
13.3
15.1
14.9
14.7
14.5
14.3
785
12.3
12.1
12.0
11.8
11.7
13.1
12.9
12.8
12.6
12.4
14.0
13.8
13.6
13.4
13.3
15.0
14.8
14.6
14.4
14.2
780
12.2
12.1
11.9
11.8
11.6
13.0
12.8
12.7
12.5
12.4
13.9
13.4
13.5
13.3
13.2
14.9
14.7
14.5
14.3
14.1
775
12.1
12.0
11.8
11.7
11.6
12.9
12.7
12.6
12.4
12.3
13.8
13.6
13.4
13.3
13.1
14.8
14.6
14.4
14.2
14.0
12.0
11.9
11.8
11.6
11.5
12.8
12.7
12.5
12.3
12.2
13.7
13.5
13.3
13.2
13.0
14.7
14.5
14.3
14.1
13.9
12.0
11.8
11.7
11.5
11.4
12.7
12.6
12.4
12.3
12.1
13.6
13.4
13.3
13.1
12.9
14.6
14.4
14.2
14.0
13.8
11.9
11.7
11.6
11.5
11.3
12.7
12.5
12.3
12.2
12.0
13.5
13.3
13.2
13.0
12.8
14.5
14.3
14.1
13.9
13.7
11.8
11.7
11.5
11.4
11.2
12.6
12.4
12.3
12.1
12.0
13.4
13.3
13.1
12.9
12.7
14.4
14.2
14.0
13.8
13.6
11.7
11.6
11.4
11.3
11.2
12.5
12.3
12.2
12.0
11.9
13.3
13.2
13.0
12.8
12.7
14.3
14.1
13.9
13.7
13.5
11.6
11.5
11.4
11.2
11.1
12.4
12.2
12.1
11.9
11.8
13.3
13.1
12.9
12.7
12.6
14.2
14.0
13.8
13.6
13.4
11.6
11.4
11.3
11.2
11.0
12.3
12.2
12.0
11.9
11.7
13.2
13.0
12.8
12.6
12.5
14.1
13.9
13.7
13.5
13.3
11.5
11.3
11.2
11.1
10.9
12.2
12.1
11.9
11.8
11.6
13.1
12.9
12.7
12.6
12.4
14.0
13.8
13.6
13.4
13.3
11.4
11.3
11.1
11.0
10.9
12.2
12.0
11.8
11.7
11.6
13.0
12.8
12.6
12.5
12.3
13.9
13.7
13.5
13.3
13.2
Atmospheric pressure, in millimeters of mercury

770 765 760 755 750 745 740 735 730 725
720
11.3
11.2
11.1
10.9
10.8
12.1
11.9
11.8
11.6
11.5
12.9
12.7
12.6
12.4
12.2
13.8
13.6
13.4
13.2
13.1
715
11.3
11.1
11.0
10.8
10.7
12.0
11.8
11.7
11.5
11.4
12.8
12.6
12.5
12.3
12.1
13.7
13.5
13.3
13.2
13.0
710
11.2
11.0
10.9
10.8
10.6
11.9
11.7
11.6
11.5
11.3
12.7
12.5
12.4
12.2
12.1
13.6
13.4
13.2
13.1
12.9
705
11.1
11.0
10.8
10.7
10.6
11.8
11.7
11.5
11.4
11.2
12.6
12.5
12.3
12.1
12.0
13.5
13.3
13.2
13.0
12.8
700
11.0
10.9
10.7
10.6
10.5
11.7
11.6
11.4
11.3
11.1
12.5
12.4
12.2
12.0
11.9
13.4
13.2
13.1
12.9
12.7
384
14.2
14.0
13.8
13.6
13.4
15.2
15.0
14.7
14.5
14.3
790
Solubility of Oxygen in Water at Various Temperatures and Pressures (Temp C, temperature in degrees Celsius;
atmospheric pressures from 695 to 600 millimeters mercury begin after 40C)
Temp
C
Table B2
11.8
11.7
11.5
11.4
11.3
11.1
11.0
10.9
10.8
10.6
10.5
10.4
10.3
10.2
10.1
10.0
9.9
9.8
9.7
9.6
9.5
9.4
9.3
9.2
9.1
10.0
10.5
11.0
11.5
12.0
12.5
13.0
13.5
14.0
14.5
15.0
15.5
16.0
16.5
17.0
17.5
18.0
18.5
19.0
19.5
20.0
20.5
21.0
21.5
22.0
9.4
9.3
9.2
9.2
9.1
9.9
9.8
9.7
9.6
9.5
10.5
10.4
10.2
10.1
10.0
11.1
10.9
10.8
10.7
10.6
11.7
11.6
11.4
11.3
11.2
9.4
9.3
9.2
9.1
9.0
9.9
9.8
9.7
9.6
9.5
10.4
10.3
10.2
10.1
10.0
11.0
10.9
10.7
10.6
10.5
11.6
11.5
11.4
11.2
11.1
10.8
10.7
10.6
10.5
10.4
11.5
11.4
11.2
11.1
11.0
10.8
10.7
10.5
10.4
10.3
11.4
11.3
11.2
11.0
10.9
10.7
10.6
10.5
10.4
10.2
11.3
11.2
11.1
11.0
10.8
10.6
10.5
10.4
10.3
10.2
11.3
11.1
11.0
10.9
10.8
10.6
10.4
10.3
10.2
10.1
11.2
11.1
10.9
10.8
10.7
9.3
9.2
9.1
9.0
9.0
9.8
9.7
9.6
9.5
9.4
9.3
9.2
9.1
9.0
8.9
9.7
9.6
9.5
9.4
9.3
9.2
9.1
9.0
8.9
8.8
9.7
9.6
9.5
9.4
9.3
9.1
9.0
8.9
8.9
8.8
9.6
9.5
9.4
9.3
9.2
9.1
9.0
8.9
8.8
8.7
9.5
9.4
9.3
9.3
9.2
9.0
8.9
8.8
8.7
8.7
9.5
9.4
9.3
9.2
9.1
10.3 10.3 10.2 10.1 10.1 10.0

10.2 10.2 10.1 10.0 10.0 9.9
10.1 10.0 10.0 9.9 9.8 9.8
10.0 9.9 9.9 9.8 9.7 9.7
9.9 9.8 9.8 9.7 9.6 9.6
10.9
10.8
10.7
10.6
10.4
11.6
11.4
11.3
11.2
11.0
8.9
8.9
8.8
8.7
8.6
9.4
9.3
9.2
9.1
9.0
9.9
9.8
9.7
9.6
9.5
10.5
10.4
10.3
10.1
10.0
11.1
11.0
10.9
10.7
10.6
8.9
8.8
8.7
8.6
8.5
9.3
9.3
9.2
9.1
9.0
9.9
9.8
9.7
9.5
9.4
10.4
10.3
10.2
10.1
10.0
11.0
10.9
10.8
10.7
10.5
10.9
10.8
10.6
10.5
10.4
10.8
10.7
10.6
10.4
10.3
10.7
10.6
10.5
10.4
10.3
10.7
10.5
10.4
10.3
10.2
10.6
10.5
10.3
10.2
10.1
8.8
8.7
8.6
8.6
8.5
9.3
9.2
9.1
9.0
8.9
9.8
9.7
9.6
9.5
9.4
8.8
8.7
8.6
8.5
8.4
9.2
9.1
9.0
8.9
8.9
9.7
9.6
9.5
9.4
9.3
8.7
8.6
8.5
8.4
8.4
9.2
9.1
9.0
8.9
8.8
9.7
9.6
9.5
9.4
9.3
8.6
8.6
8.5
8.4
8.3
9.1
9.0
8.9
8.8
8.7
9.6
9.5
9.4
9.3
9.2
8.6
8.5
8.4
8.3
8.2
9.0
8.9
8.8
8.8
8.7
9.5
9.4
9.3
9.2
9.1
8.5
8.4
8.4
8.3
8.2
9.0
8.9
8.8
8.7
8.6
9.5
9.4
9.3
9.2
9.1
10.4 10.3 10.2 10.1 10.1 10.0

10.2 10.2 10.1 10.0 10.0 9.9
10.1 10.1 10.0 9.9 9.8 9.8
10.0 9.9 9.9 9.8 9.7 9.7
9.9 9.8 9.8 9.7 9.6 9.6
11.0
10.8
10.7
10.6
10.5
8.5
8.4
8.3
8.2
8.1
8.9
8.8
8.7
8.6
8.5
9.4
9.3
9.2
9.1
9.0
9.9
9.8
9.7
9.6
9.5
10.5
10.4
10.3
10.2
10.0
8.4
8.3
8.2
8.1
8.1
8.8
8.7
8.7
8.6
8.5
9.3
9.2
9.1
9.0
8.9
9.9
9.7
9.6
9.5
9.4
10.4
10.3
10.2
10.1
10.0
8.3
8.3
8.2
8.1
8.0
8.8
8.7
8.6
8.5
8.4
9.3
9.2
9.1
9.0
8.9
9.8
9.7
9.6
9.5
9.4
10.4
10.2
10.1
10.0
9.9
USEFUL INFORMATION FOR BIOGEOCHEMICAL SAMPLING

385
795
9.0
9.0
8.9
8.8
8.7
8.6
8.5
8.5
8.4
8.3
8.2
8.2
8.1
8.0
8.0
7.9
7.8
7.8
7.7
7.6
22.5
23.0
23.5
24.0
24.5
25.0
25.5
26.0
26.5
27.0
27.5
28.0
28.5
29.0
29.5
30.0
30.5
31.0
31.5
32.0
7.8
7.8
7.7
7.6
7.6
8.2
8.1
8.0
8.0
7.9
7.8
7.7
7.7
7.6
7.5
8.1
8.1
8.0
7.9
7.9
8.5
8.4
8.4
8.3
8.2
8.9
8.8
8.8
8.7
8.6
785
7.7
7.7
7.6
7.5
7.5
8.1
8.0
7.9
7.9
7.8
8.5
8.4
8.3
8.2
8.2
8.9
8.8
8.7
8.6
8.5
780
7.7
7.6
7.6
7.5
7.4
8.0
8.0
7.9
7.8
7.8
8.4
8.3
8.3
8.2
8.1
8.8
8.7
8.6
8.6
8.5
775
7.6
7.6
7.5
7.5
7.4
8.0
7.9
7.8
7.8
7.7
8.3
8.3
8.2
8.1
8.0
8.8
8.7
8.6
8.5
8.4
7.6
7.5
7.5
7.4
7.3
7.9
7.9
7.8
7.7
7.6
8.3
8.2
8.1
8.1
8.0
8.7
8.6
8.5
8.4
8.4
7.5
7.5
7.4
7.4
7.3
7.9
7.8
7.7
7.7
7.6
8.2
8.2
8.1
8.0
7.9
8.6
8.6
8.5
8.4
8.3
7.5
7.4
7.4
7.3
7.2
7.8
7.7
7.7
7.6
7.5
8.2
8.1
8.0
8.0
7.9
8.6
8.5
8.4
8.3
8.3
7.4
7.4
7.3
7.3
7.2
7.8
7.7
7.6
7.6
7.5
8.1
8.0
8.0
7.9
7.8
8.5
8.4
8.4
8.3
8.2
7.4
7.3
7.3
7.2
7.1
7.7
7.6
7.6
7.5
7.4
8.1
8.0
7.9
7.8
7.8
8.5
8.4
8.3
8.2
8.1
7.3
7.3
7.2
7.1
7.1
7.7
7.6
7.5
7.5
7.4
8.0
7.9
7.9
7.8
7.7
8.4
8.3
8.2
8.2
8.1
7.3
7.2
7.1
7.1
7.0
7.6
7.5
7.5
7.4
7.3
8.0
7.9
7.8
7.7
7.7
8.3
8.3
8.2
8.1
8.0
7.2
7.2
7.1
7.0
7.0
7.5
7.5
7.4
7.3
7.3
7.9
7.8
7.8
7.7
7.6
8.3
8.2
8.1
8.0
8.0
7.2
7.1
7.0
7.0
6.9
7.5
7.4
7.4
7.3
7.2
7.8
7.8
7.7
7.6
7.6
8.2
8.1
8.1
8.0
7.9

770 765 760 755 750 745 740 735 730 725
7.1
7.1
7.0
6.9
6.9
7.4
7.4
7.3
7.2
7.2
7.8
7.7
7.6
7.6
7.5
8.2
8.1
8.0
7.9
7.9
720
7.1
7.0
6.9
6.9
6.8
7.4
7.3
7.3
7.2
7.1
7.7
7.7
7.6
7.5
7.5
8.1
8.0
8.0
7.9
7.8
715
7.0
7.0
6.9
6.8
6.8
7.3
7.3
7.2
7.1
7.1
7.7
7.6
7.5
7.5
7.4
8.0
8.0
7.9
7.8
7.7
710
7.0
6.9
6.8
6.8
6.7
7.3
7.2
7.1
7.1
7.0
7.6
7.6
7.5
7.4
7.3
8.0
7.9
7.8
7.8
7.7
705
6.9
6.9
6.8
6.7
6.7
7.2
7.2
7.1
7.0
7.0
7.6
7.5
7.4
7.4
7.3
7.9
7.9
7.8
7.7
7.6
700
386
8.6
8.5
8.4
8.3
8.3
9.0
8.9
8.8
8.7
8.7
790
atmospheric pressures from 695 to 600 millimeters mercury begin after 40C) (Continued)
Temp
C
Table B2
7.6
7.5
7.4
7.4
7.3
7.3
7.2
7.2
7.1
7.0
7.0
6.9
6.9
6.8
6.8
6.7
32.5
33.0
33.5
34.0
34.5
35.0
35.5
36.0
36.5
37.0
37.5
38.0
38.5
39.0
39.5
40.0
6.7
6.9
6.9
6.8
6.8
6.7
7.2
7.2
7.1
7.0
7.0
7.5
7.5
7.4
7.3
7.3
6.6
6.9
6.8
6.8
6.7
6.7
7.2
7.1
7.1
7.0
6.9
7.5
7.4
7.3
7.3
7.2
6.6
6.8
6.8
6.7
6.7
6.6
7.1
7.1
7.0
7.0
6.9
7.4
7.4
7.3
7.2
7.2
6.5
6.8
6.7
6.7
6.6
6.6
7.1
7.0
7.0
6.9
6.9
7.4
7.3
7.2
7.2
7.1
6.5
6.8
6.7
6.6
6.6
6.5
7.0
7.0
6.9
6.9
6.8
7.3
7.3
7.2
7.1
7.1
6.4
6.7
6.7
6.6
6.5
6.5
7.0
6.9
6.9
6.8
6.8
7.3
7.2
7.1
7.1
7.0
6.4
6.7
6.6
6.6
6.5
6.5
6.9
6.9
6.8
6.8
6.8
7.2
7.2
7.1
7.0
7.0
6.4
6.6
6.6
6.5
6.5
6.4
6.9
6.8
6.8
6.7
6.7
7.2
7.1
7.1
7.0
6.9
6.3
6.6
6.5
6.5
6.4
6.4
6.8
6.8
6.7
6.7
6.6
7.1
7.1
7.0
6.9
6.9
6.3
6.5
6.5
6.4
6.4
6.3
6.8
6.7
6.7
6.6
6.6
7.1
7.0
7.0
6.9
6.8
6.2
6.5
6.4
6.4
6.3
6.3
6.7
6.7
6.6
6.6
6.5
7.0
7.0
6.9
6.8
6.8
6.2
6.4
6.4
6.3
6.3
6.2
6.7
6.6
6.6
6.5
6.5
7.0
6.9
6.9
6.8
6.7
6.1
6.4
6.3
6.3
6.2
6.2
6.6
6.6
6.5
6.5
6.4
6.9
6.9
6.8
6.7
6.7
6.1
6.3
6.3
6.2
6.2
6.1
6.6
6.5
6.5
6.4
6.4
6.9
6.8
6.8
6.7
6.6
6.0
6.3
6.2
6.2
6.1
6.1
6.5
6.5
6.4
6.4
6.3
6.8
6.8
6.7
6.7
6.6
6.0
6.2
6.2
6.1
6.1
6.0
6.5
6.4
6.4
6.3
6.3
6.8
6.7
6.7
6.6
6.5
5.9
6.2
6.1
6.1
6.0
6.0
6.4
6.4
6.3
6.3
6.2
6.7
6.7
6.6
6.6
6.5
5.9
6.1
6.1
6.0
6.0
6.0
6.4
6.3
6.3
6.2
6.2
6.7
6.6
6.6
6.5
6.5
5.9
6.1
6.0
6.0
6.0
5.9
6.3
6.3
6.2
6.2
6.1
6.6
6.6
6.5
6.5
6.4

387
695
13.3
13.1
13.0
12.8
12.6
12.4
12.3
12.1
12.0
11.8
11.6
11.5
11.4
11.2
11.1
10.9
10.8
10.7
10.5
10.4
0.0
0.5
1.0
1.5
2.0
2.5
3.0
3.5
4.0
4.5
5.0
5.5
6.0
6.5
7.0
7.5
8.0
8.5
9.0
9.5
10.9
10.7
10.6
10.5
10.3
11.6
11.4
11.3
11.1
11.0
10.8
10.6
10.5
10.4
10.3
11.5
11.3
11.2
11.0
10.9
12.3
12.1
11.9
11.8
11.9
13.1
13.0
12.8
12.6
12.4
685
10.7
10.6
10.4
10.3
10.2
11.4
11.2
11.1
11.0
10.8
12.2
12.0
11.8
11.7
11.5
13.0
12.9
12.7
12.5
12.3
680
10.6
10.5
10.4
10.2
10.1
11.3
11.2
11.0
10.9
10.7
12.1
11.9
11.8
11.6
11.5
12.9
12.8
12.6
12.4
12.2
675
10.5
10.4
10.3
10.2
10.0
11.2
11.1
10.9
10.8
10.7
12.0
11.8
11.7
11.5
11.4
12.8
12.7
12.5
12.3
12.2
10.5
10.3
10.2
10.1
10.0
11.1
11.0
10.9
10.7
10.6
11.9
11.7
11.6
11.4
11.3
12.8
12.6
12.4
12.2
12.1
11.0
10.8
10.7
10.6
10.4
11.7
11.6
11.4
11.3
11.1
12.6
12.4
12.2
12.0
11.9
10.9
10.7
10.6
10.5
10.3
11.6
11.5
11.3
11.2
11.0
12.5
12.3
12.1
12.0
11.8
10.8
10.7
10.5
10.4
10.3
11.5
11.4
11.2
11.1
10.9
12.4
12.2
12.0
11.9
11.7
10.7
10.6
10.4
10.3
10.2
11.4
11.3
11.1
11.0
10.9
12.3
12.1
11.9
11.8
11.6
10.6
10.5
10.4
10.2
10.1
11.4
11.2
11.1
10.9
10.8
12.2
12.0
11.8
11.7
11.5
10.4 10.3 10.2 10.1 10.1 10.0

10.2 10.2 10.1 10.0 9.9 9.9
10.1 10.0 10.0 9.9 9.8 9.7
10.0 9.9 9.8 9.8 9.7 9.6
9.9 9.8 9.7 9.7 9.6 9.5
11.1
10.9
10.8
10.6
10.5
11.8
11.7
11.5
11.3
11.2
12.7
12.5
12.3
12.1
12.0
9.9
9.8
9.7
9.5
9.4
10.5
10.4
10.3
10.1
10.0
11.3
11.1
11.0
10.8
10.7
12.1
11.9
11.7
11.6
11.4
9.8
9.7
9.6
9.5
9.4
10.5
10.3
10.2
10.1
9.9
11.2
11.0
10.9
10.7
10.6
12.0
11.8
11.6
11.5
11.3

670 665 660 655 650 645 640 635 630 625
620
615
11.0
10.9
10.7
10.6
10.4
11.8
11.6
11.5
11.3
11.1
610
10.9
10.8
10.6
10.5
10.3
11.7
11.5
11.4
11.2
11.1
605
10.8
10.7
10.5
10.4
10.3
11.6
11.4
11.3
11.1
11.0
600
10.7
10.6
10.4
10.3
10.2
11.5
11.3
11.2
11.0
10.9
9.7
9.6
9.5
9.4
9.3
9.7
9.5
9.4
9.3
9.2
9.6
9.5
9.3
9.2
9.1
9.5
9.4
9.3
9.2
9.0
9.4
9.3
9.2
9.1
9.0
10.4 10.3 10.2 10.1 10.0

10.2 10.2 10.1 10.0 9.9
10.1 10.0 9.9 9.9 9.8
10.0 9.9 9.8 9.7 9.7
9.9 9.8 9.7 9.6 9.5
11.1
10.9
10.8
10.7
10.5
11.9
11.7
11.6
11.4
11.2
388
12.4
12.2
12.0
11.9
11.7
13.2
13.1
12.9
12.7
12.5
690
Temp
C
Table B2
10.3
10.2
10.1
9.9
9.8
9.7
9.6
9.5
9.4
9.3
9.2
9.1
9.0
8.9
8.8
8.7
8.6
8.5
8.4
8.4
8.3
8.2
8.1
8.0
8.0
10.0
10.5
11.0
11.5
12.0
12.5
13.0
13.5
14.0
14.5
15.0
15.5
16.0
16.5
17.0
17.5
18.0
18.5
19.0
19.5
20.0
20.5
21.0
21.5
22.0
8.2
8.1
8.1
8.0
7.9
8.6
8.6
8.5
8.4
8.3
9.1
9.0
8.9
8.8
8.7
9.6
9.5
9.4
9.3
9.2
8.2
8.1
8.0
7.9
7.8
8.6
8.5
8.4
8.3
8.2
9.1
9.0
8.9
8.8
8.7
9.6
9.5
9.4
9.3
9.2
8.1
8.0
7.9
7.9
7.8
8.5
8.4
8.3
8.3
8.2
9.0
8.9
8.8
8.7
8.6
9.5
9.4
9.3
9.2
9.1
8.0
7.9
7.9
7.8
7.7
8.5
8.4
8.3
8.2
8.1
8.9
8.8
8.7
8.6
8.5
9.4
9.3
9.2
9.1
9.0
10.2 10.1 10.1 10.0

10.1 10.0 9.9 9.9
10.0 9.9 9.8 9.8
9.9 9.8 9.7 9.6
9.8 9.7 9.6 9.5
8.0
7.9
7.8
7.7
7.7
8.4
8.3
8.2
8.1
8.0
8.8
8.8
8.7
8.6
8.5
9.4
9.3
9.1
9.0
8.9
9.9
9.8
9.7
9.6
9.5
7.9
7.8
7.8
7.7
7.6
8.3
8.2
8.2
8.1
8.0
8.8
8.7
8.6
8.5
8.4
9.3
9.2
9.1
9.0
8.9
9.8
9.7
9.6
9.5
9.4
7.8
7.8
7.7
7.6
7.5
8.3
8.2
8.1
8.0
7.9
8.7
8.6
8.5
8.4
8.3
9.2
9.1
9.0
8.9
8.8
9.8
9.7
9.5
9.4
9.3
7.8
7.7
7.6
7.6
7.5
8.2
8.1
8.0
7.9
7.9
8.6
8.6
8.5
8.4
8.3
9.1
9.0
8.9
8.8
8.7
9.7
9.6
9.5
9.4
9.2
7.7
7.6
7.6
7.5
7.4
8.1
8.0
8.0
7.9
7.8
8.6
8.5
8.4
8.3
8.2
9.1
9.0
8.9
8.8
8.7
9.6
9.5
9.4
9.3
9.2
7.7
7.6
7.5
7.4
7.4
8.1
8.0
7.9
7.8
7.7
8.5
8.4
8.3
8.2
8.2
9.0
8.9
8.8
8.7
8.6
9.5
9.4
9.3
9.2
9.1
7.6
7.5
7.5
7.4
7.3
8.0
7.9
7.8
7.8
7.7
8.4
8.4
8.3
8.2
8.1
8.9
8.8
8.7
8.6
8.5
9.5
9.4
9.2
9.1
9.0
7.5
7.5
7.4
7.3
7.2
7.9
7.9
7.8
7.7
7.6
8.4
8.3
8.2
8.1
8.0
8.9
8.8
8.7
8.6
8.5
9.4
9.3
9.2
9.1
9.0
7.5
7.4
7.3
7.3
7.2
7.9
7.8
7.7
7.6
7.6
8.3
8.2
8.1
8.0
8.0
8.8
8.7
8.6
8.5
8.4
9.3
9.2
9.1
9.0
8.9
7.4
7.3
7.3
7.2
7.1
7.8
7.7
7.7
7.6
7.5
8.2
8.2
8.1
8.0
7.9
8.7
8.6
8.5
8.4
8.3
9.2
9.1
9.0
8.9
8.8
7.4
7.3
7.2
7.1
7.1
7.7
7.7
7.6
7.5
7.4
8.2
8.1
8.0
7.9
7.8
8.6
8.5
8.5
8.4
8.3
9.2
9.1
9.0
8.8
8.7
7.3
7.2
7.2
7.1
7.0
7.7
7.6
7.5
7.4
7.4
8.1
8.0
7.9
7.8
7.8
8.6
8.5
8.4
8.3
8.2
9.1
9.0
8.9
8.8
8.7
7.2
7.2
7.1
7.0
7.0
7.6
7.5
7.5
7.4
7.3
8.0
8.0
7.9
7.8
7.7
8.5
8.4
8.3
8.2
8.1
9.0
8.9
8.8
8.7
8.6
7.2
7.1
7.0
7.0
6.9
7.6
7.5
7.4
7.3
7.2
8.0
7.9
7.8
7.7
7.6
8.4
8.3
8.2
8.2
8.1
8.9
8.8
8.7
8.6
8.5
7.1
7.0
7.0
6.9
6.8
7.5
7.4
7.3
7.3
7.2
7.9
7.8
7.7
7.7
7.6
8.4
8.3
8.2
8.1
8.0
8.9
8.8
8.7
8.6
8.5

389
695
7.9
7.8
7.7
7.7
7.6
7.5
7.4
7.4
7.3
7.2
7.2
7.1
7.0
7.0
6.9
6.9
6.8
6.7
6.7
6.6
22.5
23.0
23.5
24.0
24.5
25.0
25.5
26.0
26.5
27.0
27.5
28.0
28.5
29.0
29.5
30.0
30.5
31.0
31.5
32.0
6.8
6.7
6.7
6.6
6.6
7.1
7.1
7.0
6.9
6.9
6.8
6.7
6.6
6.6
6.5
7.1
7.0
6.9
6.9
6.8
7.4
7.3
7.3
7.2
7.1
7.8
7.7
7.6
7.5
7.5
685
6.7
6.6
6.6
6.5
6.5
7.0
6.9
6.9
6.8
6.8
7.3
7.3
7.2
7.1
7.1
7.7
7.6
7.6
7.5
7.4
680
6.7
6.6
6.5
6.5
6.4
7.0
6.9
6.8
6.8
6.7
7.3
7.2
7.2
7.1
7.0
7.6
7.6
7.5
7.4
7.4
675
6.6
6.5
6.5
6.4
6.4
6.9
6.8
6.8
6.7
6.7
7.2
7.2
7.1
7.0
7.0
7.6
7.5
7.4
7.4
7.3
6.5
6.5
6.4
6.4
6.3
6.8
6.8
6.7
6.7
6.6
7.2
7.1
7.0
7.0
6.9
7.5
7.5
7.4
7.3
7.2
6.5
6.4
6.4
6.3
6.3
6.8
6.7
6.7
6.6
6.6
7.1
7.1
7.0
6.9
6.9
7.5
7.4
7.3
7.3
7.2
6.4
6.4
6.3
6.3
6.2
6.7
6.7
6.6
6.6
6.5
7.1
7.0
6.9
6.9
6.8
7.4
7.3
7.3
7.2
7.1
6.4
6.3
6.3
6.2
6.2
6.7
6.6
6.6
6.5
6.5
7.0
6.9
6.9
6.8
6.7
7.3
7.3
7.2
7.1
7.1
6.3
6.3
6.2
6.2
6.1
6.6
6.6
6.5
6.5
6.4
6.9
6.9
6.8
6.8
6.7
7.3
7.2
7.2
7.1
7.0
6.3
6.2
6.2
6.1
6.1
6.6
6.5
6.5
6.4
6.3
6.9
6.8
6.8
6.7
6.6
7.2
7.2
7.1
7.0
7.0
6.2
6.2
6.1
6.1
6.0
6.5
6.5
6.4
6.4
6.3
6.8
6.8
6.7
6.6
6.6
7.2
7.1
7.0
7.0
6.9
6.2
6.1
6.1
6.0
6.0
6.5
6.4
6.4
6.3
6.2
6.8
6.7
6.7
6.6
6.5
7.1
7.0
7.0
6.9
6.8
6.1
6.1
6.0
6.0
5.9
6.4
6.4
6.3
6.2
6.2
6.7
6.7
6.6
6.5
6.5
7.1
7.0
6.9
6.9
6.8

670 665 660 655 650 645 640 635 630 625
6.1
6.0
6.0
5.9
5.9
6.4
6.3
6.2
6.2
6.1
6.7
6.6
6.5
6.5
6.4
7.0
6.9
6.9
6.8
6.7
620
6.0
6.0
5.9
5.9
5.8
6.3
6.3
6.2
6.1
6.1
6.6
6.6
6.5
6.4
6.4
6.9
6.9
6.8
6.7
6.7
615
6.0
5.9
5.9
5.8
5.8
6.3
6.2
6.1
6.1
6.0
6.6
6.5
6.4
6.4
6.3
6.9
6.8
6.7
6.7
6.6
610
5.9
5.9
5.8
5.8
5.7
6.2
6.1
6.1
6.0
6.0
6.5
6.4
6.4
6.3
6.3
6.8
6.8
6.7
6.6
6.6
605
5.9
5.8
5.8
5.7
5.7
6.2
6.1
6.0
6.0
5.9
6.4
6.4
6.3
6.3
6.2
6.8
6.7
6.6
6.6
6.5
600
390
7.5
7.4
7.3
7.2
7.2
7.8
7.7
7.7
7.6
7.5
690
Temp
C
Table B2
6.3
6.2
6.2
6.1
6.1
6.0
6.0
6.0
5.9
5.9
5.8
35.0
35.5
36.0
36.5
37.0
37.5
38.0
38.5
39.0
39.5
40.0
5.8
6.0
6.0
5.9
5.9
5.8
6.3
6.2
6.1
6.1
6.1
6.5
6.5
6.4
6.4
6.3
5.7
6.0
5.9
5.9
5.8
5.8
6.2
6.2
6.1
6.1
6.0
6.5
6.4
6.4
6.3
6.3
5.7
5.9
5.9
5.8
5.8
5.7
6.2
6.1
6.1
6.0
6.0
6.4
6.4
6.3
6.3
6.2
5.6
5.9
5.8
5.8
5.7
5.7
6.1
6.1
6.0
6.0
5.9
6.4
6.3
6.3
6.2
6.2
5.6
5.8
5.8
5.7
5.7
5.6
6.1
6.0
6.0
5.9
5.9
6.3
6.3
6.2
6.2
6.1
5.5
5.8
5.7
5.7
5.6
5.6
6.0
6.0
5.9
5.9
5.8
6.3
6.2
6.2
6.1
6.1
5.5
5.7
5.7
5.6
5.6
5.5
6.0
5.9
5.9
5.8
5.8
6.2
6.2
6.1
6.1
6.0
5.4
5.7
5.6
5.6
5.5
5.5
5.9
5.9
5.8
5.8
5.7
6.2
6.1
6.1
6.0
6.0
6.6
6.5
6.5
6.4
6.4
32.5
33.0
33.5
34.0
34.5
5.4
5.6
5.6
5.5
5.5
5.4
5.9
5.8
5.8
5.7
5.7
6.1
6.1
6.0
6.0
5.9
5.4
5.6
5.5
5.5
5.4
5.4
5.8
5.8
5.7
5.7
5.6
6.1
6.0
6.0
5.9
5.9
5.3
5.5
5.5
5.4
5.4
5.4
5.8
5.7
5.7
5.6
5.6
6.0
6.0
5.9
5.9
5.8
5.3
5.5
5.4
5.4
5.4
5.3
5.7
5.7
5.6
5.6
5.5
6.0
5.9
5.9
5.8
5.8
5.2
5.4
5.4
5.4
5.3
5.3
5.7
5.6
5.6
5.5
5.5
5.9
5.9
5.8
5.8
5.7
5.2
5.4
5.3
5.3
5.3
5.2
5.6
5.6
5.5
5.5
5.4
5.9
5.8
5.8
5.7
5.7
5.1
5.3
5.3
5.3
5.2
5.2
5.6
5.5
5.5
5.4
5.4
5.8
5.8
5.7
5.7
5.6
5.1
5.3
5.3
5.2
5.2
5.1
5.5
5.5
5.4
5.4
5.3
5.8
5.7
5.7
5.6
5.6
5.0
5.3
5.2
5.2
5.1
5.1
5.5
5.4
5.4
5.3
5.3
5.7
5.7
5.6
5.6
5.5
5.0
5.2
5.2
5.1
5.1
5.0
5.4
5.4
5.3
5.3
5.3
5.7
5.6
5.6
5.5
5.5
5.0
5.2
5.1
5.1
5.0
5.0
5.4
5.3
5.3
5.2
5.2
5.6
5.6
5.5
5.5
5.4

391
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
0.0
1.0
2.0
3.0
4.0
5.0
6.0
7.0
8.0
9.0
10.0
11.0
12.0
13.0
14.0
15.0
16.0
17.0
18.0
19.0
0.997
0.997
0.997
0.997
0.997
0.996
0.996
0.997
0.997
0.997
0.993
0.993
0.993
0.993
0.993
0.993
0.993
0.993
0.993
0.993
0.993
0.993
0.993
0.993
0.993
0.992
0.992
0.992
0.993
0.993
2000
0.990
0.990
0.990
0.990
0.990
0.989
0.989
0.989
0.990
0.990
0.989
0.989
0.989
0.989
0.989
0.989
0.989
0.989
0.989
0.989
3000
0.986
0.986
0.986
0.987
0.987
0.986
0.986
0.986
0.986
0.986
0.985
0.985
0.985
0.986
0.986
0.985
0.985
0.985
0.985
0.985
0.983
0.983
0.983
0.983
0.983
0.982
0.982
0.982
0.983
0.983
0.981
0.982
0.982
0.982
0.982
0.981
0.981
0.981
0.981
0.981
0.979
0.979
0.980
0.980
0.980
0.979
0.979
0.979
0.979
0.979
0.978
0.978
0.978
0.978
0.978
0.977
0.977
0.977
0.977
0.978
0.976
0.976
0.976
0.976
0.976
0.975
0.975
0.975
0.975
0.976
0.974
0.974
0.974
0.975
0.975
0.973
0.973
0.973
0.974
0.974
0.972
0.972
0.973
0.973
0.973
0.971
0.971
0.972
0.972
0.972
0.970
0.970
0.971
0.971
0.971
0.969
0.969
0.970
0.970
0.970
0.969
0.969
0.969
0.969
0.970
0.968
0.968
0.968
0.968
0.969
0.966
0.967
0.967
0.967
0.967
0.965
0.965
0.966
0.966
0.966
0.965
0.966
0.966
0.966
0.966
0.964
0.964
0.965
0.965
0.965
0.963
0.963
0.963
0.963
0.964
0.961
0.962
0.962
0.962
0.962
0.962
0.962
0.962
0.963
0.963
0.960
0.961
0.961
0.961
0.961
0.959
0.959
0.959
0.960
0.960
0.957
0.958
0.958
0.958
0.959
0.958
0.958
0.959
0.959
0.959
0.957
0.957
0.957
0.958
0.958
0.955
0.955
0.956
0.956
0.956
0.953
0.954
0.954
0.954
0.955
0.955
0.955
0.955
0.956
0.956
0.953
0.953
0.954
0.954
0.954
0.951
0.952
0.952
0.952
0.953
0.950
0.950
0.950
0.951
0.951
0.951
0.951
0.952
0.952
0.952
0.949
0.950
0.950
0.950
0.951
0.947
0.948
0.948
0.949
0.949
0.946
0.946
0.946
0.947
0.947
0.947
0.948
0.948
0.949
0.949
0.946
0.946
0.946
0.947
0.947
0.944
0.944
0.944
0.945
0.945
0.942
0.942
0.942
0.943
0.943
0.944
0.944
0.945
0.945
0.945
0.942
0.942
0.943
0.943
0.943
0.940
0.940
0.941
0.941
0.941
0.938
0.938
0.938
0.939
0.939
Conductivity, in microsiemens per centimeter at 25C

4000 5000 6000 7000 8000 9000 10000 11000 12000 13000 14000 15000 16000
392
0.996
0.996
0.996
0.996
0.996
0.996
0.996
0.996
0.996
0.996
1000
Salinity Correction Factors for Dissolved Oxygen in Water (based on conductivity) (Temp C, temperature in degrees Celsius;
salinity correction factors at 30 to 35C are shown at the end of this table)
Temp
C
Table B3
0.934
0.934
0.935
0.935
0.935
0.936
0.936
0.937
0.937
0.937
0.938
0.939
0.939
0.939
0.940
0.0
1.0
2.0
3.0
4.0
5.0
6.0
7.0
8.0
9.0
10.0
11.0
12.0
13.0
14.0
0.934
0.935
0.935
0.936
0.936
0.932
0.933
0.933
0.933
0.934
0.930
0.930
0.931
0.931
0.932
0.931
0.931
0.932
0.932
0.933
0.928
0.929
0.929
0.930
0.930
0.926
0.926
0.927
0.927
0.928
0.927
0.927
0.928
0.928
0.929
0.924
0.925
0.925
0.926
0.926
0.922
0.922
0.923
0.923
0.924
0.990
0.990
0.991
0.991
0.991
0.923
0.924
0.924
0.925
0.925
0.920
0.921
0.922
0.922
0.922
0.918
0.918
0.919
0.919
0.920
0.987
0.987
0.987
0.987
0.988
0.919
0.920
0.920
0.921
0.922
0.917
0.917
0.918
0.918
0.919
0.914
0.914
0.915
0.915
0.916
0.984
0.984
0.984
0.984
0.984
0.983
0.984
0.984
0.984
0.984
0.916
0.916
0.917
0.917
0.918
0.913
0.913
0.914
0.914
0.915
0.910
0.910
0.911
0.911
0.912
0.981
0.981
0.981
0.981
0.981
0.980
0.980
0.980
0.980
0.981
0.912
0.912
0.913
0.914
0.914
0.909
0.909
0.910
0.911
0.911
0.905
0.906
0.907
0.907
0.908
0.977
0.978
0.978
0.978
0.978
0.977
0.977
0.977
0.977
0.977
0.908
0.909
0.909
0.910
0.911
0.905
0.905
0.906
0.907
0.907
0.901
0.902
0.903
0.903
0.904
0.974
0.974
0.975
0.975
0.975
0.973
0.973
0.974
0.974
0.974
0.904
0.905
0.906
0.906
0.907
0.901
0.902
0.902
0.903
0.904
0.897
0.898
0.899
0.899
0.900
0.971
0.971
0.971
0.972
0.972
0.970
0.970
0.970
0.971
0.971
0.900
0.901
0.903
0.902
0.903
0.897
0.898
0.898
0.899
0.900
0.893
0.894
0.895
0.895
0.896
0.968
0.968
0.968
0.968
0.969
0.966
0.967
0.967
0.967
0.967
0.897
0.897
0.898
0.899
0.899
0.893
0.894
0.894
0.895
0.896
0.889
0.890
0.891
0.891
0.892
0.964
0.965
0.965
0.965
0.965
0.963
0.963
0.964
0.964
0.964
0.893
0.894
0.894
0.895
0.896
0.889
0.890
0.891
0.891
0.892
0.885
0.886
0.887
0.887
0.888
0.961
0.961
0.962
0.962
0.962
0.960
0.960
0.960
0.960
0.961
0.889
0.890
0.890
0.891
0.892
0.885
0.886
0.887
0.887
0.888
0.881
0.882
0.883
0.883
0.884
0.958
0.958
0.958
0.959
0.959
0.956
0.957
0.957
0.957
0.957
0.885
0.886
0.887
0.887
0.888
0.881
0.882
0.883
0.884
0.884
0.877
0.878
0.879
0.879
0.880
0.954
0.955
0.955
0.955
0.956
0.953
0.953
0.953
0.954
0.954
0.881
0.882
0.883
0.884
0.884
0.877
0.878
0.879
0.880
0.880
0.873
0.874
0.875
0.875
0.876
0.951
0.951
0.952
0.952
0.952
0.949
0.950
0.950
0.950
0.951
0.877
0.878
0.879
0.880
0.881
0.873
0.874
0.875
0.876
0.877
0.869
0.870
0.871
0.871
0.872
0.948
0.948
0.948
0.949
0.949
0.946
0.946
0.947
0.947
0.947

17000 18000 19000 20000 21000 22000 23000 24000 25000 26000 27000 28000 29000 30000 31000 32000 33000
0.994
0.994
0.994
0.994
0.994
0.987
0.987
0.987
0.987
0.987
Temp
C
0.997
0.997
0.997
0.997
0.997
0.990
0.990
0.990
0.990
0.990
1.000
1.000
1.000
1.000
1.000
0.993
0.993
0.993
0.994
0.994
25.0
26.0
27.0
28.0
29.0
0.997
0.997
0.997
0.997
0.997
1.000
1.000
1.000
1.000
1.000
20.0
21.0
22.0
23.0
24.0

393
0.0
1.0
2.0
3.0
4.0
0.865
0.866
0.867
0.867
0.868
0.861
0.862
0.862
0.863
0.864
0.856
0.857
0.858
0.859
0.860
0.852
0.853
0.854
0.855
0.856
0.934
0.935
0.935
0.936
0.936
0.848
0.849
0.850
0.851
0.852
0.931
0.931
0.932
0.932
0.933
0.844
0.845
0.846
0.847
0.848
0.927
0.928
0.928
0.929
0.929
0.840
0.841
0.842
0.843
0.844
0.924
0.925
0.925
0.926
0.926
0.921
0.922
0.922
0.923
0.923
0.836
0.837
0.838
0.839
0.840
0.921
0.921
0.922
0.922
0.923
0.918
0.918
0.919
0.919
0.920
0.832
0.833
0.834
0.835
0.836
0.917
0.918
0.918
0.919
0.919
0.914
0.915
0.915
0.916
0.917
0.828
0.829
0.830
0.831
0.832
0.914
0.914
0.915
0.915
0.916
0.911
0.911
0.912
0.912
0.913
0.823
0.825
0.826
0.827
0.828
0.910
0.911
0.911
0.912
0.913
0.907
0.908
0.908
0.909
0.910
0.904
0.904
0.905
0.906
0.906
0.819
0.821
0.822
0.823
0.824
0.907
0.907
0.908
0.909
0.909
0.903
0.904
0.905
0.905
0.906
0.900
0.901
0.901
0.902
0.903
0.815
0.816
0.818
0.819
0.820
0.903
0.904
0.905
0.905
0.906
0.900
0.901
0.901
0.902
0.903
0.896
0.897
0.898
0.899
0.899
0.811
0.812
0.814
0.815
0.816
0.900
0.901
0.901
0.902
0.903
0.896
0.897
0.898
0.898
0.899
0.893
0.893
0.894
0.895
0.896
0.807
0.808
0.809
0.811
0.812
0.896
0.897
0.898
0.898
0.899
0.893
0.893
0.894
0.895
0.896
0.889
0.890
0.891
0.891
0.892
0.803
0.804
0.805
0.807
0.808
0.893
0.894
0.894
0.895
0.896
0.889
0.890
0.891
0.891
0.892
0.885
0.886
0.887
0.888
0.888
0.799
0.800
0.801
0.803
0.804
0.890
0.890
0.891
0.892
0.892
0.886
0.886
0.887
0.888
0.889
0.882
0.882
0.883
0.884
0.885

34000 35000 36000 37000 38000 39000 40000 41000 42000 43000 44000 45000 46000 47000 48000 49000 50000
0.938
0.938
0.938
0.939
0.939
0.925
0.925
0.926
0.926
0.927
0.908
0.909
0.909
0.910
0.911
Temp
C
0.941
0.941
0.942
0.942
0.943
0.928
0.929
0.929
0.930
0.930
0.911
0.912
0.912
0.913
0.914
0.944
0.945
0.945
0.946
0.946
0.932
0.932
0.933
0.933
0.934
0.915
0.915
0.916
0.917
0.917
25.0
26.0
27.0
28.0
29.0
0.935
0.936
0.936
0.937
0.937
0.918
0.919
0.920
0.920
0.921
394
0.939
0.939
0.940
0.940
0.941
0.922
0.923
0.923
0.924
0.924
0.942
0.943
0.943
0.944
0.944
0.926
0.926
0.927
0.927
0.928
20.0
21.0
22.0
23.0
24.0
0.929
0.930
0.930
0.931
0.931
0.940
0.941
0.941
0.942
0.942
15.0
16.0
17.0
18.0
19.0
0.933
0.934
0.934
0.934
0.935

17000 18000 19000 20000 21000 22000 23000 24000 25000 26000 27000 28000 29000 30000 31000 32000 33000
Temp
C
0.937
0.937
0.938
0.938
0.938
salinity correction factors at 30 to 35C are shown at the end of this table) (Continued)
Table B3
0.869
0.870
0.871
0.872
0.873
0.874
0.874
0.875
0.876
0.877
0.878
0.879
0.879
0.880
0.881
0.882
0.883
0.884
0.884
0.885
0.886
0.887
0.887
0.888
0.889
5.0
6.0
7.0
8.0
9.0
10.0
11.0
12.0
13.0
14.0
15.0
16.0
17.0
18.0
19.0
20.0
21.0
22.0
23.0
24.0
25.0
26.0
27.0
28.0
29.0
0.882
0.883
0.884
0.885
0.886
0.878
0.879
0.880
0.881
0.882
0.874
0.875
0.876
0.877
0.877
0.870
0.871
0.871
0.872
0.873
0.865
0.866
0.867
0.868
0.869
0.879
0.880
0.880
0.881
0.882
0.875
0.876
0.876
0.877
0.878
0.870
0.871
0.872
0.873
0.874
0.866
0.867
0.868
0.869
0.869
0.861
0.862
0.863
0.864
0.865
0.875
0.876
0.877
0.878
0.879
0.871
0.872
0.873
0.874
0.874
0.867
0.867
0.868
0.869
0.870
0.862
0.863
0.864
0.865
0.866
0.857
0.858
0.859
0.860
0.861
0.872
0.873
0.874
0.874
0.875
0.867
0.868
0.869
0.870
0.871
0.863
0.864
0.865
0.866
0.867
0.858
0.859
0.860
0.861
0.862
0.853
0.854
0.855
0.856
0.857
0.868
0.869
0.870
0.871
0.872
0.864
0.865
0.866
0.866
0.867
0.859
0.860
0.861
0.862
0.863
0.854
0.855
0.856
0.857
0.858
0.849
0.850
0.851
0.852
0.853
0.865
0.866
0.867
0.867
0.868
0.860
0.861
0.862
0.863
0.864
0.855
0.856
0.857
0.858
0.859
0.850
0.851
0.852
0.853
0.854
0.845
0.846
0.847
0.848
0.849
0.861
0.862
0.863
0.864
0.865
0.856
0.857
0.858
0.859
0.860
0.852
0.853
0.854
0.855
0.855
0.846
0.848
0.849
0.850
0.851
0.841
0.842
0.843
0.844
0.845
0.858
0.859
0.860
0.860
0.861
0.853
0.854
0.855
0.856
0.857
0.848
0.849
0.850
0.851
0.852
0.843
0.844
0.845
0.846
0.847
0.837
0.838
0.839
0.840
0.842
0.854
0.855
0.856
0.857
0.858
0.849
0.850
0.851
0.852
0.853
0.844
0.845
0.846
0.847
0.848
0.839
0.840
0.841
0.842
0.843
0.833
0.834
0.835
0.837
0.838
0.851
0.852
0.853
0.853
0.854
0.845
0.846
0.848
0.849
0.850
0.840
0.841
0.842
0.843
0.844
0.835
0.836
0.837
0.838
0.839
0.829
0.830
0.831
0.833
0.834
0.847
0.848
0.849
0.850
0.851
0.842
0.843
0.844
0.845
0.846
0.836
0.838
0.839
0.840
0.841
0.831
0.832
0.833
0.834
0.835
0.825
0.826
0.828
0.829
0.830
0.843
0.844
0.845
0.846
0.848
0.838
0.839
0.840
0.841
0.842
0.833
0.834
0.835
0.836
0.837
0.827
0.828
0.829
0.830
0.832
0.821
0.822
0.824
0.825
0.826
0.840
0.841
0.842
0.843
0.844
0.834
0.836
0.837
0.838
0.839
0.829
0.830
0.831
0.832
0.833
0.823
0.824
0.825
0.827
0.828
0.817
0.818
0.820
0.821
0.822
0.836
0.837
0.838
0.839
0.841
0.831
0.832
0.833
0.834
0.835
0.825
0.826
0.827
0.829
0.830
0.819
0.820
0.822
0.823
0.824
0.813
0.814
0.816
0.817
0.818
0.833
0.834
0.835
0.836
0.837
0.827
0.828
0.829
0.830
0.832
0.821
0.822
0.824
0.825
0.826
0.815
0.817
0.818
0.819
0.820
0.809
0.810
0.812
0.813
0.814
0.829
0.830
0.831
0.832
0.834
0.823
0.825
0.826
0.827
0.828
0.817
0.819
0.820
0.821
0.822
0.811
0.813
0.814
0.815
0.816
0.805
0.806
0.808
0.809
0.810

395
0.795
0.796
0.797
0.798
0.800
0.801
0.802
0.804
0.805
0.806
0.807
0.809
0.810
0.811
0.812
0.814
0.815
0.816
0.817
0.819
5.0
6.0
7.0
8.0
9.0
10.0
11.0
12.0
13.0
14.0
15.0
16.0
17.0
18.0
19.0
0.810
0.811
0.812
0.814
0.815
0.804
0.805
0.806
0.807
0.809
0.806
0.907
0.809
0.810
0.811
0.800
0.801
0.802
0.804
0.805
0.793
0.794
0.796
0.797
0.798
0.786
0.788
0.789
0.790
0.792
0.802
0.804
0.805
0.806
0.807
0.796
0.797
0.798
0.800
0.801
0.789
0.790
0.792
0.793
0.794
0.782
0.783
0.785
0.786
0.788
0.798
0.800
0.801
0.802
0.804
0.792
0.793
0.794
0.796
0.797
0.785
0.786
0.788
0.789
0.790
0.778
0.779
0.781
0.782
0.794
0.795
0.796
0.797
0.799
0.800
0.788
0.789
0.791
0.792
0.793
0.781
0.782
0.784
0.785
0.787
0.774
0.775
0.777
0.778
0.780
0.791
0.792
0.794
0.795
0.796
0.784
0.785
0.787
0.788
0.789
0.777
0.778
0.780
0.781
0.783
0.770
0.771
0.773
0.774
0.775
0.787
0.788
0.790
0.791
0.792
0.780
0.781
0.783
0.784
0.786
0.773
0.774
0.776
0.777
0.779
0.767
0.767
0.768
0.770
0.771
0.783
0.785
0.786
0.787
0.789
0.776
0.778
0.779
0.780
0.782
0.769
0.770
0.772
0.773
0.775
0.761
0.763
0.764
0.766
0.767
0.779
0.784
0.782
0.784
0.785
0.772
0.774
0.775
0.777
0.778
0.765
0.766
0.768
0.769
0.771
0.757
0.759
0.760
0.762
0.763
0.776
0.777
0.778
0.780
0.781
0.768
0.770
0.771
0.773
0.774
0.761
0.762
0.764
0.765
0.767
0.753
0.755
0.756
0.758
0.759
0.772
0.773
0.775
0.776
0.777
0.764
0.766
0.767
0.769
0.770
0.757
0.758
0.760
0.761
0.763
0.749
0.751
0.752
0.754
0.755
0.768
0.769
0.771
0.772
0.774
0.760
0.762
0.763
0.765
0.766
0.753
0.754
0.756
0.757
0.759
0.745
0.746
0.748
0.750
0.751
0.764
0.766
0.767
0.769
0.770
0.757
0.758
0.760
0.761
0.763
0.749
0.750
0.752
0.753
0.755
0.741
0.742
0.744
0.746
0.747
0.760
0.762
0.763
0.765
0.766
0.753
0.754
0.756
0.757
0.759
0.745
0.746
0.748
0.749
0.751
0.737
0.738
0.740
0.741
0.743
0.756
0.758
0.760
0.761
0.763
0.749
0.750
0.752
0.753
0.755
0.741
0.742
0.744
0.745
0.747
0.732
0.734
0.736
0.737
0.739
0.753
0.754
0.756
0.757
0.759
0.745
0.746
0.748
0.750
0.751
0.737
0.738
0.740
0.742
0.743
0.728
0.730
0.732
0.733
0.735
396
0.797
0.798
0.800
0.801
0.802
0.790
0.792
0.793
0.794
0.796

51000 52000 53000 54000 55000 56000 57000 58000 59000 60000 61000 62000 63000 64000 65000 66000 67000
Temp
C
0.0
1.0
2.0
3.0
4.0
Table B3
0.943
0.943
0.944
0.944
0.945
0.945
0.940
0.940
0.941
0.941
0.941
0.942
0.936
0.937
0.937
0.938
0.938
0.939
0.933
0.934
0.934
0.935
0.935
0.935
0.779
0.780
0.778
0.783
0.784
0.775
0.776
0.774
0.779
0.781
0.771
0.773
0.771
0.776
0.777
0.764
0.766
0.767
0.768
0.770
0.772
0.774
0.768
0.769
0.760
0.762
0.763
0.765
0.766
0.946
0.947
0.947
0.947
0.948
0.948
0.782
0.784
0.781
0.786
0.788
0.768
0.769
0.771
0.772
0.774
30.0
31.0
32.0
33.0
34.0
35.0
0.786
0.787
0.785
0.790
0.791
0.771
0.773
0.774
0.776
0.777
3300
0.789
0.791
0.789
0.794
0.795
0.775
0.777
0.778
0.779
0.781

17000 18000 19000 20000 21000 22000 23000 24000 25000 26000 27000 28000 29000 30000 31000 32000
0.988
0.988
0.988
0.988
0.988
0.988
0.793
0.794
0.792
0.797
0.798
0.779
0.780
0.782
0.783
0.785
Temp
C
0.991
0.991
0.991
0.991
0.991
0.991
0.797
0.798
0.799
0.801
0.802
0.783
0.784
0.785
0.787
0.788
0.930
0.930
0.931
0.931
0.932
0.932
0.985
0.985
0.985
0.985
0.985
0.985
0.927
0.927
0.928
0.928
0.929
0.929
0.981
0.982
0.982
0.982
0.982
0.982
0.923
0.924
0.924
0.925
0.925
0.926
0.978
0.978
0.979
0.979
0.979
0.979
0.920
0.920
0.921
0.922
0.922
0.923
0.975
0.975
0.975
0.976
0.976
0.976
0.917
0.917
0.918
0.918
0.919
0.919
0.972
0.972
0.972
0.973
0.973
0.973
0.913
0.914
0.914
0.915
0.916
0.916
0.969
0.969
0.969
0.969
0.970
0.970
0.910
0.911
0.911
0.912
0.912
0.913
0.966
0.966
0.966
0.966
0.967
0.967
0.907
0.907
0.908
0.908
0.909
0.910
0.962
0.963
0.963
0.963
0.963
0.964
0.903
0.904
0.905
0.905
0.906
0.906
0.959
0.959
0.960
0.960
0.960
0.961
0.900
0.901
0.901
0.902
0.903
0.903
0.956
0.956
0.957
0.957
0.957
0.957
0.896
0.897
0.898
0.899
0.899
0.900
0.893
0.894
0.895
0.895
0.896
0.897

5000 6000 7000 8000 9000 10000 11000 12000 13000 14000 15000 16000
0.800
0.802
0.803
0.804
0.805
0.786
0.788
0.789
0.790
0.792
0.950
0.950
0.950
0.951
0.951
0.951
0.994
0.994
0.994
0.994
0.994
0.994
4000
0.804
0.805
0.806
0.808
0.809
0.790
0.791
0.783
0.794
0.795
0.953
0.953
0.953
0.954
0.954
0.954
0.997
0.997
0.997
0.997
0.997
0.997
3000
0.808
0.809
0.810
0.811
0.812
0.794
0.795
0.796
0.798
0.799
1.000
1.000
1.000
1.000
1.000
1.000
2000
0.811
0.812
0.814
0.815
0.816
0.797
0.799
0.800
0.801
0.803
30.0
31.0
32.0
33.0
34.0
35.0
1000
0.815
0.816
0.817
0.818
0.820
0.901
0.802
0.804
0.805
0.806
0.818
0.820
0.821
0.822
0.823
0.805
0.806
0.807
0.809
0.810
Temp
C
0.822
0.823
0.824
0.825
0.827
0.809
0.810
0.811
0.812
0.814
0.826
0.827
0.828
0.829
0.830
0.812
0.814
0.815
0.816
0.817
25.0
26.0
27.0
28.0
29.0
0.816
0.817
0.818
0.820
0.821
0.820
0.821
0.822
0.823
0.824
20.0
21.0
22.0
23.0
24.0

397
0.821
0.822
0.823
0.824
0.825
0.826
0.817
0.818
0.820
0.821
0.822
0.823
0.814
0.815
0.816
0.817
0.818
0.820
0.810
0.811
0.813
0.814
0.815
0.816
0.824
0.825
0.826
0.828
0.829
0.830
0.807
0.808
0.809
0.810
0.812
0.813
0.803
0.804
0.806
0.807
0.808
0.809
0.862
0.863
0.864
0.865
0.866
0.867
0.800
0.801
0.802
0.803
0.805
0.806
0.859
0.860
0.861
0.862
0.863
0.863
0.796
0.797
0.799
0.800
0.801
0.803
0.855
0.856
0.857
0.858
0.859
0.860
0.793
0.794
0.795
0.797
0.798
0.799
0.852
0.853
0.854
0.855
0.856
0.857
0.789
0.790
0.792
0.793
0.795
0.796
0.849
0.850
0.851
0.851
0.852
0.853
0.786
0.787
0.788
0.790
0.791
0.792
0.845
0.846
0.847
0.848
0.849
0.850
0.782
0.783
0.785
0.786
0.788
0.789
0.842
0.843
0.844
0.845
0.846
0.847
0.779
0.780
0.781
0.783
0.784
0.785
0.838
0.839
0.840
0.841
0.842
0.843
0.775
0.776
0.778
0.779
0.781
0.782
0.835
0.836
0.837
0.838
0.839
8.400
398
0.828
0.829
0.830
0.831
0.832
0.833
0.866
0.867
0.868
0.868
0.869
0.870
0.831
0.832
0.833
0.834
0.836
0.837
0.869
0.870
0.871
0.872
0.873
0.874
30.0
31.0
32.0
33.0
34.0
35.0
0.873
0.873
0.874
0.875
0.876
0.877

51000 52000 53000 54000 55000 56000 57000 58000 59000 60000 61000 62000 63000 64000 65000 66000 67000
0.876
0.877
0.878
0.879
0.879
0.880
Temp
C
0.879
0.880
0.881
0.882
0.883
0.883
0.890
0.890
0.891
0.892
0.893
0.893
30.0
31.0
32.0
33.0
34.0
35.0
0.883
0.884
0.884
0.885
0.886
0.887

34000 35000 36000 37000 38000 39000 40000 41000 42000 43000 44000 45000 46000 47000 48000 49000 50000
Temp
C
0.886
0.887
0.888
0.889
0.889
0.890
Table B3
Table B4
399
Standard Half-Cell Potentials of Selected Reference Electrodes as a

Function of Temperature and Potassium Chloride Reference-Solution
Concentration, in Volts (Liquid-junction potential included multiply
volts by 1000 to convert to millivolts; KCl, potassium chloride; Temp C,
temperature in degrees Celsius; M, molar; , value not provided in
reference)
Silver:silver chloride
Calomel
Temp
C
3M
KCI
3.5M
KCI
Saturated
KCI
3M
KCI
10
15
20
25
30
35
40
0.220
0.216
0.213
0.209
0.205
0.202
0.198
0.215
0.212
0.208
0.205
0.201
0.197
0.193
0.214
0.209
0.204
0.199
0.194
0.189
0.184
0.260
0.257
0.255
0.253
0.249
3.5M
KCI
4M
KCI
Saturated
KCI
Orion 9678
Combination
Electrode
0.254
0.251
0.248
0.244
0.241
0.238
0.234
0.256
0.253
0.249
0.246
0.242
0.238
0.234
0.256
0.252
0.250 0.246
0.248 0.244
0.244 0.239
Table B5
Eh of ZoBells Solution as
a Function of Temperature
(C, degrees Celsius; mV,
millivolts)
Temperature C
Eh (mV)
10
12
14
16
18
20
22
24
25
26
28
30
32
34
36
38
40
467
462
457
453
448
443
438
433
430
428
423
418
416
407
402
397
393
Source: USGS Groundwater Sampling

Field Manual (Chapter 6).
400
Table B6
Troubleshooting Guide for Eh Measurement (, plus or minus; mV,

millivolts; emf, electromotive force)
Symptom
Eh of ZoBells solution exceeds

theoretical by 5 mV
Excessive drift
Erratic performance
Poor response when using
paired electrodes
Possible Corrective Action
Check meter operation:

Use shorting lead to establish meter reading at zero
mV.
Check/replace batteries.
Check against backup meter.
Check electrode operation:
Check that electrode reference solution level is to
the fill hole.
Plug questionable reference electrode into
reference electrode jack and another reference
electrode in good working order of the same type
into the indicator electrode jack of the meter;
immerse electrodes in a potassium chloride
solution, record mV, rinse off and immerse
electrodes in ZoBells solution. The two mV
readings should be 0 5 mV. If using different
electrodes (Ag:AgCl and Hg:HgCl2), reading
should be 44 5 mV for a good reference
electrode.
Polish platinum tip with mild abrasive (crocus cloth,
hard eraser, or a 400600-grit wet/dry
Carborundum paper), rinse thoroughly with
deionized water. Use a Kimwipe if these
abrasives are not available.
Drain and refill reference electrolyte chamber.
Disconnect reference electrode. Drain and refill
electrolyte chamber with correct filling solution.
Wipe off connectors on electrode and meter. Use
backup electrode to check the emf.
Read emf with fresh aliquot of ZoBells solution;
prepare fresh ZoBells solution if possible.
Recondition electrode by cleaning with aqua regia
and renewing filling solution this is a last
resort.
401
Test and calibrate field measurements. Select

downhole or flowthrough-chamber system.
DOWNHOLE
FLOWTHROUGH CHAMBER
Lower sensors and pump

to selected depth.
Install pump in monitoring well or plumbing

for use of existing pump in a supply well.
Install sensors in flowthrough chamber.
Adjust flow to desired purge rate and

record rate and time purging began.
Turn on pump and adjust flow to

desired purge rate, record rate and
time purging began. Allow sensors
to equilibrate at purge rate.
Divert initial water to waste.

Correct chamber in-line from pump.
Adjust flow to chamber and
eliminate backpressure: allow
sensors to equilibrate
Record and monitor sequential sets of field measurement

readings during withdrawal of trial well volume.
After two or more well volumes are purged and before
final five or more readings are made, adjust flow rate to
be used for sampling flow; flow must be sufficient for
dissolved oxygen measurements.
For pH: divert flow from chamber and record
measurement when water is quiescent. Redirect flow to
chamber for next set of readings.
NO
Extend purge time. Document

difficulty in field notes.
Are stabilization criteria being met?
YES
Record at least 5 measurements at

intervals of 3 to 5 minutes or more.
Report the median of the last 5 or more

readings and the time of measurement.
Figure B1
Field-measurement procedures using downhole and flowthrough-chamber systems for groundwater. Source: USGS Groundwater Sampling Field Manual
(Chapter 6).
L1282/Appendix B/frame Page 402 Tuesday, June 19, 2001 1:15 PM
402
Test and calibrate field instruments.
Purge well (see text for exceptions and instructions).
(2)
Field rinse precleaned sampler. Use clean/dirty hands technique.

Lower sampler smoothly, without splashing, to desired depth of screened or open interval.
(If using bailer, double check-valve type is recommended.)
Raise sampler smoothly at a constant rate, keeping lines clean and off the ground.
Place sampler in holding stand.
(3)
Withdraw subsamples from sampler.

If using bailer, insert clean bottom-emptying device with groved hands; device should fit
snugly over collection bottles and (or) measurement vessels.
If a filtered sample is needed, filter in-line from sampler to bottle/vessel.
Drain subsample without turbulence into collection bottles or measurement vessel.
Rinse collection bottle(s) three times with sample (filtrate for filtered samples), fill to brim,
cap tightly, and maintain at temperature of water source until measurement.
Rinse sensors, stir bar, and measurement vessel three times with sample.
For alkalinity, rinse with deionized water.
Step (1)
Insert sensor(s) in measurement vessel.

Wait for sensors to equilibrate to sample temperature.
Dont let sensors touch bottom or sides of vessel.
Swirl or stir gently to mix sample.

Minimize streaming potential or vortex; keep sensor out of vortex.
For pH, do not stir samples with conductivity less than 100 S/cm.
When using magnetic stirrer, use smallest stir bar.
(4)
(5)
(6)
Record field measurement and method used on field form.

Record median value of stabilized readings.
If readings do not stabilize, extend number of measurements and record median of at
least 5 or more sequential readings.
If there is a constant trend toward lower or higher values, record the first value, the range
of values, and the time period observed.
(7)
Repeat process from steps (4) through (7) on two or more subsamples from the same
sample volume to document precision.
Rinse sensors and equipment thoroughly with deionized water.
Discard sample to waste, in accordance with applicable regulations.
(8)
Figure B2
Subsample field-measurement procedures for conductivity, pH, and alkalinity of

groundwater. Source: USGS Groundwater Sampling Field Manual (Chapter 6).
403
8000
7500
7000
ELEVATION, NGVD OF 1929, IN FEET
6500
6000
5500
5000
4500
4000
3500
3000
2500
2000
1500
1000
500
0
-500
-1000
0
20
40
60 80
100 100
120 140 160 180 200
VALUE TO SUBTRACT FROM ATMOSPHERIC PRESSURE, IN MILLIMETERS OF

MERCURY
Figure B3
Factors used to correct atmospheric pressures adjusted to sea level. Source:

USGS Groundwater Sampling Field Manual (Chapter 6).
L1282/Appendix C/frame Page 405 Tuesday, June 19, 2001 1:16 PM
APPENDIX
Common and Scientific Names of

Various Plants
Common Name
Scientific Name
Alfalfa
Algae stonewort
Alyssum
Bean
Bean, bush
Bermuda grass
Birch, river
Black locust
Black willow tree
Bladder campion
Bluestem, big (prairie grass)
Bluestem, little
Bluestem, little
Boxwood
Buffalo grass
Canada wild rye (prairie grass)
Canola
Cattail
Cherry bark oak
Clover
Colonial bentgrass
Colonial bentgrass
Cottonwood, eastern
Cottonwood (poplar)
Crab apple
Medicago sativa
Nitella
Alyssum wulfenianum
Phaseolus coccineus L.
Phaseolus vulgaris cv. Tender Green
Cynodon dactylon
Betula nigra
Robinia pseudoacacia
Salix nigra
Silene vulgaris
Andropogon gerardi Vit.
Andropogon scoparius
Schizachyrium scoparius
Buxaceae
Buchloe dactyloides
Elymus canadensis
Brassica napus
Typha latifolia
Quercus falcata
Genus trifolium
Agrostis tenuis cv. Goginan
Agrostis tenuis cv. Parys
Populus deltoides
Populus
Malus fusca Raf. Schneid
405
L1282/Appendix C/frame Page 406 Tuesday, June 19, 2001 1:17 PM
406
Crested wheatgrass (Hycrest)
Agropyron desertorum (Fisher ex Link)

Schultes
Cypress, bald
Taxodium distichum
Duckweed
Lemna minor
Eastern Cottonwood
Populus deltoides
European milfoil/yarrow
Achillea millefolium
Felt leaf willow
Salix alaxensis
Fescue, hard
Festuca ovina var. duriuscula
Fescue, red
Festuca rubra cv. Merlin
Fescue, tall
Festuca arundinacea Schreb.
Four-wing saltbrush
Aicanescens
Grama, side oats (prairie grass)
Bouteloua curtipendula
Grama, blue
Bouteloua gracilis
Grass, cool season (colonial bentgrass)
Agrotis tenuis
Grass, warm season (Japanese lawngrass) Zoysia japonica
Horseradish (roots)
Armoracia rusticana
Hybrid poplar
Populus deltoides x nigra DN-34,
Imperial California;
Populus charkowiieensis x incrassata;
Populus tricocarpa x deltoides
Hycrest, crested wheatgrass
Agropyron desertorum
Indiangrass (prairie grass)
Sorghastrum nutans
Indian mustard
Brassica juncea
Indian ricegrass
Oryza sativa subsp. indica
Japanese lawngrass
Zoysia japonica
Jimson weed (thornapple)
Datura innoxia
Kenaf
Hibiscus cannabinus L. cv. Indian
Koa haole
Leucaena leuccephala
Kudzu
Pueraria lobata
Lambsquarter
Chenopodium
Legume
Lespedeza cuneata (Dumont)
Little bluestem (prairie grass)
Schizachyrium scoparius
Loblolly pine
Pinus taeda L.
Mesquite
Prosopis
Millet, Proso
Panicum miliaceum L.
Mulberry, red
Morus rubra L.
Mustard, Indian
Brassica juncea
Mustard weed
Arabidopsis thaliana
Oak, cherry bark
Quercus falcata
Oak, live
Quercus virginiana
Osage, orange
Maclura pomifera (Raf.) Schneid
Parrot feather
Myriophyllum aquaticum thlaspi
rotundifolium
Pennycress
Thlaspi rotundifolium
Pennycress, alpine
Thlaspi caerulescens
Pennyworth
Hydrocotyle umbellata
L1282/Appendix C/frame Page 407 Monday, June 18, 2001 9:14 AM
COMMON AND SCIENTIFIC NAMES OF VARIOUS PLANTS
Poplar, cottonwood
Poplar, hybrid
Poplar, yellow
Red fescue
Reeds
Rice
Sacaton, alkali
Sea pink; wild thrift
Salt marsh plant
Sand dropseed
Soybean
Spearmint
Sugarcane
Sudangrass
Sunflower
Switchgrass (prairie grass)
Tall fescue
Thornapple (jimson weed)
Thrift (wild); sea pink
Tobacco
Water hyacinth
Water milfoil
Water velvet
Wheat grass, slender
Wheat grass, western (prairie grass)
Willow tree, black
Willow tree, felt leaf
407
Populus
Populus deltoides x nigra DN-34,
Imperial California;
Populus charkowiieensis x incrassata;
Populus tricocarpa x deltoides;
Populus charkowiieensis x incrassata
Liriodendron tulipifera
Festuca rubra cv. Merlin
Phragmites
Oryza sativa L.
Sporobolus wrightii
Armeria maritima
Spartina alterniflora
Sporobolu cryptandrus
Glycine max L. Merr, cv. Davis
Mentha spicata
Saccharum officinarum
Sorghum vulgare L.
Helianthus annuus
Panicum virgatum
Festuca arundinacea Schreb.
Datura innoxia
Armeria maritima
Nicotiana tabacum
Eichhornia crassipes
Myriophyllum spicatum
Azolla pinnata
Agropyron trachycaulum
Agropyron smithii
Salix nigra
Salix alaxensis
L1282/Appendix C/frame Page 408 Monday, June 18, 2001 9:14 AM
L1282_frame_IDX Page 409 Monday, June 18, 2001 9:13 AM
Index
A
fermentation, 151
natural attenuation of, 97
sources of, 95
Bioaugmentation, 136138
Biodegradation
acceptable, 26
arsenic, 107
benzene, toluene, ethylbenzene, and xylene,
9597
chemical oxidation pretreatment effects, 223
chemical structure and, 36
chemical substrate concentration effects, 27
chlorate, 108
chlorinated aliphatics, 99
chlorinated aromatics, 100103
chlorobenzoates, 100101
chlorophenols, 100101
chromium, 106107
cometabolism effects, 32
conditions necessary for, 26
definition of, 26
electron-acceptor-limited model of, 9495
environmental impacts of, 3234
first-order decay model, 9294
lindane, 106
mercury, 107
metals, 105106
natural attenuation effects, 90109
nitrate, 107108
nitrate esters, 104
nitroaromatics, 103104
organic contaminants, 95
oxyanions, 107108
oxygenated hydrocarbons, 9899
pathways of, 35
pentachlorophenol, 101102
perchlorate, 108
phyto-cover effects, 326327
polychlorinated biphenyls, 101
polycyclic aromatic hydrocarbons, 98, 308
Absorption, 39
Acceptable biodegradation, 26
Adenosine triphosphate, 9091
Adsorption, 39
Advection dispersion equation, 8485
Aerobic oxidation
cometabolism, 202204
description of, 200201
indications for, 200
MTBE degradation, 204205
rates of, 201
Aging, 33
Alkane hydroxylase, 30
Alkane monooxygenase, 30
Alkylbenzene sulfonate, 34
Alkylhalides, aerobic oxidation of, 201
American Society of Testing and Materials,
monitored natural attenuation
support by, 64
Ammonia monooxygenase, 30
Ammonification, 197198
Anaerobic organisms, 5
Analogue enrichment, 25
Anoxic environments, oxidants in, 57
Aquifer matrix, 47
Aquifer solids, 51
Arsenic
biodegradation of, 107
in situ precipitation, 194195
Atmospheric pressures, 383, 403
B
Benzene, toluene, ethylbenzene, and xylene
description of, 6
409
410
primary, 26
rates of, 3538
selenium, 108
structural effects, 3435
treatment wetlands for, 306309
ultimate, 26
Bioemulsifiers, 165
Biogeochemical
definition of, 89
reactions, 8990
Bioremediation, 6
Biostimulation, 136138
Biosurfactants, 165166
Biphenyl dioxygenase, 30
Boiling point, 18
Butane-utilizing bacteria, 202203
C
Carbon tetrachloride, reductive dechlorination of,
159
Chelates, 247
Chemical oxidation
advantages of, 206207
applications of
1,4-dioxane, 222223
biodegradation effects, 223
chemistry of, 208218
concerns regarding, 207
mechanism of action, 206
oxidants used
hydrogen peroxide, 208209, 211213
potassium permanganate, 209, 213216
predictions, 219220
Chlorate biodegradation, 108
Chlorinated aliphatics
aerobic oxidation of, 201
biodegradation of, 99, 138139
mixture of, 156
natural attenuation of, 75, 99
Chlorinated alkanes
aerobic oxidation of, 202
treatment wetland removal of, 306
Chlorinated aromatics
Chlorinated ethenes, reductive dechlorination
using, 145, 170177
Chlorobenzene biodegradation, 100
Chlorobenzoate biodegradation, 100101
Chloroethene reductive dehalogenases, 147

Chloroform, reductive dechlorination of, 159
Chlorophenol biodegradation, 100101
Chromium
in situ precipitation, 192194
Colloidal organic matter, 49
Colloidal particles, 196197
Cometabolism
aerobic, 202204
cautions associated, 2829
chemicals subject to, 28
chlorinated solvents, 139
definition of, 27, 140
environmental consequences of, 28
polycyclic aromatic hydrocarbons, 25
reactions
co-oxidation, 140
mechanisms of, 2932
reactive dechlorination, See Reductive
dechlorination
types of, 28
Comprehensive Environmental Response,
Compensation, and Liability Act,
314
Constructed treatment wetlands
algae in, 279280
bacteria in, 278279
benefits of, 272
components of, 270271
contaminant removal mechanisms
hydraulic retention time, 297299
partitioning and storage, 295296
volatilization, 294295
description of, 270
dissolved oxygen concentration, 294
in Europe, 272273
fish in, 310
free water surface, 276
fungi in, 278279
groundwater remediation use of, 299310
horizontal flow systems
characteristics of, 276277
emergent macrophyte-based systems with,
285
hydrology of, 309310
hydroperiods, 292
inorganics removal using, 309
issues regarding, 273274
metals removal, 300305
morphology of, 309310
popularity of, 271
regulation of, 272, 275276
research of, 274
INDEX
soils
biological influences, 292
cation exchange capacity, 289290
clays, 287
hydric, 287
microbial processes, 292293
mineral, 287
organic, 287288
oxidation reactions, 290291
peats, 287288
pH, 292
reduction reactions, 290291
subsurface flow, 276277
toxic organics removal using, 306309
in United States, 272273
vegetation in
description of, 279, 281282
duckweeds, 283284
emergent macrophyte-based systems
description of, 284
with horizontal subsurface flow, 285
with vertical subsurface flow, 285
free-floating macrophyte-based systems,
282284
multistage macrophyte-based systems,
287
submerged macrophyte-based systems,
285287
water hyacinths, 282283
vertical flow systems
285
wildlife considerations, 274275, 310
Contaminants
availability of, 14
biodegradation of
acceptable, 26
chemical structure and, 36
chemical substrate concentration effects,
27
cometabolism effects, 32
conditions necessary for, 26
definition of, 26
environmental impacts of, 3234
pathways of, 35
primary, 26
rates of, 3538
structural effects, 3435
ultimate, 26
biological characteristics of, 2638
boiling point of, 18
cometabolism of, 2732
411
dense nonaqueous-phase liquid

definition of, 73
identification methods, 8889
permanganate oxidation of, 220221
transport of, 88
Henry's law constant, 1920
hydrolysis of, 2224
immobilization of, 196
inorganic
light nonaqueous-phase liquid, 73
light nonaqueous-phase liquids, 73
natural attenuation removal of, 7277
nonaqueous-phase liquid
definition of, 7374
transfer of, 88
nonaqueous-phase liquids, 7374
octanol/water partition coefficients, 20
photolytic reactions, 2425
physical properties of, 365382
sequestration of, 3334
in soil-plant system, 242243
solubility, 2022
sorption coefficient of
competitive, 49
factors that affect, 39, 4851
kinetic considerations, 50
pH effects, 49
soil, 4348
temperature effects, 48
source areas of, 8
sources zones for, 7273
subsurface movement methods
advection, 8182
dispersion, 8387
treatment wetland removal of
vapor pressure of, 18
Cooxidation, 28
Cosolvents, 49
D
Dechlorination, See Reductive dechlorination
Dehalobacgter restrictus, 145, 147
Dehalococcoides ethenogenes, 146
Dehalospirillum multivorans, 145, 147
Dehydrohalogenation, 23
Denitrification, in situ, 197198
412
Dense nonaqueous-phase liquid contaminants

definition of, 73
identification methods, 8889
permanganate oxidation of, 220221
transport of, 88
Desulfitobacterium sp., 145
Desulfuromonas chloroethenica, 146
3,5-Dichlorobenzoate, reductive dechlorination
of, 156
Dilution, natural attenuation effects, 7981
1,4-Dioxane, ozone oxidation of, 222223
Dispersion
advection dispersion equation, 8485
definition of, 83
mechanical, 84
molecular, 8384
Dissolved organic matter, 49
Dissolved oxygen
measurements of
description of, 113
electrodes, 113115
in field, 116
field calibrations, 115116
salinity correction factors, 392398
Distribution coefficient
definition of, 4546
estimating of, 87
Duckweed-based wetland systems, 283284
E
Earth
anaerobic organisms, 5
history of, 56
Electron-acceptor-limited model, 9495
Enhanced reductive dechlorination
anaerobic oxidation, 158
biostimulation vs. bioaugmentation, 136138
cometabolic, 142144
electron acceptors, 159160
electron donor selection for, 147158
field studies of, 160164
groundwater solute transport of chlorinated
ethenes, 170177
halorespiring microorganisms, 144147
high constituent concentration areas, 169170
low constituent concentration areas, 169
mechanisms of, 138142
microorganisms for
electron donors for, 147158
halorespiring, 144147
hydrogen production, 149151
nutrients, 158
mixture of compounds effect, 155158
oxidation-reduction potential effects, 142

in situ reactive zones for
biofilm, 168169
development considerations, 160163
fermentation, 167168
natural surfactant effect, 165167
performance data, 177183
reagent delivery, 164165
studies of, 135136
Enterobacter agglomerans, 146
Environment, biodegradation effects on, 3234
Environmental Protection Agency, monitored
natural attenuation support by, 64
Estuaries, natural organic material in, 42
Evapotranspiration
description of, 321
effective, 340343
potential, 337340
F
Fermentation
benzene, toluene, ethylbenzene, and xylene,
151
definition of, 150
hydrogen produced during, 149151, 153154
primary, 151
reductive dechlorination, 167168
secondary, 151
First-order decay model, 9294
Flocculation, 196
Fortuitous metabolism, 27
G
Groundwater
field-measurement procedures, 401402
mobile water phase of, 121
phytoremediation of, 259260, 263
rock/soil phase of, 121
treatment wetland remediation of, 299310
velocity of, 82
Groundwater capture zone, 267
Growth rate, 37
H
Half-velocity coefficient, 37
Halorespiration, 144145
INDEX
413
Halorespiring microorganisms
hydrogen consumption, 154
reductive dechlorination using, 144147
types of, 144
Hazard
definition of, 2
predicting of, 4
subjective probability of, 2
transport of, 45
Hazardous waste, 3
Henry's law constant, 1920
Hexachlorbutadiene, treatment wetland removal
of, 308
Hexachlorobenzene, treatment wetland removal
of, 308
High molecular weight natural organic matter, 58
Humic soil organic matter, 42
Hydrocarbons, natural attenuation of, 75
Hydrogen
fermentation-induced production of, 149151,
153154
microorganism production of
competition, 152153
Hydrogenolysis, 55
Hydrogen peroxide, in situ chemical oxidation
uses of, 208209, 211213
Hydrolysis
definition of, 22
equation, 22
plume effects, 2324
rates of, 23
reaction products produced, 2223
Hyperaccumulators, 246247
I
Inorganic contaminants
In situ chemical oxidation
applications of
1,4-dioxane, 222223
biodegradation effects, 223
chemistry of, 208218
concerns regarding, 207
oxidants used

predictions, 219220
In situ denitrification, 197198
In situ precipitation of metals
aquifer parameters, 195196
arsenic, 194195
chromium, 192194
contaminant removal, 196197
principles of, 187195
In situ reactive zones
definition of, 132
description of, 8
design of, 132
effectiveness of, 132133
metals, 134135
nano-scale particle injections
iron
history of use, 225
organic contaminants treatable using,
231232
particle production, 228230
particle size, 226, 228
reductive process, 224225
permeable sediment applications, 231
reductive dechlorination
biofilm, 168169
schematic representation of, 132133
types of, 134135
Instantaneous reaction model, 9495
Intrinsic remediation, See Monitored natural
attenuation
Ionic strength, 49
Ionizability, 5051
Iron, nano-scale injections in in situ reactive zones
history of use, 225
231232
IRZ, See In situ reactive zones
ISCO, See In situ chemical oxidation
Isotherms
definition of, 43
linear sorption, 4344
nonlinear, 44
414
L
Lakes
natural organic material in, 42
recharging, 79
Landfill
history of, 314315
leachates, 273, 317
microbial activity in, 317
moisture flow and content, 333
waste stabilization phases in, 317320
Landfill cover
barrier-type, 316
capillary barrier, 321
conventional
phyto-cover vs., 326
design features of, 316
evapotranspiration, 321
function of, 315316
phyto-cover, See Phyto-cover
requirements for, 315
Light nonaqueous-phase liquid contaminants, 73
Lindane biodegradation, 106
Liquid-filled macropores, 1415
Low molecular weight natural organic matter, 58
M
Marine waters, contaminant levels in, 33
Mass removal efficiency, 7
Maximum growth rate, 37
Mechanical dispersion, 84
Mercury, biodegradation of, 107
Metals, See also specific metal
field filtration of, 121124
filtered vs. unfiltered samples, 120124
microbial transformation of, 190
precipitates, 187
in situ precipitation
aquifer parameters, 195196
arsenic, 194195
chromium, 192194
contaminant removal, 196197
principles of, 187195
in situ reactive zones, 134135
soil concentrations of, 186, 241242
treatment wetlands for, 299310
Methane monooxygenases
description of, 30
types of, 203
Methanotrophs, 202203
Methylene chloride, reductive dechlorination of,
159
Micelles, 289290
Microbial ecology, 6
Microorganisms
electron donors, 92
hydrogen production by, 149151
inorganic contaminants transformed by, 105
reproductive mechanisms of, 9091
in rhizodegradation, 252
Molecular dispersion, 8384
Monitored natural attenuation
capacity, 7778
definition of, 64
description of, 8
documenting of, 66
evaluative approaches, 6569
monitoring and sampling of
case study, 124125
considerations, 109110
dissolved oxygen, 113116
field portable meters, 111
filtered vs. unfiltered metal samples,
120124
low-flow sampling, 124
on-site, 111
oxidation-reduction potential, 117119
pH, 119120
in situ, 112113
techniques for, 110113
organizations that support, 6465
patterns of
contaminant sources, 7277
description of, 71
questions for assessing, 7172
processes that affect
advection, 8182
biodegradation, 90109
dilution, 7981
dispersion, 8387
stabilization, 8889
volatilization, 89
protocols, 7071
terminology associated with, 6465
MTBE, aerobic oxidation of, 204205
N
Nano-scale particle injections, in in situ reactive
zones
iron
INDEX
history of use, 225

231232
permeable sediment applications, 231
Naphthalene dioxygenase, 30
Natural attenuation
capacity, 7778
definition of, 64
description of, 8
documenting of, 66
evaluative approaches, 6569
monitoring and sampling of
case study, 124125
considerations, 109110
dissolved oxygen, 113116
field portable meters, 111
filtered vs. unfiltered metal samples,
120124
low-flow sampling, 124
on-site, 111
oxidation-reduction potential, 117119
pH, 119120
in situ, 112113
techniques for, 110113
organizations that support, 6465
patterns of
contaminant sources, 7277
description of, 71
questions for assessing, 7172
processes that affect
advection, 8182
biodegradation, 90109
dilution, 7981
dispersion, 8387
stabilization, 8889
volatilization, 89
protocols, 7071
terminology associated with, 6465
Natural attenuation capacity, 7778
Natural degradation, See Monitored natural
attenuation
Natural organic matter
high molecular weight, 58
low molecular weight, 58
Natural surfactant effect, 165167
Nitrate biodegradation, 107108
Nitrate esters, 104
Nitrification, 198
Nitroaromatics
415
Nonaqueous-phase liquid contaminants

definition of, 7374
transfer of, 88
O
Octanol/water partition coefficients, 20
Organic contaminants, 95
Organic matter
colloidal, 49
dissolved, 49
soil
composition of, 42
critical level of, 46
definition of, 4142
humic, 42
nonhumic, 42
sediments vs., 4243
sorption coefficient effects, 4950
Oxidants
in chemical oxidation systems
in natural systems, 56
Oxidation-reduction, See REDOX
Oxidation-reduction potential
definition of, 117
measurement of, 117119
reductive dechlorination effects, 142
wetland soils, 290292
Oxyanions
Oxygen
dissolved
description of, 113
electrodes, 113115
in field, 116
field calibrations, 115116
salinity correction factors, 392398
solubility in water, 384391
Oxygenase, 30
Oxygenated hydrocarbons
sources of, 98
Oxyhydroxides, 123
Ozone
chemical structure of, 217
1,4-dioxane oxidation, 222223
in situ chemical oxidation uses of, 208,
216218
416
P
Particle diffusion, description of, 15
Passive remediation, See Monitored natural
attenuation
pe, 5152
Pentachlorophenol biodegradation, 101102
Perchlorate
chlorite, 199
reduction of, 199200
in situ reactive zone for, 199200
Pesticide biodegradation, 104
pH
definition of, 51
measurement of, 119120
wetland soil, 292
Photolytic reactions
definition of, 24
direct, 2425
function of, 24
indirect, 25
Photoreactions, See Photolytic reactions
Phreatophytes, 259260
Phytoaccumulation, 245248, 259, 299
Phyto-cover system
agronomic chemistry sampling of, 358359
benefits of
aesthetic, 327328
ecological, 327328
economics, 329
gas permeability, 327
maintenance, 329
public safety, 329
in situ biodegradation, 326327
case study example of, 344347
conventional covers vs., 326
designing of, 333334
examples of, 323326
illustration of, 323
irrigation/irrigation system
considerations for, 329330
guidelines for, 352356
requirements, 362
maintenance
active, 360361
passive, 361
preventive, 359
models for designing, 333335
nonsoil amendments to, 331
operation and maintenance schedule, 359362
performance of
hydrologic water balance, 332335
potential evapotranspiration, 337343
precipitation, 335
runoff, 335337
water balance model, 343
plants, 322, 331332
poplars, 321322
repairs, 359
safety considerations, 359
sample application of, 344347
schematic of, 334
site inspections, 348349
soil moisture monitoring, 349352
trees
evaluations of, 356358
leaves of, 357358
root systems of, 349
selection of, 321322, 331332
stem evaluations, 356
understory planting, 331
vegetative, 330331
water balance
model, 343
summary overview of, 347348
Phytodegradation, 248250, 258
Phytoextraction, See Phytoaccumulation
Phytoremediation
advantages of, 240
applications of, 258259
decision tree for, 262
definition of, 240
description of, 244
disadvantages of, 240
groundwater contaminants, 259260, 263
phytoaccumulation, 245248, 259, 299
phytodegradation, 248250, 258
phytostabilization, 250251, 258
phytovolatilization, 251252, 258
rhizodegradation, 252256, 258
rhizofiltration, 256259, 258, 299
sediments, 260261, 263
soil-plant system chemicals
metals, 241242
organic compounds, 242243
system design
agronomic inputs, 266
contaminant levels, 265
groundwater capture zone, 267
irrigation, 266
maintenance, 266
overview of, 261265
plant species, 265266
INDEX
417
transpiration rate, 267

treatability, 266
Phytostabilization, 250251, 258
Phytotransformation, See Phytodegradation
Phytovolatilization, 251252, 258
Plants
chemical uptake in
metals, 241242
organic compounds, 242243
enzyme systems of, 248249
phyto-cover system, 322, 331332
rhizodegradation uses of, 255
rhizofiltration uses of, 257
scientific names of, 405407
in treatment wetlands
duckweeds, 283284
description of, 284
282284
287
285287
Pollutants, 5
Pollution evaluations, 2
Polychlorinated biphenyls
plant uptake of, 243
sources of, 101
Polycyclic aromatic hydrocarbons
cometabolism of, 25
half-life of, 295
hydrolysis of, 25
sources of, 98
Poplars, phyto-cover use of, 321322
Potassium permanganate, in situ chemical
oxidation uses of, 209, 213216
Precipitate, 187
Primary biodegradation, 26
Proton, 51
R
Reactive zones, See In situ reactive zones
Recharge
definition of, 79
dilution estimations, 80
REDOX
contaminant transformation, 58
measurement of, 111, 119
poise, 5253
reactions
description of, 53
oxidants, 5657
oxidations, 5354
reductants, 5758
reductions, 5456
wetland soils, 291
zones, 51
Reductants, abiotic environmental, 57
Reductive dechlorination
anaerobic oxidation, 158
cometabolic, 142144
description of, 55
electron acceptors, 159160
electron donor selection for, 147158
field studies of, 160164
groundwater solute transport of chlorinated
ethenes, 170177
halorespiring microorganisms, 144147
high constituent concentration areas, 169170
low constituent concentration areas, 169
microorganisms for
electron donors for, 147158
halorespiring, 144147
hydrogen production, 149151
nutrients, 158
mixture of compounds effect, 155158
oxidation-reduction potential effects, 142
in situ reactive zones for
biofilm, 168169
tetrachloroethane, 141144
Remediation
evolution of, 711
extractive techniques, 78
goal of, 14
phytoremediation, See Phytoremediation
Resource Conservation and Recovery Act, 314
Retardation, equations, 8586
Rhizodegradation, 252256, 258
Rhizofiltration, 256259, 258, 299
Rhizosphere, 254
Risk
assessment of, 23
418
description of, 2
S
Sediments
phytoremediation of, 260261, 263
soil organic matter vs., 4243
treatment wetland, 293
Selenium biodegradation, 108
Sequestration, 33
Smectites, 40
Sodium permanganate, 214
Soil
distribution coefficient of, 45
metals concentration in, 186, 241242
sorption coefficients, 4348
in treatment wetlands
clays, 287
hydric, 287
mineral, 287
organic, 287288
peats, 287288
pH, 292
Soil organic matter
composition of, 42
critical level of, 46
definition of, 4142
humic, 42
nonhumic, 42
sediments vs., 4243
Soil water
composition of, 42
functions of, 42
Solid waste, 318
Solubility
definition of, 2021
single compound in an immiscible liquid, 21
single compound is an immiscible liquid, 22
SOM, See Soil organic matter
Sorption coefficients
competitive, 49
factors that affect, 39, 4851
kinetic considerations, 50
pH effects, 49
soil, 4348
wetland soils, 289
Source areas, 8
Source zones
definition of, 72
types of, 72, 76
Streams, recharging, 79
T
Temperature
reductive dechlorination effects, 158
Tetrachloroethane
hydrogenolysis of, 141
phytodegradation of, 250
reductive dechlorination of, 135, 141144,
152153
1,1,2,2-Tetrachloroethane, treatment wetland
removal of, 306
Toluene dioxygenase, 3031
Toluene monooxygenase, 30
Toxicity characteristic leaching procedure, 241
Transport processes, description of, 1415
Treatment wetlands, See Wetlands, constructed
treatment
Trees, in phyto-cover system
evaluations of, 356358
leaves of, 357358
replacement of, 362
root systems of, 349
selection of, 321322, 331332
stem evaluations, 356
1,1,1-Trichloroethane
hydrolysis effects, 2324
reductive dechlorination of, 159
Trichloroethylene, enhanced reductive
dechlorination of, 135
Trinitrotoluene biodegradation, 104
U
Ultimate biodegradation, 26
V
Vapor pressure, 18
Vicinal dehalogenation, 55
INDEX
419
Volatile organic compounds, Henry's law

constant, 19
Volatilization
definition of, 89
treatment wetland use of, 294295
W
Water hyacinth-based wetland systems, 282283
Wetlands, constructed treatment
algae in, 279280
bacteria in, 278279
benefits of, 272
contaminant removal mechanisms
description of, 270
dissolved oxygen concentration, 294
in Europe, 272273
fish in, 310
free water surface, 276
fungi in, 278279
groundwater remediation use of, 299310
horizontal flow systems
285
hydrology of, 309310
hydroperiods, 292
inorganics removal using, 309
issues regarding, 273274
metals removal, 300305
morphology of, 309310
popularity of, 271
regulation of, 272, 275276
research of, 274
soils

clays, 287
hydric, 287
mineral, 287
organic, 287288
peats, 287288
pH, 292
subsurface flow, 276277
toxic organics removal using, 306309
in United States, 272273
vegetation in
duckweeds, 283284
description of, 284
282284
287
285287
vertical flow systems
285
wildlife considerations, 274275, 310
Z
ZoBell's solution, 399400
Zwitterions, 217

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NATURAL and

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Library of Congress Cataloging-in-Publication Data

Visit the CRC Press Web site at www.crcpublications.com

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Sincere Thanks To:

Dedicated with utmost humility to the heroes and heroines of

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Protocols for Natural Attenuation......................................................70

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Electron Acceptors and Nutrients.....................................158

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Treatment Wetlands for Groundwater Remediation....................................299

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7.11.6 Safety and Preventative Maintenance..............................................359

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Hazardous Wastes Pollution and

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NATURAL AND ENHANCED REMEDIATION SYSTEMS

Rate and Mass

Evaluation of pollution damage.

THE CONCEPT OF RISK

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HAZARDOUS WASTES POLLUTION AND EVOLUTION OF REMEDIATION

The Decision Making Framework

In the face of the many uncertainties surrounding hazardous waste management

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NATURAL AND ENHANCED REMEDIATION SYSTEMS

Cost of Remediation ($)

A hypothetical analysis of cost to risk reduction benefit ratios during remediation

EVOLUTION OF UNDERSTANDING OF FATE AND

Predicting the hazard of an organic contaminant to humans, animals, and plants

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HAZARDOUS WASTES POLLUTION AND EVOLUTION OF REMEDIATION

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NATURAL AND ENHANCED REMEDIATION SYSTEMS

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HAZARDOUS WASTES POLLUTION AND EVOLUTION OF REMEDIATION

use estimation methods. The evolution of understanding of half-lives of chlorinated

EVOLUTION OF REMEDIATION TECHNOLOGIES

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NATURAL AND ENHANCED REMEDIATION SYSTEMS

MNA with Source Reduction

MNA - Monitored Natural Attenuation

Conventional Pump and Treat

In Situ Reactive Zones (IRZ)

Evolution of in situ remediation technologies and improvements in efficiencies.

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HAZARDOUS WASTES POLLUTION AND EVOLUTION OF REMEDIATION

MNA Monitored Natural Attenuation