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Washington, D.C. 1996

National Academy Press
the Hydrologic
Water Science and Technology Board

Geological Survey
Hazardous Materials in
of Research by the U.S.

Environment: The Role
Commission on Geosciences, Environment, and Resources

Committee on U.S. Geological Survey Water Resources Research
i
ii
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NOTICE: The project that is the subject of this report was approved by the Governing Board of the
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iii
COMMITTEE ON U.S. GEOLOGICAL SURVEY WATER

RESOURCES RESEARCH
GEORGE M. HORNBERGER, Chairman, University of Virginia, Charlottesville

LISA ALVAREZ-COHEN, University of California, Berkeley
KENNETH R. BRADBURY, Wisconsin Geological and Natural History
Survey, Madison
CONSTANCE HUNT, World Wildlife Fund, Washington, D.C.
DAWN S. KABACK, Colorado Center for Environmental Management, Denver
DAVID H. MOREAU, North Carolina State University, Raleigh
FREDERICK G. POHLAND, University of Pittsburgh, Pittsburgh, Pennsylvania
FRANK W. SCHWARTZ, The Ohio State University, Columbus
LEONARD SHABMAN, Virginia Polytechnic Institute and State University,
Blacksburg
MITCHELL J. SMALL, Carnegie Mellon University, Pittsburgh, Pennsylvania
ALAN T. STONE, The Johns Hopkins University, Baltimore, Maryland
DAVID A. WOOLHISER, Colorado State University, Fort Collins
National Research Council Staff

STEPHEN D. PARKER, Project Director
ANITA A. HALL, Project Assistant
iv
WATER SCIENCE AND TECHNOLOGY BOARD
DAVID L. FREYBERG, Chair, Stanford University, Stanford, California

BRUCE E. RITTMANN, Vice Chair, Northwestern University, Evanston, Illinois
LINDA M. ABRIOLA, University of Michigan, Ann Arbor
PATRICK L. BREZONIK, Water Resources Research Center, St. Paul,
Minnesota
JOHN BRISCOE, The World Bank, Washington, D.C.
WILLIAM M. EICHBAUM, The World Wildlife Fund, Washington, D.C.
WILFORD R. GARDNER, University of California, Berkeley
THOMAS M. HELLMAN, Bristol-Myers Squibb Company, New York, New
York
CAROL A. JOHNSTON, University of Minnesota, Duluth
WILLIAM M. LEWIS, JR., University of Colorado, Boulder
JOHN W. MORRIS, J.W. Morris Ltd., Arlington, Virginia
CAROLYN H. OLSEN, Brown and Caldwell, Pleasant Hill, California
CHARLES R. O'MELIA, The Johns Hopkins University, Baltimore, Maryland
REBECCA T. PARKIN, American Public Health Association, Washington, D.C.
IGNACIO RODRIGUEZ-ITURBE, Texas A&M University, College Station
FRANK W. SCHWARTZ, Ohio State University, Columbus
HENRY J. VAUX, JR., University of California, Riverside
Staff
STEPHEN D. PARKER, Director
SHEILA D. DAVID, Senior Staff Officer
CHRIS ELFRING, Senior Staff Officer
GARY D. KRAUSS Staff Officer
JACQUELINE MACDONALD Senior Staff Officer
JEANNE AQUILINO Administrative Associate
ETAN GUMERMAN Research Associate
ANGELA F. BRUBAKER Research Assistant
ANITA A. HALL Administrative Assistant
MARY BETH MORRIS Senior Project Assistant
ELLEN DEGUZMAN Senior Project Assistant
v
COMMISSION ON GEOSCIENCES, ENVIRONMENT,

AND RESOURCES
M. GORDON WOLMAN, Chair, The Johns Hopkins University, Baltimore,

Maryland
PATRICK R. ATKINS, Aluminum Company of America, Pittsburgh,
Pennsylvania
JAMES P. BRUCE, Canadian Climate Program Board, Ottawa, Canada
WILLIAM L. FISHER, University of Texas, Austin
JERRY F. FRANKLIN, University of Washington, Seattle
GEORGE M. HORNBERGER, University of Virginia, Charlottesville
DEBRA S. KNOPMAN, Progressive Foundation, Washington, D.C.
PERRY L. MCCARTY, Stanford University, Stanford, California
JUDITH E. MCDOWELL, Woods Hole Oceanographic Institution,
Massachusetts
S. GEORGE PHILANDER, Princeton University, Princeton, New Jersey
RAYMOND A. PRICE, Queen's University at Kingston, Ontario
THOMAS C. SCHELLING, University of Maryland, College Park
ELLEN K. SILBERGELD, University of Maryland Medical School, Baltimore
STEVEN M. STANLEY, The Johns Hopkins University, Baltimore, Maryland
VICTORIA J. TSCHINKEL, Landers and Parsons, Tallahassee, Florida
Staff
STEPHEN RATTIEN, Executive Director
STEPHEN D. PARKER, Associate Executive Director
MORGAN GOPNIK, Assistant Executive Director
GREGORY SYMMES, Reports Officer
JAMES E. MALLORY, Administrative Officer
SANDI FITZPATRICK, Administrative Associate
SUSAN SHERWIN, Project Assistant
retained, and some typographic errors may have been accidentally inserted. Please use the print version of this publication as the authoritative version for attribution.vi
PREFACE vii
Preface
This report is a product of the Committee on USGS Water Resources

Research, which provides consensus advice to the Water Resources Division
(WRD) of the U.S. Geological Survey (USGS) on scientific, research, and
programmatic issues. The committee is one of the groups that works under the
auspices of the Water Science and Technology Board (WSTB) of the National
Research Council. The committee considers a variety of topics that are
important scientifically and programmatically to the USGS and the nation and
issues reports when appropriate.
This report concerns the WRD science and technology that is relevant to
hazardous materials in the soil and water environment, including the subsurface,
stream and lake sediments, and surface waters. Within the USGS, this work is
dispersed in a number of WRD program areas, including basic research,
regional and site assessments, and data collection activities.
In the United States, a massive effort is in progress to remediate sites at
which hazardous materials threaten the environment. For perspective, it has
been estimated that there may be as many as 300,000 sites where soil and/or
ground water may require remediation to reverse the negative impacts of past
industrial, military, agricultural, and commercial activity. Estimates of the costs
of this effort over the next several decades approach a trillion dollars. The
science and technology carried out in the WRD, though modest in terms of
investment, contributes significantly to the national effort by continually
imparting new understanding about the natural processes relevant to the
transport, fate, and remediation of hazardous substances in the soil and water
environments.
PREFACE viii
This report attempts to help shape the overall framework for the agency's
research in hazardous materials science and technology, while pointing up
general areas of scientific opportunity, including communications and
education. As such, the report does not represent an in-depth review of all
germane WRD programs and projects, but instead is a more general document
intended to provide strategic advice to WRD management.
The committee began its review in late 1993, when most members
participated in the regular meeting of the USGS Toxic Substances Hydrology
Program in Colorado Springs, Colorado. Subsequently, the committee met five
more times before completing this report. At meetings, members were briefed
by USGS personnel on a variety of programs and toured field sites—such as the
contaminated ground water sites at Otis Air Force Base on Cape Cod, and a site
of mining-related metals transport into the Arkansas River in Leadville,
Colorado—to acquire information for review. The members wrote individual
contributions and deliberated as a group to achieve consensus on the content of
this report. It is hoped that by maintaining a broad, forward-looking perspective,
this assessment will prove useful.
As the committee deliberated and became more cognizant of USGS
activities, productive discussions occurred between the members and USGS
personnel. This interaction was critical to success of this project. The committee
is particularly grateful to Dr. Robert M. Hirsch, Chief Hydrologist, Dr. Gail E.
Mallard, Acting Assistant Chief Hydrologist for Research and External
Coordination, and their colleagues for all the information and cooperation they
provided.
It is hoped that this report will help promote the understanding of natural
processes relevant to hazardous materials science and technology, and that in
turn, this improved understanding will lead to advances in public policy and
environmental management. The work of the USGS in this area is key to
making progress on one of the most crucial natural resources science policy
issues of our time.
George M. Hornberger
Chair, Committee on USGS
Water Resources Research
CONTENTS ix
Contents
EXECUTIVE SUMMARY 1
1 INTRODUCTION 3
2 OVERVIEW OF THE FEDERAL EFFORT IN HAZARDOUS 8

MATERIAL REGULATION AND REMEDIATION
Legislative Background 8
The Evolution of Research in Hydrology 11
Overview of Relevant USGS Programs 13
Comparison of USGS Hydrologic Research to That of Other 17
Organizations
From Process Discovery to Application: The Role of the USGS 20
3 CHARACTERIZATION: PROCESSES AND METHODS FOR 23

IMPROVING UNDERSTANDING
The Need 23
State-of-the-art of Characterization 24
Critical Areas of Research 34
Opportunities for the USGS 35
4 REMEDIATION 37
Introduction 37
CONTENTS x
State-of-the-Art in the Field 38

Critical Areas for Research 44
Opportunities for the USGS 45
5 MATHEMATICAL MODELS AND DECISION SUPPORT 48

Predictive Flow and Transport Models 49
Decision Support Systems 61
Optimization and Decision Analysis 64
Decision Support in the USGS Hazardous Materials Science Pro- 67
gram
Opportunities for the USGS in Modeling 68
6 CONCLUSIONS 70
Overall Program Framework 70
USGS Collaboration With Other Agencies 71
Some Critical Issues 72
Educational Opportunities 73
Issues in Planning and Implementation 73
REFERENCES 75
APPENDIXES
A U.S. Geological Survey Water Resources Division Plan for Haz- 90

ardous Materials Science
B Biographical Sketches of Committee Members 106

EXECUTIVE SUMMARY 1
Executive Summary
This report focuses on the programs in science and technology of the U.S.
Geological Survey's Water Resources Division (WRD) that are relevant to
hazardous materials in soil and water. In the United States, a massive effort is in
progress to remediate sites at which hazardous materials threaten the
environment. The science and technology programs of the WRD, with a
heritage of over 100 years, contribute significantly to the national remediation
effort by continually imparting new and credible understanding about soil and
water contamination. This report attempts to help shape the overall framework
of the agency's research in hazardous materials science and technology, and
identifies general areas of scientific opportunity. It is not a detailed critique but
instead contains strategic advice to WRD management.
The report was developed over a two-year period, during which time
information was acquired and assessed and conclusions and recommendations
were formulated with respect to: an overall research framework for the agency's
pertinent programs, critical areas of research, educational opportunities,
methods to evaluate research success, and approaches to improve coordination
with others. This report reinforces the widely-held viewpoint that addressing the
nation's hazardous materials problems is a large and challenging undertaking
involving many entities in a cooperative fashion. Among these entities, the
USGS has important roles to play.
From a strategic perspective, the agency must affect a shift in emphasis
from addressing basic questions in hydrogeological sciences toward solving
generic applied problems as congressional attention becomes more oriented
toward practical results and as additional methods
EXECUTIVE SUMMARY 2
for solving problems become available. This will require application of a risk-
based approach for setting research priorities to assure that resources are
directed to activities with the greatest potential benefits to public health and the
environment. As part of this risk-based approach, priorities for research and the
evaluation of research results must involve input from cooperating agencies and
peer review of planning strategies and research results.
Although relevant activities in the hazardous materials science and
technology program are dispersed throughout the WRD, this study revealed no
cause for significant reorganization. Nevertheless, the importance of both
internal and external coordination and cooperation will likely increase in the
future in response to strong pressure from Congress to increase productivity
through interagency cooperation. In many cases this cooperation and proactive
outreach will mean maintaining a keen sensitivity to the needs of those entities
who are effectively consumers of research and information generated by USGS
scientists.
The characterization of processes relevant to the transport and fate of
hazardous materials in soils and waters is a significant strength of the USGS.
Long-term, field-based studies, for example, have been one of the agency's
greatest strengths. This type of research should continue and be expanded to
integrate methods to evaluate the effectiveness of remediation efforts. Such an
approach will require continued dedication to research, together with the
development and implementation of new modeling capabilities and decision-
support tools. The USGS should lead the effort to perform the long-term
assessments that are essential to both technology refinement and informed
policy decisions.
INTRODUCTION 3
1
Introduction
The U.S. Geological Survey (USGS) has addressed problems related to the
contamination of surface waters and ground waters since shortly after its
establishment by Congress in 1879. As former USGS hydrologist Walter
Langbein recounts (1981), the first USGS paper on the quality of water
concerned the use of sewage for irrigation (Rafter, 1897). Studies on the effects
of waterborne contaminants have continued to be a focus of the USGS,
especially its Water Resources Division (WRD), which was formed in 1949.
(The 1949 date is deceptively late. Forerunners of the WRD, the “Irrigation
Survey”, the “Hydrologic Branch”, and the “Water Resources Branch” date
from before 1900.)
During the early part of this century, the majority of the contaminant-
related work by the USGS was done under the auspices of the Federal-State
Cooperative Program (Langbein, 1981). This program, in which the federal
investment is matched by a cooperator (typically a state), but in which the work
is performed by USGS personnel, addresses a variety of problems of local
urgency (e.g., sewage discharges, waste storage, urban runoff, etc.). From the
mid-1950's to the early 1970's, the research program of the USGS WRD
burgeoned (Langbein, 1981). In that era, federal programs within the USGS
grew as did the work done for other federal agencies. Subsequent to the 1970s,
WRD programs in hazardous materials science and technology have diversified
and come into their own as the “bread and butter” of the USGS. The Toxic
Substances Hydrology Program was established in 1983, the Nuclear Waste
Hydrology Program was established as a separate program in 1985 (although
the WRD has had a significant effort in this area since the early
INTRODUCTION 4
1960s), and the National Water Quality Assessment (NAWQA) Program was
established as a pilot program in 1986 and as a full-scale program in 1991.
Langbein (1981) pointed out the increasingly important niche that was
being occupied by studies related to water quality within research programs of
the WRD:
Over the years there has been a considerable change in the subject matter of
research due mainly to corresponding changes in the nation's water problems,
especially water quality. Fortunately, the division began to broaden its research
in the 1960's with research into water chemistry as such, and soon expanded
the scope to include geochemical relations. During the 1950's nuclear bomb
testing and the resulting radioactive fallout, and the environmental movement
set in motion in the late 1960's both created a vast explosion of interest in
water quality, so that it is now the dominant feature of the division's research
and includes not only the physical and chemical properties of water, but the
biological and ecological as well.
The USGS focus on developing the geoscience knowledge base that is
required to address the difficult problems facing the nation regarding the need
to maintain good quality waters can be seen as part of a broad effort by many
federal, state, and local agencies to come to grips with issues related to the
disposal and inadvertent releases of hazardous materials in the natural
environment. (In this report, the term “hazardous material” refers to any
substance that poses a substantial risk to human health or the environment as a
result of contamination of water, air, or soil.) In this sense, several programs of
the USGS are related to the science and technology of dealing with hazardous
materials in our society.
The role of the USGS in the hazardous materials arena lies squarely in the
geosciences, the traditional strength of the USGS. The remediation of sites that
have already been contaminated is a daunting task. In addition, the development
of new sites for disposal of wastes, the determination of allowable discharges
into waterways, and the assessment of the efficacy of remediation efforts must
proceed with the very best
INTRODUCTION 5
scientific and technical base if the mistakes of the past are to be avoided in the
future. The potential roles for the USGS in addressing these serious national
problems draw on the experience that the USGS has developed over many
decades (Figure 1-1).
Recognizing that problems related to hazardous materials research and
technology are both national and international in scope, and that the USGS is an
agency charged with providing information to resolve important water-related
problems of the nation, the Committee on USGS Water Resources Research
undertook a review of the research efforts and an assessment of the directions
the WRD should take in this area. In support of the USGS's general objective to
expand the body of scientific knowledge relevant to hazardous materials and
their behavior in the environment, this project sought to:
(1) help establish an overall framework for the USGS's research plan;
(2) identify critical research areas for the coming decade;
(3) advise on educational opportunities in the context of research;
(4) provide guidance on processes and measures for evaluating the
success of research in this area; and
(5) advise on improved approaches for involving “consumers” of the
science and technology in program planning and the
implementation of results.
The committee focused much of its attention on the first two items listed
above. With regard to educational opportunities, the general advice to the WRD
in Preparing for the Twenty-First Century: A Report to the USGS Water
Resource Division (National Research Council, 1991) holds in particular for the
hazardous materials programs. With regard to measures for evaluating research,
the use of peer review is highly recommended. By involving “consumers” of
research in the peer review, the process would also serve to address item 5.
Some of these items will be discussed more fully in the final chapter of this
report, although the bulk of the technical material in this report will concentrate
on a discussion of a framework for research and the identification of some
critical areas of research.
Technology.
INTRODUCTION
FIGURE 1.1 Potential roles for the USGS in Hazardous Materials Science and
6
INTRODUCTION 7
The research conducted by the WRD on topics related to hazardous

materials is spread over many complex WRD programs (as described in
Appendix A). This report is not a detailed review of work within these diverse
programs. Rather, the report is a general review that seeks to provide overall
strategic perspective. It concentrates on four main themes: the understanding of
natural processes that affect the fate and transport of hazardous substances, the
understanding of processes that are useful for remediation of contaminated
sites, the use of research results in the decision-making process, and methods to
assess the success of the various programs in reaching some of the goals within
the critical research areas.
OVERVIEW OF THE FEDERAL EFFORT IN HAZARDOUS MATERIAL REGULATION 8
AND REMEDIATION
2
Overview of the Federal Effort in
Hazardous Material Regulation and
Remediation
LEGISLATIVE BACKGROUND
Efforts of the federal government to regulate toxic and hazardous materials
during the past 40 years have revealed the lack of available knowledge
regarding the extent and severity of hazardous material impacts on human
health and the environment. It is difficult, for example, to state precisely how
many potentially toxic materials are in use, how many enterprises are involved
in hazardous waste management, the total volume of chemical wastes generated
in the United States each year, and the total number of sites used for hazardous
waste management. In addition, very little is known about the toxic effects or
environmental fate of many chemicals. Thus, there are abundant research
challenges in the area of hazardous materials.
The primary role of the USGS in reducing public risks associated with
hazardous materials is to provide scientific support, primarily to other agencies.
As the nation's leading geoscience agency, the USGS provides analyses of the
fate and transport of hazardous substances through natural environments that
are crucial to assessing risks and devising remediation strategies. Because the
USGS is a public agency, its main responsibility is to perform research that will
assist in addressing issues that are most relevant to the public interest: in the
case of hazardous materials, those issues that pose the greatest risk to human
health and the environment.
The federal government first became involved in the regulation of toxic
and hazardous substances with the 1958 Food Additives Amendment to the
Food, Drug, and Cosmetic Act. This amendment contained the
AND REMEDIATION
“Delaney Clause”, which prohibited the addition of a known carcinogen into

human food.
In 1972, the federal government began to regulate hazardous materials that
are released into the environment with the passage of the Federal Insecticide,
Fungicide and Rodenticide Act (FIFRA). This law authorizes the U.S.
Environmental Protection Agency (EPA) to register and regulate the sale and
distribution of pesticides in the United States. And although FIFRA has limited
somewhat the use of pesticides, and thus has produced environmental benefits,
it has also resulted in disposal problems, for example, on farms where disposal
options are limited.
The Toxic Substances Control Act (TSCA), enacted in 1976, was also
designed to manage releases of hazardous substances into the environment.
TSCA gives EPA the authority to restrict the use of substances that are likely to
present an unreasonable risk of injury to human health or to the environment. In
the same year, Congress also authorized the first law regulating hazardous
wastes—the Resources Conservation and Recovery Act (RCRA). Although this
act was passed largely in response to the growing public awareness of serious
problems related to disposal, the RCRA actually regulates the generation and
transport of hazardous wastes.
The Clean Water Act of 1977 as a general pollution statute contains
multiple provisions, the most relevant of which pertains to defining EPA's
mission in the restoration of the physical, chemical, and biological integrity of
the nation's waters. The act prescribes a list of toxic water pollutants and
provides that they are subject to effluent limitations based on a “best available
technology” standard, with EPA having discretion to impose more stringent
limitations based on an “ample margin of safety” standard. This act, of course,
has its roots in the 1948 Federal Water Pollution Control Act, the initial federal
legislation regarding water quality control, which defined the federal role
concerning water quality monitoring and research.
Public concern over hazardous substances increased throughout the late
1970s and early 1980s as the Love Canal incident became national news and
policymakers began to confront the technical complexities of regulating these
substances (Barke, 1988). EPA has estimated that U.S. industries produced
approximately 290 million tons of hazardous wastes
AND REMEDIATION
in 1981, and that prior to RCRA, up to 90 percent of hazardous wastes was

disposed of improperly (Finley and Farber, 1992).
The substantial public concern over hazardous waste disposal sites
climaxed with the 1980 enactment of the Comprehensive Environmental
Response, Compensation, and Liability Act (CERCLA), commonly known as
Superfund, and the 1986 Superfund Reauthorization and Amendment Act
(SARA). CERCLA established an information gathering and analysis system to
help government agencies characterize and prioritize remediation of hazardous
waste sites; it also provided the federal authority to respond to emergencies and
remediate sites. The law also created a trust fund to pay for site remediation,
and made parties responsible for releases of hazardous substances on lands for
which they are liable. SARA requires that priority be given to remediation
methods that reduce the toxicity, mobility, and volume of waste rather than
trying to contain waste by transferring it to another land disposal facility. As a
result of amendments to RCRA and CERCLA, there has been a move away
from land disposal of hazardous wastes.
In the mid to late 1980s, following the end of the cold war, the nation
began to recognize the extent of radioactive and other hazardous wastes
stockpiled at Department of Defense (DOD) and Department of Energy (DOE)
facilities. Potential threats to human health and the environment near these sites
come not only from the millions of gallons of wastes that are currently awaiting
proper disposal, but also from seriously contaminated soil, ground water and
surface water, and from releases to the air. Estimated costs for remediation of
these sites exceed $100 billion (World Resources Institute, 1993).
The U.S. Environmental Protection Agency began to question the high
priority placed on remediation of hazardous waste sites in the late 1980s, as the
agency broadened its use of scientific risk assessment. In February 1987, the
EPA released a report on the relative risk of environmental problems in an
attempt to set priorities for its own activities (U.S. Environmental Protection
Agency, 1987). The report concluded that areas related to ground water
consistently ranked medium or low in terms of the relative risk they pose to
human health and the environment. The report found that active hazardous
waste sites ranked relatively high in cancer risks but relatively low in non-
cancer human health risks and ecological effects. These sites can also depress
property
AND REMEDIATION
values. Overall, they were ranked medium in terms of risks to welfare. The
report further concluded that RCRA sites, Superfund sites, underground storage
tanks, and municipal non-hazardous waste sites were among areas of high EPA
effort but relatively medium or low risk (Environmental Protection Agency,
1990).
Methods for evaluating risks posed by environmental contamination also
began to change significantly in the late 1980s. Conclusions about the relative
risks to human health and the environment historically have been derived from
in vitro tests of toxic pollutants for acute problems such as skin rashes, eye
sensitivity, and immediate mortality to test species such as fish or algae. Cancer
risk also has been evaluated for many chemicals based on laboratory tests.
Within the last decade, however, scientists have been accumulating more
information regarding chronic effects of toxic pollutants largely from field
studies of wildlife and accidental exposures of humans to organohalogens such
as polychlorinated biphenyls, or PCBs (see for example, Colburn et al., 1990).
These studies indicate a correlation between toxic pollutants, particularly
persistent, bioaccumulative, organohalogen compounds, and teratogenic effects
in humans and wildlife. More recent research has discovered that a number of
synthetic chemicals, including pesticides, components in plastics and
detergents, and other industrial products and by-products, are capable of
disrupting the endocrine system. Humans and other organisms are exposed to
these substances primarily through air, water, and ingestion.
These findings, like much of scientific research, tend to raise more
questions than they answer. A substantial amount of public funds is expended
on hazardous material research, regulation, and remediation. In an area of
environmental management where so much uncertainty continues to exist, it is
difficult, but vitally important, to set priorities for research that will be of most
benefit to the public interest over the long term by assuring that remedial
actions are based on sound science and that regulations are formulated and
enforced in an informed manner.
THE EVOLUTION OF RESEARCH IN HYDROLOGY

The National Research Council recently described a conceptual model of
the evolutionary stages of research in hydrogeology (National Research
Council, 1992). Taking a process-oriented viewpoint, the report illus
AND REMEDIATION
trates how research follows a well-defined pathway that leads from process
discovery to process description and finally to process application. Process
discovery is concerned with the original characterization of a process and often
its mathematical formulation. Such a discovery may derive from experiments,
field studies, or theoretical analyses. In most instances, contributions are
required from all areas.
A case in point is the study of dispersion in porous media. The original
studies on the process of dispersion occurred in the early 1950's with simple
column experiments and the development of the theoretical-mathematical
description of the component processes. The role of dispersion at field scales
remained poorly understood until the late 1970's when appropriate theoretical
studies combined with subsequent large-scale field experiments were advanced.
Thus, process discovery depends upon a complementary collection of research
techniques involving laboratory, field, and theoretical approaches.
After a process is discovered, the thrust of research shifts to process
description. This research expands the knowledge base about processes,
detailing how the process works, determining its relative importance to other
processes, and establishing values for characteristic parameters of the process.
The main investigative approaches involve carefully controlled field and
laboratory experiments, and sensitivity analyses with mathematical models.
Returning again to the study of dispersion, examples of research on process
discovery include the many laboratory experi-experiments designed to establish
“characteristic” values of dispersion lengths for different types of media, and
field studies to quantify correlation structures that give rise to macro-scale
dispersion.
After a process and its controlling parameters are well understood, it is
possible to utilize this knowledge to solve practical problems through process
application. For example, after discovering the ability of indigenous populations
of microbes to biodegrade some organic contaminants, and describing the
conditions under which these processes occur, it is possible to focus on the
development of related remedial methodologies.
The conceptual model described above portrays how research in process-
oriented hydrology should proceed, and serves as a basis for this report. The
remainder of this report examines the state-of-the-art of research in areas related
to hazardous materials science and technology, explains how the USGS is
presently positioned for this research, and
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explains how the USGS is presently positioned for this research, and describes
opportunities for the USGS in addressing critical needs in these areas.
The character of scientific research has changed with time. For instance,
from relatively humble beginnings in the 1920's, 1930's, and 1940's, hydrology
has developed into a complex science embodying elements of physics,
chemistry, mathematics, and biology. The research categorization methodology
developed in the previous section can be used as a measure of research progress
in the study of flow and mass transport processes. In general, as fundamental
problems are solved and experience is gained, the research emphasis logically
shifts to applications. For example, such is the case with ground water flow
through saturated media. After over 100 years of research, the continuing focus
in the area of saturated flow is mainly to develop flow codes (e.g., MODFLOW;
McDonald and Harbaugh, 1988), or computational enhancements to codes (e.g.,
Hill, 1990). The study of coupled flow processes (complex problems where, for
example, mass transport depends upon fluid flow and fluid flow depends upon
mass transport), however, remains at the process discovery stage and will
require extensive research to sort out a large array of complex effects.
The emphasis on research related to problems of hazardous waste will
almost certainly shift toward applications. What remains to be discussed is what
ultimately brings about this shift to applications, and when it is likely to occur
in the various process areas. Analysis of these questions should be useful in
planning future USGS research efforts on hazardous materials science and
technology.
OVERVIEW OF RELEVANT USGS PROGRAMS

The WRD of the USGS has a number of programs in which studies are
conducted to aid in resolving problems related to the contamination of surface
and ground waters by hazardous materials (see Appendix A). Funding for
projects related to hazardous materials in various programs within the USGS
has reflected priorities established both by the USGS and by Congress
(Figure 2.1).
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FIGURE 2.1 Expenditures on USGS programs related to hazardous materials:

Federal-State Cooperative Program, Toxic Substances Hydrology Program,
Low-Level Nuclear Waste Hydrology Program, Department of Defense
Environmental Contamination Program.
Note: The values for the Federal-State Cooperative Program are estimated by assuming
that approximately 14 percent of the total Federal-State budget, the future reported by
Gilbert et al. (1987) for FY 1986, is devoted to contaminant-related work.
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Funding for the Federal-State Cooperative Program for projects on

hazardous materials has increased fairly substantially, although in terms of
constant dollars, the funding for the program has been essentially flat. Funding
for the Toxic Substances Program, by the same reasoning, has decreased
slightly in constant dollars. Funding for the Nuclear Waste Hydrology Program
declined to zero in 1994. In addition to programs funded internally by the
USGS, other federal agencies also fund work related to hazardous materials that
is performed by USGS personnel. In recent years, work in support of
environmental restoration and waste management at Department of Defense
(DOD) sites has increased drammatically. Over the past eight years, the relative
contribution of the various major programs has shifted somewhat, with an
increase in the percent of the work funded other federal agencies being related
to growth in work related to hazardous materials (Figure 2.2).
Within and across USGS programs related to hazardous materials science
and technology, there is a spectrum of activities that ranges from pure research
to what may be called service—the problem-solving function of the Water
Resources Division within government. Separating research from service is not
an easy task. Langbein (1981) addressed this question by starting with
Webster's definition of research “(1) careful or diligent search (2) studious
inquiry or examination esp....having for its aim the discovery of new facts and
their correct interpretation, the revision of accepted conclusions, theories or
laws, ...or the practical application of such new or revised conclusions, theories,
or laws.” He pointed out that with a definition as broad as (1), virtually every
program of the USGS, including data collection, would constitute “research”.
He preferred instead the more narrow definition implied in (2), which he
interpreted to mean new techniques, instruments, and exploration (Langbein,
1981).
By this latter definition, research constitutes a relatively small proportion
of the activities of the Water Resources Division. Activities related to hazardous
materials science and technology that concentrate almost exclusively on
research are found mainly in the Toxic Substances Hydrology Program, which
involves researchers in USGS district offices and the national centers. In
addition, core funding for the National Research Program (NRP) contributes
significantly to the overall research effort in hazardous materials science and
technology. There are also
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FIGURE 2.2 Breakdown of funding by major source of funds: Federal

appropriations, state and local government contributions to lthe Federal-State
Cooperative Program, and reimbursements from Other Federal Agencies.
Source: Data for FY 1986 from Gilbert et al. (1987). Data for FY 1994 from
material provided by G. Mallard, USGS, Reston, VA.
many projects under the Federal-State Cooperative Program that have a

substantial research component. NAWQA, which has a small research
component, also provides opportunities for integration of research from other
USGS programs within the framework of issues of national concern.
In this study, the research and service activities of the USGS have been
differentiated in order to concentrate primarily on research. It is recognized that
the service functions can and do contribute to research, but a more intensive
focus on the issue of research per se was chosen.
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COMPARISON OF USGS HYDROLOGIC RESEARCH TO

THAT OF OTHER ORGANIZATIONS
Hazardous material and toxic waste research in the United States is
conducted by a variety of organizations including universities, federal and state
government agencies, and large and small corporations. Historically, the type of
research each has conducted has been framed by a variety of factors, such as the
mission of the organization, history, and circumstance. Federal agencies with
missions related to regulating hazardous materials (e.g., EPA) or with extensive
remediation problems at agency sites (e.g., DOD, DOE) have a perspective
toward research strongly oriented toward short-term results. The USGS is one
of the few federal agencies with a more long-term view, having a broad
program in field-oriented, multidisciplinary research in hazardous materials
science as related to problems in the natural environment. The USGS is known
throughout the world for its experience in monitoring the natural environment
and for the collection of high-quality, consistent data sets. The USGS is
particularly well versed in taking an integrated approach to the study of systems
and for including the important details regarding temporal and spatial variability
in characterizing natural constituents.
Universities, by virtue of the discontinuous funding they receive for
research and the relatively more limited infrastructure, typically restrict their
research to aspects of process discovery. Much of the work involves computer
simulation or laboratory experimentation. Field-related hazardous material
remediation studies, when they are undertaken, often require strong support
from organizations like the USGS, ARS, or the DOE that have ongoing field
operations. Some programs have been able to fund field research at high levels
from a variety of funding sources, but this is the exception rather than the rule.
Programs of the USGS related to hazardous materials science and
technology are dominated by field studies that have as their goal the discovery
and description of surface and ground water flow and mass transport processes.
This focus is understandable, given the historical roots of research within the
Water Resources Division, and the distributed character of the organization
where many researchers work in district offices. The USGS is one of a very few
organizations among all of the
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groups (universities, other federal agencies, and states) that has the ability to
conduct long-term research in field settings.
EPA, DOD, and DOE focus much of their research efforts on applications
owing to their cleanup responsibilities. These agencies have large and active
programs concerned with developing new remedial strategies for the cleanup of
hazardous and mixed wastes. Much of this research has a strong engineering
orientation directly related to waste (ex situ and in situ waste treatment). All
three agencies support fundamental process studies through their large
extramural grant programs and their own laboratories. Research and
development work in industry is mainly concerned with the commercialization
of new remedial processes and the development of new measurement processes.
The research and development work being performed is tied closely to practice.
Interestingly, the focus of research also can be influenced by the nature of
the reward system. For example, excellence in research at the discovery end of
the spectrum often is “measured” by papers published in high quality scientific
journals that stress innovation in research. Relatively little attention is paid to
whether the research is “industrially relevant”. At the applications end of the
spectrum, success is measured by patents, licenses, and commercialization. In
many cases, research is presented in the scientific literature for reasons other
than to advance science.
This discussion raises important questions concerning the future direction
of research related to hazardous materials. For example, are there reasons why
the USGS or any of the other organizations should reallocate their activities
differently across the research sub-divisions—discovery, description and
application? Are there factors that would favor one given research topic over
another?
Clearly, the assessment of what research will be most important in the next
decade depends upon the selection of rational criteria that might serve to
identify critical research. To a large extent, the “consumer” of the research
determines the prioritization of research foci or areas. Some organizations, like
the National Science Foundation, are responsive to national and international
needs and initiate research in critical areas such as “Global Change and
Continental Hydrology” and “Math and Science Education”. Another large
body of research consumers is represented by industrial hydrogeologists. To
this group, critical research is that with the
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potential to affect the practice of hydrogeology. It is more difficult to support

research programs in the area of process discovery and term them as critical.
However, programs such as the “solvents in ground water program” at the
University of Waterloo, and the “microbial processes program” and the
“passive bioremediation program” developed within the USGS under the
leadership of Derek Lovely and Mary Jo Baedecker, respectively, are examples
of successful research.
Another, slightly different consumer of critical research is the organization
that is conducting the research. For example, critical research for AT&T or IBM
is that research that has the potential to develop new products within the
organization. Critical research at the USGS might involve research that creates
opportunities for technological leadership or increases the effectiveness of its
district efforts. Critical research also may advance specific goals or missions of
the agency, or the public and political perception of what the agency mission is
all about.
To date, individual researchers within the hazardous waste programs bear
the major responsibility for determining the direction and focus of future
studies. In many respects, such an approach provides the academic freedom of a
university researcher with the added benefit of at least some assured funding.
This emphasis on curiosity-driven research has served both the USGS and
individuals well in the past. It could be argued that political and economic
realities have eclipsed this research model, however. The major corporations
cited above all have restructured their research programs in fundamental ways
that emphasize corporate needs for research and development. For example,
although some may lament the passing of the “old” Bell Laboratories as the
premier basic research organization of its kind in the world, AT&T has adapted
to the realities of the market place.
The Toxic Substances Hydrology Program has developed and flourished as
a curiosity-driven research program that has capitalized on the particular
abilities of the USGS to conduct large-scale interdisciplinary field studies.
Nevertheless, there are important ways in which the Toxic Substances Program
must evolve to ensure that the work of the USGS is focused on work of highest
importance to the nation. First, more of the work must be made immediately
relevant to the major cleanup issues that the country is presently facing at
industrial and defense facilities. The report's recommendations in the areas of
remedial technologies provide
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an overview of how to address this problem. Second, complementary laboratory

and modeling studies must be used to support and to generalize field
investigations, which have been the focus of much of the work to date.
FROM PROCESS DISCOVERY TO APPLICATION: THE

ROLE OF THE USGS
As pointed out above, the research programs of the USGS related to
hazardous materials are focused on studies of surface and ground water flow
and mass transport processes. The endpoints for this research—the applications
—are: 1) the analysis of water resources and of sites as to their suitability for
waste disposal; 2) the analysis of contaminated resources and sites to evaluate
the need for cleanup and to determine effective strategies for cleanup; and 3)
the provision of unbiased information to guide legislation and governmental
policy decisions. These are topics of critical concern to the nation. Conservative
estimates of the cost of cleaning up contaminated sites in the United States are
very large. Considering only ground water and soil remediation, and
considering only DOE sites, estimated costs over the next three decades are
several hundreds of billions of dollars (National Research Council, 1994c).
When surface waters, wetlands, and sediments are included and attention is not
focused solely on DOE, it is clear that solutions to the problems associated with
hazardous materials in the environment are both costly and daunting.
Potentially toxic chemicals are now present, at least in trace quantities,
essentially everywhere. For example, polychlorinated biphenyls (PCBs), DDT,
dioxins, hexachlorocyclohexane (HCH), dibenzofurans, chlordane, and
toxaphene have been found in arctic air, surface water, snow, suspended
sediments, fish, marine mammals, seabirds, terrestrial animals and humans
(Barrie et al., 1992; Lockhart et al., 1992; Muir et al., 1992; O'Connor et al.,
1992; Thomas et al., 1992). The nearly ubiquitous nature of hazardous materials
presents two key challenges to those involved in research on hazardous
materials in the environment: defining the major problems (with regard to risk
to human health and
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ecosystem functioning) and determining practical alternatives for alleviating the

problems.
A broad range of problems involving the contamination of water resources
affect the United States. Surface waters, including streams, rivers, wetlands,
lakes, reservoirs, and estuaries, are contaminated with organics, metals,
nutrients, and sediments. Sources of the contamination range from industrial
discharges to agricultural runoff to direct deposition from the atmosphere.
Because many of the contaminants that are released into surface waters partition
onto sediments, there are also significant problems associated with hazardous
materials in deposits of sediments in waterways and wetland areas. A recent
NRC report (National Research Council, 1990a) summarizes some of the
problems related to contamination of surface waters and sediments, and
provides recommendations for restoration of these aquatic systems.
Ironically, laws passed between 1952 and 1977 to control air and water
pollution caused many industries and municipalities to turn to land disposal for
wastes, an action that has contributed to some of the most difficult problems of
ground water and soil contamination now faced. Estimates of the number of
contaminated sites in the United States range in the hundreds of thousands, with
a variety of contaminants present in the soils and ground waters. Some of the
issues related to hazardous substances in ground water are addressed in a recent
NRC report (National Research Council, 1994a).
The long-term outlook for environmental cleanup at contaminated sites is
not clear. Nor are all of the requisite tools available to determine in a cost-
effective manner when natural processes will suffice, i.e., when “passive” or
“intrinsic” remediation will be adequate to protect humans and ecosystems in
the final analysis. Moreover, the scientific understanding and methods needed
to assess the appropriateness of a given site as a waste-disposal facility are not
all yet available.
The strength of the USGS has been in areas of geoscience: in collecting
data that allow assessment of the quality of water, in gaining a fundamental
understanding of what natural processes are important in the transport of
contaminants (including biogeochemical reactions), and in developing models
that are useful in analyzing contaminant transport in natural systems. Building
on these strengths, the USGS should pursue a strategy in the area of hazardous
materials science and technology that
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stresses: 1) improvements in the ability to characterize natural environments in

terms of the transport of contaminants and of the biogeochemical reactions that
affect these contaminants (i.e., gaining an understanding of the nature of
different environments, including processes that affect contaminants); 2)
improvements in methods for remediating contaminated sites (i.e., gaining an
understanding of the processes and techniques that are useful for containing and
for cleaning up contaminated sites); and 3) improvements in the way
information gained from scientific studies can be used to reach decisions about
appropriate actions in cases where cleanup is likely to be difficult and costly. It
is in these areas that the USGS can make important contributions toward
solving the problems associated with remediation of contaminated sites and
with protection of the environment, especially with regard to proposed new
waste-disposal sites. Some of these issues are explored in the remainder of this
report.
CHARACTERIZATION: PROCESSES AND METHODS FOR IMPROVING 23
UNDERSTANDING
3
Characterization: Processes and Methods
for Improving Understanding
THE NEED
Contamination of the environment (surface and subsurface; waters, soils,
sediments, and biota) with hazardous materials has occurred through a variety
of mechanisms induced by humans. Sources of contamination are classified as
either point (a single, concentrated, identifiable source) or nonpoint (a diffuse
source). For example, a chemical spill is a point source of contamination,
whereas runoff from fertilized farmland is a nonpoint source of contamination.
Since the industrial revolution, human activities have served to introduce both
anthropogenic and natural materials to the environment in unnatural ways. For
example, certain mining operations have produced widespread contamination of
surface waters and stream sediments with elevated levels of metals.
A broad spectrum of contaminants have been introduced to the
environment in a variety of ways, including surface spills, underground pipeline
leaks, surface seepage basins, direct releases to streams or lakes, and
underground injection wells. Many industrial operations have resulted in
subsurface contamination by solvents. Many facilities that handled petroleum
hydrocarbons (tank farms, refineries, pipelines, and gasoline stations) have
contaminated the subsurface. Organic contaminants such as solvents and
petroleum hydrocarbons have migrated rapidly in the subsurface at these sites,
often creating large ground water plumes. Naturally-occurring toxic substances
that present human health concerns also have been identified in ground water
and surface water. In a number of cases, radioactive materials and trace metals
from natural sources have
UNDERSTANDING
been found in ground water at levels that exceed public health drinking water
standards. For example, LeGrand (1988) reported elevated activities of radium
and radon in ground waters of the Piedmont Plateau and the Blue Ridge
Mountains. Other toxic substances known to occur naturally at levels exceeding
drinking water standards include arsenic, fluoride, lead, strontium, and selenium
(Hem, 1992). The USGS maintains and distributes a data base containing
chemical analyses of ground water and surface water for many areas of the
United States (Hoffman and Buttleman, 1994).
STATE-OF-THE-ART OF CHARACTERIZATION
The characterization of sites containing hazardous materials must involve
an interdisciplinary approach with personnel with expertise in the fields of
hydrology, geology, geochemistry (contaminant distribution), analytical
chemistry, microbiology, ecology, statistics, and image processing. Improved
understanding of the processes involved in, or affecting, contaminant transport
is critical to developing innovative approaches to characterizing both the
surface and the subsurface, and ultimately preventing future contamination or
remediating sites already contaminated. According to a previous NRC report
“the greatest progress will be made if site cleanups are accompanied by
investigations aimed at identifying the critical conditions and processes
controlling contaminant behavior...” (National Research Council, 1994b).
Improvements in process understanding and the development of innovative
tools for characterization are needed to advance the state of knowledge of
contaminated sites.
In situ remediation represents an attempt to change the physical, chemical,
and biological attributes of natural systems to mitigate the adverse effects of
hazardous materials in the environment. In order for in situ remediation to be
successful, the link between particular attributes of natural systems and the
processes affecting the hazardous constituents must be established clearly.
UNDERSTANDING
Constituents
The physical, chemical, and biological attributes of natural systems vary
from site to site. Characterizing these properties is important because they
determine the response of natural systems to contamination by hazardous
materials. The geology and hydrology define the transport characteristics of the
system. Dissolved anions and cations, mineral surfaces, and natural organic
matter all represent chemical “reagents” that react in distinctive ways with
hazardous waste chemicals. In addition, distribution of bacteria, plants, and
other organisms and their level of metabolic activity are affected by the amount
of organic carbon sources and the nature and amounts of electron acceptors
available.
In recent years significant advances have been made in the characterization
of the chemical and biological constituents of natural systems and in the
understanding of how they react with hazardous materials. The composition,
physical structure, and chemical properties of oxides, clays, and other products
of rock weathering have been extensively characterized (Banfield et al., 1991),
and have been examined within the context of prevailing hydrologic and
biogeochemical conditions (Hem and Lind, 1994; Webster and Jones, 1994).
Information of this kind is important for establishing the types of mineral
surfaces present in soils and aquifer sediments capable of sorbing pollutant ions
(Balistrieri and Chao, 1990; Fuller et al., 1993). For example, iron (II) as a
component of silicate and other minerals commonly found in most aquifer
materials, has been demonstrated as a strong reducing agent with the capacity to
remove many contaminants from the ground water (White, 1990). The efficacy
of the iron (II) reduction process has been demonstrated on chromium (VI) in
the laboratory (Anderson et al., 1994), and several field-based researchers are
examining the efficacy of solids containing both elemental iron and iron (II) as
a reactive barrier to remove organic solvents from ground water (Wilson, 1995).
Natural organic matter is an exceedingly complex material that
significantly affects fate and transport of pollutants in the environment.
Methods have been developed to divide organic matter samples into distinct
molecular size and chemical property fractions (Aiken et al., 1992). Chemical
derivatization and spectroscopic methods have been used to substantially
improve understanding of functional groups and
UNDERSTANDING
other structures within natural organic matter (Leenheer et al., 1995). Further
research is needed to evaluate sorption of organic pollutants onto soils (Chiou et
al., 1983) and to evaluate the role of organic matter in oxidation/reduction
reactions, precipitation/dissolution reactions, and complex formation reactions
with naturally-occurring and contaminant-derived metals (McKnight and
Bencala, 1990).
Bacteria, plants, fungi, and other biological species play an important role
in the transformation of both naturally-occurring and contaminant chemicals
within the environment. Documenting the distribution and metabolic activity of
microorganisms, particularly in subsurface environments, is important for
evaluating the potential for biodegradation of contaminants (Vroblesky and
Chapelle, 1994; Chapelle et al., 1995). Much has been learned in recent years
about the types and abilities of microbial populations indigenous to the
subsurface (Thiem et al., 1994). The reduction of selenium (Oremland et al.,
1994) and uranium (Lovley and Phillips, 1992) by bacteria has been established
recently, providing good evidence that microorganisms play a greater role in the
redox transformations of inorganic contaminants than was previously suspected.
As additional synthetic organic compounds are shown to biodegrade (Visscher
et al., 1994), and as biodegradation in field settings is better understood
(Cozzarelli et al., 1994), the need to properly assess the potential for
biodegradation becomes more readily apparent. Indeed, a remediation strategy
involving no additional active measures is being considered for some
contaminated sites where the processes of natural attenuation and
biodegradation are acting to remediate the site. This new approach to cleanup of
hazardous waste sites is highly dependent on a good characterization of the
environment and a sufficient understanding of these processes.
Processes
It is important to understand the processes governing natural systems on
several temporal and spatial scales. Pertinent temporal scales are linked to a
number of factors: the rates of chemical and biological process, the transport of
solutes and sediments in the hydrologic cycle, the ecosystem response, and
possible human disturbance. Pertinent
UNDERSTANDING
spatial scales range from the molecular (where fundamental chemical and
biological processes take place) through intermediate scales that govern flow
through porous media and the distribution of microorganisms and invertebrates,
to scales applicable to human activities and whole ecosystems, to the global
scale.
Processes such as precipitation/dissolution, adsorption, complexation, and
dispersion, and factors such as oxidation/reduction and pH, control the
migration of many constituents in the environment. A better understanding of
these processes and controls with a focus on hazardous constituents, will
enhance the ability to characterize sites with known contamination and to
design effective remediation systems.
Prior environmental research has focused primarily on processes occurring
in a single medium: air, soil, or water. Natural environments are open systems,
however, and processes acting across media are of fundamental importance. In
order to understand the dynamic behavior of natural systems, an
interdisciplinary approach is required.
Subsurface Processes
Significant advances in knowledge of subsurface contaminant migration
processes have occurred in the last thirty years. Improvements in understanding
of processes such as facilitated transport, adsorption, and dispersion have
enhanced contaminant distribution prediction and remediation systems design.
Progress also has been made in understanding the geological processes that
formed most subsurface units. In particular, more has been learned about
depositional models, diagenetic processes that alter geologic materials,
subsurface heterogeneities, and the hydrology of ground waters that flow
through complex subsurface matrices. Additional advances are needed to
achieve a better understanding of the heterogeneous nature of the subsurface,
however.
Significant progress has been made in the last 20 years in understanding
the ecology of subsurface microorganisms and the role they play in the fate and
mobility of contaminants. Microorganisms have been shown to transform
hazardous materials to products that are either harmless or less hazardous, to
convert them to forms with differing solubility, or to sorb them onto cell
surfaces. In addition, notable advances have been
UNDERSTANDING
made in knowledge of the degradability of numerous hazardous compounds,

including the identification of specific degradation pathways. Many questions
with respect to biological processes in the subsurface, such as microbial
transport (Hurst, 1991), and the fate and degradability of contaminants, still
remain unanswered, however.
Because contaminants such as gasoline and solvents have entered the
subsurface as separate phases (i.e., not as a dissolved phase in water) it is also
necessary to understand multiphase flow in the subsurface. Most research in this
area has concentrated on model studies and well-controlled laboratory
investigations. This theoretical work, originally developed within the petroleum
industry, provides an important theoretical and methodological framework for
subsequent work that has occurred in the field of hydrogeology. The problems
are even more complex in the field of contaminant transport because they
involve interphase mass transfers. Compositional models that incorporate
interphase transfer (Abriola and Pinder, 1985a,b; Baehr and Corapciouglu,
1987) have been used as the principal approach to modeling nonaqueous phase
liquid (NAPL) flow. True multiphase capabilities incorporating complex
patterns of gas flow and mass removal have been developed to support
theoretical investigation of remedial approaches such as gas sparging or soil
venting. Mass transfer between NAPLs and water and between aqueous and gas
phases is being studied to improve the knowledge of contaminant migration
through the subsurface (Anderson et al, 1992; Miller et al., 1990; Whelan et al.,
1994).
There is a deficiency of fundamental field and laboratory data concerning
multiphase flow parameters relevant to contaminant systems. Physical models
have been utilized to improve the state of understanding. Mass transfer
reactions typically encompass families of nuclear, chemical, and biological
processes. Although some of these processes like radioactive decay are well
understood, those processes involving multiple chemical species and biological
reactions are much less understood and provide a major focal point of
contemporary research in contaminant hydrogeology. Valid conceptual and
mathematical representations exist for many of these processes, but they have
not yet been applied to solving real world problems. For example, the use of
overly simplistic models such as distribution coefficients to describe sorption is
now being re-evaluated in terms of better conceptual and mathematical models
(Barber,
UNDERSTANDING
1994; Harvey et al., 1989; Harvey and Garabedian, 1991; Stollenwerk, 1991).
Other important areas of research include the modeling of complex species in
solution (MINTEQ: Felmy et al, 1983; EQ3/EQ6: Wolery, 1979) and the
incorporation of inorganic reactions into flow and mass transport models
(Cederberg, 1985; Liu and Narasimhan, 1989; Narasimhan et al., 1986).
The diversity and complexity of subsurface systems require an
understanding of coupled flow processes. Coupling of thermal, hydrologic,
mechanical, biological, and chemical processes is required to obtain a complete
understanding of the subsurface. Tsang (1987) provided a general overview of
the commonly studied coupled problems in hydrology. The most advanced
studies to date involve codes such as V-TOUGH, developed for the Yucca
Mountain nuclear waste repository program to predict the response of the
hydrologic system to significant repository heating (Buscheck and Nitao, 1992).
Other studies have examined density-driven transport of dense hydrocarbon
vapors in partially saturated media (Mendoza and Frind, 1990a,b) and the
development of instabilities in variable density flow (Schincariol and Schwartz,
1993).
The study of fractured media has been a major focus of a group of
researchers over the last 30 years. New knowledge about how fluids move in
the subsurface through fractured media has been obtained through
advancements in fracture flow modeling and field experiments. For example,
the USGS has recently conducted in-depth, multidisciplinary studies of site
characterization and ground water movement in fractured rocks at the Mirror
Lake site in New Hampshire (Hsieh et al., 1993). These studies have brought
together hydrogeologists, geophysicists, geochemists, structural geologists, and
numerical modelers to address fundamental questions of fluid flow in such
environments. Theoretical work in this field has continued to progress through
the development of more realistic fracture flow codes. The state-of-the-art in
discrete fracture models is represented by codes such as NAPSAC (UK
Harwell) and FracMan/MAFIC (Golder Associates, 1988). Recent work
(Sudicky and McLaren, 1992) has extended the discrete modeling approach to
accommodate complex fracture matrix coupling in both flow and contaminant
transport. Most field and laboratory studies related to fractured rock problems
continue to be motivated by the need to assess the implication of fracturing in
relation to waste storage and contaminant transport.
UNDERSTANDING
Surface Processes
When potentially hazardous materials are accidentally spilled or are
deliberately applied on vegetation or soils, they may be transported to surface
waters by direct surface runoff, or to aquifers by water percolating through the
unsaturated zone. Surface waters deserve a great deal of attention because of
their widespread use as drinking water sources, their importance to fisheries and
as habitats for wildlife, and their role in the hydrologic cycle. Energy
production, manufacturing, agricultural production, mining, and waste
treatment all are performed in close proximity to surface waters, and all
represent potential sources of contamination. In addition, surface waters receive
both ground water and atmospheric inputs of contaminants. Sediments, which
often contain considerable contaminant levels as a result of past activities, are
both contaminant sources and sinks with respect to the water column.
Intensive field and analytical research on the fate and transport of surface
applied chemicals has been carried out since the mid-1960s. Much of this
research has been done by the Agricultural Research Service (ARS) of the U.S.
Department of Agriculture (USDA) and by universities. These groups have
developed several computer models that predict the fate and transport of
agricultural chemicals in order to assist policy-makers in making regulatory and
policy decisions (U.S. Department of Agriculture, 1980; Smith, 1992).
However, there are many uncertainties involved in predicting the fate and
transport of surface applied chemicals because of the complicated nature of the
processes and the unpredictability of factors such as precipitation (Woolhiser,
1976).
The flow and chemical composition of upland streams and rivers are
strongly linked to hydrologic processes and biogeochemical processes within
the watershed. There is a clear need to evaluate the causative factors in temporal
variability, especially as they pertain to the movement of hazardous materials.
McKnight and Bencala (1990) and McKnight et al. (1992) of the USGS have
made significant progress in understanding the temporal behavior of iron,
aluminum, and natural organic matter in streams and rivers, and their
biogeochemical linkages. In these studies, the exchange of water and solutes
with adjoining sediments and aquifers has been found to be significant.
UNDERSTANDING
Lowland rivers, lakes, and estuaries are linked to larger and more complex
watersheds. Establishment of sources and sinks to such systems is essential, as
is the development of a hydrologic model that can account for mass transport.
The dynamic behavior of pesticides and other organic contaminants in San
Francisco Bay has been found to be a strong function of the distribution
between water and suspended sediment (Domagalski and Kuivila, 1993).
Distinguishing hydrologic inputs from atmospheric inputs is important for
evaluating the efficacy of existing regulatory controls on contaminant release.
Estimates of atmospheric inputs into the Chesapeake Bay, for example, have
been revised upward in recent years (Baker et al., 1994).
When dealing with sites contaminated at the ground surface, ecological
characterization is essential. Improving the understanding of stresses and
changes that have occurred as a result of contamination at a site is critical to the
long-term goal of site restoration. Ecological processes must be understood so
that contaminant migration and processes of natural attenuation can be better
understood.
Characterization Methods
Characterization methods available to the geosciences community have
improved vastly in recent years. Some new methods represent cost-effective
and reliable alternatives to existing characterization methods, whereas others
provide insight into parameters and processes that was not available in the past.
In order to obtain information about the geology of a site, samples are
generally collected by drilling holes into the subsurface. Indirect information
about the subsurface geology also can be obtained using both surface and
downhole geophysical tools. Existing methods for characterizing the hydrology
of a site include the installation of wells and piezometers from which aquifer
tests and tracer tests can be performed. In order to obtain information about the
geochemistry of a site (contaminant distribution), samples are collected from
soils (both at the surface and downhole), from ground water, and from vapor
samples in the unsaturated zone.
UNDERSTANDING
Innovations in characterization technology have been developed to

promote collection of better data at lower cost. Emphasis has been placed on
innovative drilling technologies that minimize the amount of hazardous waste
extracted while maintaining the integrity of samples collected. New techniques
to perform chemical analyses in the field have been developed to lower overall
analytical costs and allow for real-time data collection. Innovative geophysical
tools have been developed recently to enable collection of better data about the
geology, geochemistry, and hydrology of the subsurface, while also minimizing
the amount of intrusion into contaminated zones and reducing costs. Chemical
isotopes have been utilized to characterize the age of ground waters and to trace
or delineate ground water flow paths. All this information is used to improve
the understanding of the migration of contaminants with the ultimate goal of
promoting better design of remediation systems.
Innovative drilling technologies recently applied to hazardous waste site
applications include the cone penetrometer, which collects geologic and
geochemical data before new drilling locations are selected. These data are used
to design a more standard drilling program for characterization of the site and
for installation of monitoring wells. Other innovative drilling technologies
include sonic drilling, which minimizes hazardous waste materials extracted
during drilling while maintaining the quality of the core that can be obtained
from the subsurface (Barrow, 1994). Horizontal drilling has been modified for
drilling at hazardous waste sites, enhancing access to the subsurface and
promoting characterization and remediation of sites otherwise inaccessible,
such as under large buildings or under landfills (Kaback et al., 1989).
Innovative sampling technologies include the SEAMIST™ liner that
collects vapor samples at discrete depths in the unsaturated zone. The
HydroPunch™ and the BAT™ sampler have been used to collect depth-discrete
ground water samples from a single borehole (Kaback et al., 1990). Fiber optic
sensors have been developed to detect subsurface contamination in monitoring
wells and have been adapted to the cone penetrometer to provide real-time data
in the field (Colston et al., 1992). Innovations in three-dimensional image
analysis have allowed scientists to create better visualizations of subsurface
contamination (Eddy and Looney, 1993). Geophysical methods for imaging the
subsurface also have been improved. For example, crosshole tomography using
electrical
UNDERSTANDING
resistivity, electromagnetics, and seismic sources has been demonstrated as a

tool to image subsurface geology, hydrology, and the effects of in situ
remediation on the subsurface.
Fate and transport modeling has been advanced using new codes
developed to mimic real subsurface conditions, such as heterogeneity, fractured
bedrock, and adsorption. The understanding of subsurface microorganisms,
their diversity, and their innate ability to remediate contaminants in the
subsurface has developed recently into an important research area. Innovative
techniques to characterize these intrinsic inhabitants of the subsurface using
DNA probes are an example of recent advances in the state-of-the-art (Hazen
and Jimenez, 1988).
The quality and utility of analytical results depend upon many elements of
the research protocol. Samples must be collected over spatial and temporal
scales that capture systematic and stochastic variations in the parameters under
study. Numerous precautions must be taken to maintain the integrity of samples
and minimize contamination. Because each analytical technique has its
strengths and limitations, it is important to perform several complementary
techniques on the same field samples.
Surface water contamination by toxic elements is often demonstrated by
comparing total concentrations in waters receiving anthropogenic inputs to
concentrations from upstream, pristine waters. Ultraclean sampling, handling,
and analysis and careful comparison with reagent and instrument blanks are
necessary to obtain reliable trace metal data from surface waters. Failure to
follow these procedures can yield estimates of toxic metal concentrations that
are two orders-of-magnitude too high (Benoit, 1994). In combination with
ultraclean techniques, resolution of naturally-occurring isotopes (e.g. Erel et al.,
1991) and rare earth element profiles (Olmez et al., 1991) can be used to resolve
anthropogenic inputs from those derived from natural sources.
Characterization of natural organic matter is needed to evaluate its ability
to form complexes with toxic metals, form covalent compounds with pesticides,
participate in dissolution/precipitation reactions of minerals, serve as a carbon
source for bacteria, and form chlorination byproducts during drinking water
chlorination (Aiken and Cotsaris, 1995). USGS scientists have been at the
forefront of developing new and innovative means of collecting (Aiken et al.,
1992) and characterizing (Leenheer et al. 1995) natural organic matter, and
have developed a comprehensive
UNDERSTANDING
understanding of its role in natural biogeochemical processes (Averett et al.,

1989). In addition, Nitrogen-15 and carbon-13 Nuclear Magnetic Resonance
(NMR) methods to obtain fundamental information regarding natural organic
matter functional groups are currently under development (Thorn et al., 1992).
Capillary electrophoresis, which separates organic molecules according to
molecular charge and hydrodynamic radius, has been shown to resolve natural
organic matter sub-fractions (Garrison et al., 1995). In combination with
established detection methods, capillary electrophoresis should be an effective
new tool for characterizing natural organic matter.
Gas chromatography, in combination with electron capture detection or
with mass spectrometry, represents one of the most powerful analytical
techniques available today. Neutral, hydrophobic organic contaminants are most
amenable to such analysis. In the case of polychlorinated biphenyls (PCBs),
resolution of individual congeners at environmentally-relevant levels is now
possible (Eganhouse and Gossett, 1991). Changes in congener profiles in space
and in time are now widely used to explore the physical, chemical, and
biological processes acting upon them. Ionized organic contaminants frequently
require derivatization and sample enrichment. The determination of anionic
surfactants in sewage effluent and ground water samples has, however, been
effectively demonstrated (Field et al., 1992).
CRITICAL AREAS OF RESEARCH

Better understanding of the processes that affect contaminant migration are
critical to cleaning up the nation's hazardous waste sites. Good characterization
data are required to design effective and efficient remediation systems.
Improved understanding of processes such as adsorption, desorption, facilitated
transport, and sediment-water interactions are required so that superior systems
for removing or immobilizing contaminants can be designed and developed.
Characterization of sites with separate phase contaminants such as light
nonaqueous phase liquids (LNAPLs) and dense nonaqueous phase liquids
(DNAPLs) is critical to remediation of sites contaminated with organics. The
principles developed within the petroleum industry regarding petroleum
migration and
UNDERSTANDING
extraction from the subsurface have been, and should be applied to studies of
contaminant fate and transport and remediation designs.
Improvements in the understanding of subsurface heterogeneities also will
be required for better predictions of contaminant fate and transport. A major
research need with respect to characterizing biological processes in the
subsurface is to improve the fundamental understanding of microbial
populations in context with the heterogeneous physical and chemical conditions
of the subsurface. Questions remain as to how microbial populations develop
and are maintained in aquifers through periods of environmental stress caused
by insufficient substrates, nutrients, moisture, or other undesirable conditions.
Associated with these questions are the issues of microbial transport and
survival within saturated and unsaturated, aerobic and anaerobic zones, as well
as the issue of relating microbial populations to flow patterns within an aquifer.
More tools are needed to characterize the subsurface non-invasively or
with minimal invasion. Improved field screening of contaminants could save
millions of dollars. Development of tools to characterize sites with mixtures of
contaminants will be necessary as more is learned about the nature of
contaminant problems. Future research must integrate the understanding of
surface and subsurface processes and closely examine the interaction between
ground water and vadose zone processes. Hazardous waste systems must be
examined as a whole by integrating concepts from a variety of fields.
OPPORTUNITIES FOR THE USGS

The USGS has made significant contributions to the understanding of the
hydrologic cycle and the subsurface in both pristine and contaminated settings.
This research has concentrated on improved understanding of processes rather
than the creation of new technologies. Future opportunities within this arena
will likely be extensions of previous or existing work, rather than totally new
endeavors. Process-related research topics of broad scope that require the
multidisciplinary resources and expertise available within the USGS are listed
below:
UNDERSTANDING
• Hydrological, biological and geochemical processes within fractured

and heterogeneous media.
• The effects of physical form or phase (e.g., NAPLs, gases, sorbed) on
the availability of contaminants to geochemical and microbial actions
and reactions.
• Incorporation of biological processes into contaminant fate modeling.
• Microbial transport through the subsurface.
• Microbiological adaptation and contaminant degradation under
conditions of typical subsurface physical and chemical stresses.
• Development of analytical tools to evaluate chemical, hydrological, and
biological processes directly within the subsurface environment.
• Improved prediction capability for heterogeneities in the subsurface.
• The effect of nutrient levels (nitrogen and phosphorus) on the
chemistry, biology, and transport of contaminants in surface waters.
• Sediment-water interactions, such as contaminant entrainment in
sediments by particle settling, resuspension by storms, and release
caused by chemical and biological processes within the sediment.
• Direct photolysis of contaminants in surface waters, and the reaction of
contaminants with reactive species generated through the photolysis of
organic matter and other natural solutes.
• The production and decomposition of natural organic matter.
REMEDIATION 37
4
Remediation
INTRODUCTION
Although the USGS is unlikely to become directly engaged in either
developing or implementing technologies for remediation, it is likely that the
USGS increasingly will be called on to support cleanup efforts by providing
high quality data on natural systems and processes necessary for the proper
design of remediation options, and to evaluate the efficacy of remediation
efforts through field measurement programs. Moreover, the USGS is well
positioned to further understanding of intrinsic bioremediation, the process that
occurs when natural conditions at a contaminated site promote in situ
bioremediation in the absence of engineering intervention. With appropriate
monitoring, intrinsic bioremediation can be a successful treatment strategy if
the rate of contaminant destruction outpaces contaminant migration such that
the contaminant plume shrinks over time without causing a significant threat of
exposure. Thus, it is considered appropriate for the USGS to participate in the
identification and solution of problems associated with remediation of
contaminated land and water resources. This chapter briefly reviews the state-of-
the-art of remediation technology and monitoring, identifies critical areas for
remediation research, and describes specific research opportunities where the
USGS can contribute to meeting the challenges of remediation contaminated
sites.
REMEDIATION 38
STATE-OF-THE-ART IN THE FIELD

Remedial technologies can be grouped into the following categories, based
upon levels of development as well as effectiveness in providing environmental
remediation.
• Emerging Technology. A technology that requires additional

laboratory or pilot-scale testing to document the technical viability of
the process.
• Innovative Technology. A technology for which cost or performance
information is incomplete, thus impeding routine use. An innovative
technology may require additional full-scale field testing before it is
considered proven and ready for commercialization and routine use.
• Established/Available Technology. A technology that is fully proven,
in routine commercial use, and for which sufficient performance and
cost information is available.
The development and application of many remedial alternatives has

occurred largely in response to the mandates of state and federal regulations
such as “Superfund” (CERCLA and SARA), as discussed in chapter 2. The
range of options that has become available includes emerging concepts with
bench-scale testing, field demonstrations, and techniques approved for full-scale
use and commercialization. For example, the state of technology development
for options applicable to soils, sediments, ground waters, and other matrices
(Table 4.1) includes both ex situ and in situ techniques that are based on
biological, physical, and chemical processes, either in separate or combined
systems. Technology applications for soils, sediments, and ground waters have
been, or are being developed to destroy, detoxify, separate, recover, or
immobilize contaminants according to their functional identity (Figure 4.1 and
Figure 4.2). Many of these same technologies also may be applied to sludges
and dredge spoils. In addition, augmentation and/or enhancement may be
required to optimize in situ biological and physical-chemical techniques, and in
situ immobilization may be but one consequence of an applied technology
rather than its primary intent. Therefore, techniques for contaminant access,
isolation or capture, as well as extraction and ex situ
Table 4.1 Status of Remedial Technologies (Soils, Sediments, Sludges, Ground Waters, and Solid-Matrix Wastes)
Emerging Innovative Established/Available
Bench-Scale Testing Field Demonstration Selected for Remediation Limited Full-Scale Use or Common Full-Scale Use
Limited Data
In situ electrokinetics Radio-frequency heating Solvent extraction Thermal desorption Incineration
REMEDIATION
Land treatment Solidification/stabilization

X-ray treatment Ex situ furnace vitrification In situ soil flushing Soil vapor extraction Above-ground treatment
Electron irradiation Pneumatic or hydraulic Dechlorination Soil washing
fracturing Bioventing
Laser-induced oxidation Treatment wall Air sparging In situ bioremediation
Slurry-phase bioremediation
In situ vitrification
Source: U.S. Environmental Protection Agency, 1994; Kovalick, 1994; and WASTECH, 1995.
39
REMEDIATION 40
FIGURE 4.1 Technologies applicable to soils and sediments.
aqueous-phase treatment, may provide supplemental alternatives for an

integrated remedial approach.
New remedial technologies continue to be developed (WASTECH, 1995),
and the use of innovative options has already surpassed established or
conventional alternatives for remediation at Superfund sites. There has been a
significant trend toward innovation as new technologies are demonstrated and
applied for the remediation of contaminated ground waters,
REMEDIATION 41
FIGURE 4.2 Technologies applicable to ground waters.
soils and sediments (Figure 4.3 and Figure 4.4). Moreover, depending on
site-specific circumstances, more than one technology or process may be
needed to achieve remediation goals. Combinations of technologies that have
already been implemented at Superfund sites include (U.S. Environmental
Protection Agency, 1993a, b):
• soil washing, followed by bioremediation, incineration, or solidification/

stabilization of soil fines;
• thermal desorption, followed by incineration, solidification/-
stabilization, or dehalogenation to treat PCBs;
• soil vapor extraction, followed by in situ bioremediation, in situ
flushing, solidification/stabilization, or soil washing to remove
semivolatile organics;
retained, and some typographic errors may have been accidentally inserted. Please use the print version of this publication as the authoritative version for attribution.REMEDIATION
FIGURE 4.3 Status of treatment technologies at Superfund sites.

Source: EPA, 1994; Kovalick, 1994.
42
retained, and some typographic errors may have been accidentally inserted. Please use the print version of this publication as the authoritative version for attribution.REMEDIATION
FIGURE 4.4 Status of alternative technologies for Superfund Remedial Action.

Source: EPA, 1994; Kovalick, 1994.
43
REMEDIATION 44
• dechlorination, followed by soil washing for inorganics;

• solvent extraction, followed by solidification/stabilization or
incineration of extracted contaminants and solvents;
• bioremediation, followed by solidification/stabilization of inorganics; and
• in situ flushing, followed by in situ bioremediation of organic residuals.
Nearly 50 emerging, innovative, or established/conventional technologies

have been identified for contaminated soils, sediments, sludges, and ground
waters (U.S. Environmental Protection Agency, 1993b). Many include in situ
and ex situ biological, thermal, physical, and chemical processes, which are
supplemented by techniques primarily used for containment, separation, or
enhanced recovery or off-gas treatments. Each involves a variety of challenges,
including cost, performance, technical, developmental, and institutional issues.
Collectively, these challenges constitute screening factors influencing the
efficacy of a particular remedial technology, and range from overall cost to
community acceptability. Some of these factors pose performance-related
questions, whereas the others present opportunities to assign comparative
ratings (i.e., better, average, worse, or inadequate information) based on
available knowledge, experience and expertise. Such an approach has led to the
development of an interagency DOD/EPA remedial technologies matrix (U.S.
Environmental Protection Agency, 1993b), and resource documents that
describe remediation case studies (U.S. Environmental Protection Agency,
1995).
CRITICAL AREAS FOR RESEARCH

Technology development and deployment are in considerable flux, even
for those technologies ranked as having full-scale or conventional status.
Further, technologies currently not highly rated in terms of various screening
factors may become attractive in the future as more is learned. There is
considerable opportunity for additional discovery in terms of basic scientific
principles and their applications to remediation, whether for characterization of
processes or the environmental setting that
REMEDIATION 45
is the ultimate target for remediation. For example, heterogeneities within

hydrogeological environments, and the complexities of contaminant partitioning
behavior, can hinder the effectiveness of remediation technologies in the field.
Therefore, in order to improve understanding of contaminant transport and fate
within natural systems, research priorities should emphasize studies that employ
direct measurements from field investigations rather than from more easily
controlled laboratory experiments.
A research area that would have major impacts on improved application of
in situ remediation technologies is the development of methods for evaluating
remediation success or progress in the field. Currently, evidence that applied
remediation technologies are responsible for the removal or detoxification of
contaminants is difficult to collect and rarely convincing (National Research
Council, 1993 and 1994b). Similarly, as the limitations of currently applied
physical, chemical, and biological remediation processes, including the
uncertainties of retardation, attenuation, and/or mobility enhancement
mechanisms, become more evident through the increasing numbers of
laboratory field demonstration studies, it will become clear that future priorities
in field-scale development should be directed toward application of
combinations of remediation technologies or remediation technologies that are
designed to work together with natural attenuation processes. Growing out of
these integrations will be the need to understand the complex responses
resulting from multiple processes, in order to more confidently evaluate the
overall effectiveness of complex remediation schemes.
OPPORTUNITIES FOR THE USGS

The research challenges associated with remedial technologies represent an
important avenue of opportunity for the USGS, because the experience and
expertise required to assess and characterize the nation's water resources as
impacted by hazardous materials are the same as those needed to successfully
engage in the assessment of the effectiveness of remediation. Therefore, the
USGS should embark on a focused strategy to position itself as an active
participant in decisions that involve environmental assessments associated with
contaminated soils, sediments,
REMEDIATION 46
ground waters, and surface waters, and the application of innovative

technologies for effective remediation. This strategy is consonant with the
USGS's general objective to expand the body of scientific knowledge relevant
to the behavior of hazardous materials in the environment.
The USGS, as the principal federal nonregulatory organization charged
with investigating water resources problems, is positioned to extend its national
agenda beyond characterization of contaminants and their transport and fate in
the natural environment, to the science and technology of source remediation.
This added dimension is justified because one of the historical strengths of the
USGS has been its long-term involvement in field research. In the area of
hazardous waste remediation, field research should continue to have a high
priority, with the understanding that laboratory studies that support work in the
field will also be necessary and beneficial.
In establishing an agenda for future research emphasis, the USGS should
not specifically direct efforts towards the development of new remediation
technologies, but should capitalize on its field experience and research
capabilities in evaluating the effectiveness of technologies developed and
implemented by others. Because the USGS is not directly associated with
contaminated site liability or directly responsible for cleanup, it should play a
significant role in providing objective and unbiased assessment of results. This
will require close coordination among researchers involved in diverse
applications. For example, researchers studying metals transformation in anoxic
sediments may greatly benefit by frequent communication with those studying
acid mine drainage in surface waters and vice versa.
The programmatic structure of the USGS also is well suited to integrating
short- and long-term field studies with directed laboratory research in the area
of hazardous materials science and technology. The Federal-State Cooperative
Program supports specific site-related studies that are short term and may
include site characterization and monitoring as well as the evaluation of
remedial technologies. The evaluation of more broadly applicable field methods
and techniques may be funded by the Department of Defense Environmental
Contamination Program, whereas the Core Hydrologic Research and Toxic
Substances Hydrology Programs provide long-term funding that supports
scientific work with more prospective potential. Thus, the potential for
integration of exper
retained, and some typographic errors may have been accidentally inserted. Please use the print version of this publication as the authoritative version for attribution. REMEDIATION
be one of the USGS's most valuable assets.

of advancing the science and technology of hazardous materials research, may
tise across disciplinary boundaries, and the associated ability to perform
multidisciplinary short- and long-term research using field sites for the purposes
47
MATHEMATICAL MODELS AND DECISION SUPPORT 48
5
Mathematical Models and Decision Support
Mathematical models are indispensable tools in ground and surface water

hydrology. They provide a basic framework useful in codifying knowledge
concerning the fundamental laws describing the flow of water and mass and
energy transport. Beyond their use in fundamental studies of hydrologic
processes and theory, models assist in decision making in relation to site- or
region-specific problems. In such applications, models can reduce the
uncertainty in decision making by providing a rational, self-consistent structure
for data collection, site characterization, hypothesis testing, quantification of
uncertainty, risk assessment, and the evaluation and design of remediation
alternatives (National Research Council, 1992).
Through the years, the USGS has undertaken a spectrum of modeling
activities, including those that pertain to contaminant transport and multiphase
flow in ground and surface waters (Appel and Reilly, 1994). This chapter
examines recent USGS activities in modeling related to hazardous materials
research and examines opportunities for future work. Three general modeling
types considered include: (1) predictive flow and transport models and their
applications, (2) decision support models, and (3) optimization/decision support
systems. The predictive models include those concerned with the solution of the
classical differential equations for single and multiphase flow, as well as mass
and energy transport. These models commonly find their most important
applications in the elucidation of basic theory and the evaluation of actual
problems. Optimization models represent mathematical approaches for the
analysis of very complex systems with the specific view of finding the best
course of action
from a set of alternatives. They differ from the trial and error approach of
conventional models in that they represent a more formal mathematical
approach to decision making.
A decision support system can be broadly defined as a collection of data,
models, process information, and other expertise that is integrated in a unified
way for analysis and evaluation of problems and alternative solutions to these
problems. Decision support systems differ from the conventional modeling
approaches in that they typically address less well-defined problems,
managerial or planning in nature, without established approaches for solution.
In addition, they stress flexibility to allow for ongoing changes in the situation
or approach of the decision maker (Sprague and Carlson, 1982; Newell et al.,
1990).
Because the USGS has been historically active in the development of
mathematical models for ground water flow and transport, and because similar
activity for surface water quality models has been (at least in recent years)
limited to the integration of existing models in decision support systems, the
following discussion of predictive models for water quality is largely limited to
ground water, whereas the analysis of decision support systems considers both
ground water and surface water models.
PREDICTIVE FLOW AND TRANSPORT MODELS

Flow and transport models are now widely utilized and accepted as tools
for basic scientific study and management of hazardous materials in surface and
ground water environments (Friedman et al., 1984; National Research Council,
1990b). In assessing the state-of-the-art with respect to modeling and
opportunities for research, this study refers to and builds on a recent National
Research Council assessment of modeling carried out for the U.S. Army
(National Research Council, 1992). The development of conventional modeling
approaches is cast in the same framework developed earlier, with a pathway of
evolution leading from process discovery to model application.
Within the context of this modeling approach, process discovery considers
the mathematical formulation of the processes of interest. Process description
refers to detailed studies to examine how the process works, the importance of
one process relative to another, and the worth
of modeling parameters (National Research Council, 1992). The application of

models usually involves the use of the model in a predictive mode to site-
specific problems of assessment and remediation. The extent to which models
can be productively used in practice is mixed. In many cases, such as
multicomponent flow involving NAPLs and water or multispecies transport,
there are usually insufficient data to routinely apply models in a predictive
mode. Models can be used productively for sensitivity analysis to better
understand real problems, however. In other areas, such as aquifer analysis,
models are used routinely in practice. In terms of overall directions for research,
ground water modeling issues with respect to problems of saturated and
unsaturated flow in simple porous media therefore do not present the most
important challenges. Similarly, hydrologic and hydrodynamic models for the
quantity and velocity of surface water flow provide only a portion of the
information needed to predict pollutant fate and transport in surface water
systems, with effective representation of chemical and biological
transformations also required. The difficulties in using more sophisticated
models is well known, and it is in these areas where the greatest potential
remains for research at the USGS.
Table 5.1 represents the committee's view of progress with respect to some
of the most important flow and mass transport processes in ground water. The
list of processes is divided into three parts, representing a set of flow processes,
a set of mass transport and chemical mass transfer processes, and a set of other,
generally more complicated processes. This latter category represent
complexities in the manifestation of processes due to fractures and coupling
among the flow and transport processes.
Saturated Flow in Porous Media

A previous National Research Council report determined that the state of
knowledge with respect to the saturated flow of ground water in porous media
is well developed, with the bulk of research activities at the applications end
(National Research Council, 1992). This finding is not surprising given that
problems of this type have formed the scientific basis of hydrogeology for more
than 100 years. The pioneering efforts in the development of numerical
approaches for the simulation of complex aqui
retained, and some typographic errors may have been accidentally inserted. Please use the print version of this publication as the authoritative version for attribution.MATHEMATICAL MODELS AND DECISION SUPPORT
51
fer systems began in the USGS with the work of Pinder and Bredehoeft
(1968), Pinder and Frind (1972), and Trescott et al. (1976).
Significant efforts have continued within the USGS in the area of aquifer
simulation. The most well-known development in this area is MODFLOW
(McDonald and Harbaugh, 1988), which is the industry standard code for
aquifer analysis. In recent years, USGS efforts have been concerned with
improving the efficiency and robustness of MODFLOW (e.g., Hill, 1990), and
expanding the codes capabilities through useful extensions such as parameter
estimation procedures in MODFLOWP (Hill, 1992), and the capability to treat
narrow horizontal barriers.
A related code, directly relevant to the analysis of contamination problems,
is MODPATH (Pollock, 1989). This code takes flow information from
MODFLOW and computes three-dimensional pathlines. It is used extensively
in industry to estimate directions and spreading rates for plumes and for the
design of pump-and-treat systems.
The potential for scientific work in this area is on the applied side with
prospects for algorithm refinement, improved design interfaces, and the further
development of related “packages.” The MODFLOW family of codes in
particular represent a significant achievement of the USGS. However, USGS
efforts in recent years appear to have lagged behind many of the newest
developments from other government agencies and industry. It is believed that
the USGS must reassert its leadership role in the enhancement of this code, its
distribution, and training in its use. Efforts should focus on ease of use,
visualization technologies, and package integration. Additionally, there is a
need for better links between data input for model codes and real-world spatial
data. For example, the USGS is ideally suited to improve the somewhat crude
links between model inputs and GIS systems. Such efforts would be very useful
to those working in the area of hazardous waste.
Unsaturated Flow in Porous Media

Unsaturated flow processes refer to the flow of a single fluid (in this case,
water) coexisting with a static gas phase. Traditionally, work on this problem
has resided in the domain of soil physicists concerned with local scale fluxes of
water in the vadose zone.
Flow in an unsaturated medium is more complicated than saturated flow.

Hydraulic conductivity, which is constant for saturated flow, varies as a
function of moisture content and ultimately pressure head. In order to model
unsaturated flow, information therefore must be provided on the form of soil
hydraulic conductivity curves (hydraulic conductivity versus pressure head) or
soil-water characteristic curves (soil moisture versus pressure head) (National
Research Council, 1990b). Because the resulting equation of flow is generally
nonlinear, the possibility of analytical modeling of flow is limited to
exponential hydraulic conductivity curves that lead to linearized forms of the
flow equation. Numerical solutions to forms of the unsaturated flow problem
have existed for a long time (e.g., Freeze, 1969; Freeze, 1971).
There is relatively limited theoretical work underway for simple
unsaturated flow problems. Research is now focused on problems involving
dual porosity systems that develop due to the presence of fractures or
macropores, and the more complex problem of mass transport through porous
media. Although this area of modeling research has not received a high priority
within the USGS, there has been work in the development of unsaturated flow
and transport codes (e.g., Lappala et al., 1987).
Much of the most recent theoretical work in unsaturated flow is being
carried out by the national laboratories (e.g., Lawrence Berkeley and Sandia
National Laboratories) in relation to the proposed high-level nuclear waste
repository project at Yucca Mountain, Nevada. In terms of code development
for the assessment of industrial problems of contamination, much of the existing
work is being conducted or sponsored by the U.S. Environmental Protection
Agency and the U.S. Department of Agriculture.
Multiphase Flow in Porous Media

In this report, multiphase flow is used to refer to the simultaneous flow of
water and other liquids or gases. Examples of these problems include the flow
of a nonaqueous phase liquid (NAPL) such as gasoline in a medium that is
saturated or partially saturated with water, or simply water and gases in the
unsaturated zone. Given this report's emphasis on
the USGS hazardous materials initiatives, the discussion will be restricted to

NAPLs.
The basic theory of multiphase flow was developed in the petroleum
industry. These fundamental concepts were adopted in the 1980s by
hydrogeologists concerned with modeling the migration of NAPLs and
developing technologies for their remediation. The NAPL problem, however,
provided significant challenges because of the range in properties of organic
contaminants, and the complex interphase mass transfers due to volatilization or
dissolution of soluble compounds.
Several theoretical approaches were listed in National Research Council
(1992) as available to model multiphase flow of contaminants. These include:
sharp interface approaches, immiscible phase approaches incorporating
capillarity, and compositional models that incorporate interphase transfer. Much
of the ongoing research in the field is targeting the development of
compositional models. However, the U.S EPA is sponsoring the development of
simpler sharp interface models for the application to practical problems. The
inherent complexity of multiphase models and relatively limited availability of
appropriate flow parameters for various materials of interest has unfortunately
limited the application of these models. In industry, there is nonetheless a
history of modeling experience with immiscible approaches, using codes like
SWANFLOW (Faust, 1985; Faust et al., 1989) and ARMOS (Parker et al.,
1990). Table 5.1 reflects the need for considerably more work before the
modeling technology evolves to a completed state, however.
Significant opportunities remain in the modeling and estimation of field
parameters related to multicomponent systems. Continued work can be justified
on the basis of fundamental interest in science, and the seriousness of the
problem posed by LNAPLs and DNAPLs. Historically, little modeling work of
this kind has been undertaken by the USGS. The main emphasis of research in
the Toxic Waste Hydrology Program related to multiphase contamination
problems has been in the geochemical and microbiological investigations of an
oil spill at Bemidji, Minnesota, and a gasoline spill in New Jersey—both
influenced by the unique compositional and chemical characteristics of organic
contaminants. Given the recommendation of this report that the USGS move
into the field aspects of remediation, and the large number of sites where
multiphase contamination is present, there is a critical need for more research on
multiphase problems and for the development of expertise in modeling to

support this work.
Advection and Dispersion

Advection and dispersion together account for the physical transport of
mass from one point to another in a ground water system. Although research on
aspects of dispersion began in the 1950s, the first quantitative description of
advection and dispersion were published by Bear (1972) and USGS scientists
(Bredehoeft and Pinder, 1973). Although the mathematical framework for
describing dispersive processes has been known for more than two decades, it
has been only in the last few years that these processes have been understood
with the confidence represented in Table 5.1.
As National Research Council (1992) points out, the main difficulty in this
area has been in explaining the complexity of dispersion at various scales.
Although theoretical studies of macroscopic dispersion paved the way, it has
been the large-scale field experiments at Canadian Forces Base Borden (e.g.,
Mackay et al., 1986, Sudicky, 1986) and the USGS Cape Cod research site that
have provided the most important new insights on field-scale mass transport.
Mass transport models are now used routinely to model advection and
dispersive processes. Analytical approaches work very well for simple problems
and have formed the basis for practical inverse methods (Domenico and
Robbins, 1985; Ala and Domenico, 1992). More complex problems must rely
on powerful numerical approaches that are embodied in industry-standard codes
like MOC (Konikow and Bredehoeft, 1978).
The number of theoretical studies of advection and dispersion has begun to
decrease after decades of research elucidating the key features of these
processes. Work continues on the development of sophisticated numerical
approaches that overcome limitations with the current generation of codes. It
appears, however, that much of this work is being conducted outside of the
USGS, with noteworthy efforts at the University of Waterloo, Lawrence
Berkeley National Laboratory, and the University of Alabama.
Work remains to be done in this area, although much of the future

emphasis will likely shift to model applications. The USGS could productively
work in the area of new modeling technologies through the development of
refinements designed to improve the robustness and usability of models.
Radioactive Decay, Biological Processes, and Multiphase

Interactions
A variety of chemical, nuclear, and biological processes influence the
transport of mass in geological systems. Due to the number and complexity of
these processes, the list in Table 5.1 is illustrative rather than comprehensive.
As indicated previously (National Research Council, 1992), a few simple
processes such as radioactive decay are well known and can be modeled with
relatively little uncertainty. Several other transport processes that are
represented generally as biological processes and multiphase interactions are
generally poorly known, however. Work to describe these latter groups of
processes constitutes a major new focus of the hazardous substances programs
at the USGS.
Generally speaking, most of the key processes have been “discovered.”
Whether the processes involve biotransformation, surface reactions or mineral
dissolution/precipitation reactions, there are valid mathematical representations
of the processes in terms of several key parameters. Significant gaps in
knowledge exist, however, in terms of the complex interactions that may occur
among constituents, and with natural geological materials.
The USGS efforts in many of the field-oriented programs are targeted
towards understanding diversity and complexity in biological systems, as well
as chemical reactions involving organic and inorganic chemical systems.
Limited knowledge of biological systems means that the fate of only a few
common contaminants under relatively simple geochemical conditions can be
predicted with any certainty. Data necessary to model the kinetic character of
biological reactions are rudimentary. Although considerable research is needed
to fully understand the operation of biological systems, some transport models
have attempted to include biological effects. The simplest models represent the
biotransformation
of organic compounds simply as a first-order kinetic process (Bouwer and

McCarty, 1984). Other more mechanistic transport models (e.g., Borden and
Bedient, 1986; Molz et al., 1986) incorporate kinetic models of the microbial
populations. However, the kinetic (and other necessary) parameters for these
formulations are poorly known and there has yet to be a field-scale validation of
the approach.
Of all the chemical reactions that can affect contaminant fate, sorption is
among the most important. Sorption effectively couples mass in solution to the
solid surfaces, and in so doing can retard the rate of contaminant migration
relative to that of ground water. Compared to biological processes, the problem
of parameterizing such a system is a little less severe for two reasons. First, an
extensive base of information on the equilibrium partitioning of hydrophobic
organic compounds, appears to work reasonably well in ground water systems
(Curtis et al., 1986). The situation is complicated, however, by the fact that
desorption reactions often occur at rates different than sorption reactions.
Second, it is believed that for engineering decisions, metal sorption can be
modeled using site-specific estimates of distribution coefficients. It is generally
conceded, however, that the K d approach to modeling the surface behavior of
metals is seriously flawed. Some of the first field oriented attempts to adapt
more sophisticated process models (e.g., surface complexation, or cation
exchange) are underway at Cape Cod (e.g., Stollenwerk, 1991).
Another type of multiphase process is that involving the redistribution of
mass among the solids, other liquids, and gases that water encounters in moving
through a ground water system. The simplest models of these processes are
based on equilibrium mass law relationships for which relatively complete data
bases of equilibrium constants are available. However, if the reactions of
interest are best described using a kinetic viewpoint, then there are virtually no
existing data to model these processes.
The state-of-practice in the application of transport models that can
account for nuclear, chemical, and biological processes has advanced very little
in recent years. Most codes used in applications typically work with a small
subset of the possible reactions, and avoid coupling among the constituents
through the use of first-order kinetic rate laws for biotransformation reactions,
and simple equilibrium linear or Freundlich models for
sorption. More comprehensive codes have been developed (e.g., Lin and
Narasimhan, 1989), but they are rarely used in solving practical problems.
Beyond the considerable problem of collecting the necessary data to use the
more complex models at a given site, is the more fundamental research need to
validate the modeling approach at both laboratory and field scales.
Significant opportunities remain for field-oriented research in the
elucidation of processes and the characterization of mass transfer parameters.
The existing program in hazardous materials is exceptionally strong in this area
and should continue. Progress in the modeling of complex geochemical systems
has been much more modest and could be improved to take advantage of the
impressive field-scale contributions.
Coupled Flow Processes

The term “coupled flow” is used to describe interdependent flow and
transport processes where, for example, the flow of water depends strongly
upon the concentration and/or temperature distributions, and the concentration
and/or temperature distributions depend upon the flow of water. In even more
complex situations, coupling may involve flow, transport, and mechanical
contributions. The details of coupled flow processes will not be described in
this report; interested readers can refer to a collection of papers on this topic by
Tsang (1987).
Progress in the mathematical modeling of these kinds of problems has
been mixed. For certain problems, such as the interaction between fresh water
and sea water, there has been considerable effort in model development. In
general, however, progress in modeling complex coupled processes is relatively
limited (see Table 5.1). The most serious modeling effort in the area of coupled
flow has been that associated with the proposed high-level nuclear waste
repository at Yucca Mountain, Nevada. In particular, the coupled thermal
hydrologic models V-TOUGH and NUFT likely will form the technical basis
for the license application.
Historically, the USGS has played a role in the development of codes to
simulate coupled phenomena. Examples include the work of Kipp (1987) with
HST3D and Voss (1984) with SUTRA. In recent years, it appears that little
further development work has been undertaken on these
codes. In relation to conventional problems of ground water contamination,

recent modeling studies are examining the density driven transport of dense
hydrocarbon vapors in partially saturated media (Mendoza and Frind, 1990a,b)
or unstable mixed flows (Schincariol et al., 1993).
Coupled process modeling is emerging as a fertile area for both theoretical
and applied research. Coupled systems represent the new frontier for research in
computational hydrogeology. The field has been slow to develop in part
because of the high level of sophistication needed to solve systems of partial
differential equations, and because of the tremendous computational power
required to solve even relatively small problems. Run times of days on state-of-
the-art workstations, and many hours on supercomputers are the norm for even
quite simple problems. The lack of clearly identified practical problems has also
tended to limit development of the field. The emphasis on thermal approaches
to contaminant remediation is one area likely to spur new research, however.
Flow and Transport in Fractured Media

Research efforts to model flow and transport in fractured media have been
ongoing for several decades and are continuing. The main motivation for this
work is the importance of fractured media in relation to contamination
problems, and the scientific and computational challenges in the modeling of
fractured rock systems. The earliest combined flow and transport models
represented fractured systems either as an equivalent porous medium, or as a
discrete network of fractures. With the first of these approaches, it is assumed
that the behavior of the fractured system is describable in a straightforward
manner with porous medium models once an appropriate choice of parameters
is made. In the second approach, each fracture is represented discretely in terms
of its geometry, mean aperture roughness, and interconnection with other
fractures. Codes of this type (e.g., NAPSAC, UK Harwell; FracMan/MAFIC,
Golder Associates, 1988) have been developed to handle flow and transport in
relatively large and complex fracture networks, and have been applied to assess
practical fractured rock problems related to the Stripa Project in Sweden.
One limitation of the current generation of discrete fracture codes is the

inability to handle fracture matrix coupling. Work underway at the University
of Waterloo (Sudicky and McLaren, 1992), however, has led to a powerful new
modeling approach that incorporates fracture matrix coupling. This work
exemplifies the continuing interest in fractured media applied to many different
types of process modeling. Fracture flow and transport codes are also being
used in DOE sponsored studies on both the Waste Isolation Pilot Plant (WIPP)
site in New Mexico and the Yucca Mountain site in Nevada.
The complexity of basic theory and computational burden associated with
the discrete modeling approaches has limited progress in research. Considerable
potential remains in the study of fractured rock problems, however.
Detailed information on the geometry and hydraulic characteristics of
fracture networks is a necessary requirement for the application of sophisticated
modeling codes. Not surprisingly, acquiring this kind of detailed information
requires careful field measurements. The USGS has taken a valuable step
forward in this regard with the initiative at the Mirror Lake Basin in New
Hampshire. The new downhole, and cross-hole testing technologies being
developed at this site will be of great assistance in the characterization of
fractured rock systems.
Issues in Flow and Transport Modeling at the USGS

The leadership role that the USGS has played in the development of
modeling methodologies is reflected in the extent to which models like
MODFLOW, MODPATH, MOC, and others have been accepted by industry.
This role has diminished in recent years, however, as the national laboratories,
other government agencies (e.g., U.S. EPA, U.S. Army), universities and
private industry have taken the lead role in many areas of the modeling field. In
vitally important areas of multicomponent flow and transport, and reactive
transport modeling, the USGS has minimal ongoing efforts.
The USGS should reinvigorate its internal modeling capabilities, and add
to existing capabilities as practicable. Besides the addition of personnel, there is
a critical need for new facilities to support high-speed
computation and visualization. Advanced modeling capabilities are a

requirement for the detailed, field-oriented research programs now operated as
part of the toxic materials program. The design of appropriate experiments, the
interpretation of experimental results, and the development of initiatives in
remediation all require the integration of modeling. It is not in the interest of the
hazardous materials programs to be seen only as an investigator of field-
oriented processes.
The emphasis in research in many areas is rapidly shifting away from
process studies toward applications involving models. It is important for the
USGS to recognize this change in emphasis and diversify activities to some
extent toward the modeling areas. This diversification makes sense
scientifically and tactically, for it is an imperative to develop new modeling
capabilities within the districts as a follow on to the successful Regional
Aquifer-System Analysis (RASA) Program.
Mathematical models for flow and transport are most useful for decision
support when they can be interfaced with an effective data base management
system. The ability to allow flexible data input, storage, retrieval, analysis, and
visualization is an important part of advanced modeling systems. One important
development in recent years is the ability to interface models with Geographic
Information Systems (GIS). An obvious development of this capability would
involve codes like MODFLOW and MODPATH. Basin-scale hydrologic
models are particularly rich in these kinds of applications, including
topographically-based modeling of watershed stream flow with digital terrain
data (e.g., Hornberger and Boyer, 1994) and nonpoint source identification,
modeling and control (e.g., Sivertum et al., 1988; Vieux, 1991; Tim et al., 1992;
Srinivasan and Engel, 1994; Srinivasan and Arnold, 1994; Yoon and
Padmanabhan, 1994).
DECISION SUPPORT SYSTEMS

In most current applications and usage, the concept of a decision support
system is associated with computer-based tools and software packages used in
support of decision making. However, decision support in a more general sense
involves the unified application of information, expertise and experts from
several related fields (such as hydrology,
geology, geochemistry, statistics, and database management) for problem

solution. To a growing extent, these are the types of environmental problems
faced by the USGS and its cooperators, where a range of hydrologic, chemical,
biochemical, and economic factors must be integrated in a consistent, but often
unique manner, in different problem applications.
A decision support system for an environmental problem can serve as a
platform for integrating existing scientific knowledge and data sources on
chemical transport, transformation, and exposure processes in the natural
environment, and allow this information to be used to address critical decisions
and policy concerns. It also can aid in the ability to characterize and assess
current water quality problems, predict the effect of alternative management
strategies, and guide in the selection and implementation of these management
strategies. For example, in watershed-scale assessments, a decision support
system would allow users to:
a. input site or watershed data on hydrogeologic characteristics,

meteorology, water flow, contaminant sources, and water quality
directly or through remote data collection systems;
b. access, manipulate, and utilize data files, including those from
Geographic Information Systems (GIS), for visualization and input
into predictive models;
c. call and test alternative models for chemical transport and
transformation for the site or watershed;
d. allow assessments of the reliability and uncertainty of model
predictions;
e. use the models to examine alternative management options and aid
in the selection of optimal strategies;
f. identify data needs and the value of information to improve models
and associated decisions;
g. track ongoing implementation and monitoring of the management
strategy; and
h. encourage education and participation in the decision process by a
wide range of user groups.
Although this or a similar list of objectives can provide a target for much
of the current research and development in decision support systems, available
systems to date have only been able to provide some of these capabilities.
Development efforts by the USGS should focus most appropriately on a subset
of these capabilities. For example, automated data collection, input to GIS data
base management systems and utilization for site characterization and
assessment fit naturally with the historic mission of the USGS for resource
description. The tracking of implementation of management strategies is
heavily weighted towards the application end of resource management, and may
thus involve more significant efforts by agencies such the EPA, DOD, or DOE.
Even so, at the discovery end, when new decision support system technologies
are developed, these eventual applications must be anticipated.
Existing and Potential USGS Initiatives

The USGS currently has underway a number of projects to support the
development of decision support systems for evaluating surface water flow and
quality. The center-piece of the USGS effort is the Modular Modeling System
(MMS) of Leavesley et al. (1992, 1994, 1995), developed as part of the USGS
initiative on Watershed Modeling Systems. The MMS is an integrated system of
computer software developed to support the development, testing, and
evaluation of hydrologic and ecosystem impact models for watersheds. It
includes a GIS interface for input and management of the watershed data
needed for hydrologic and water quality models, libraries for the selection of
component models, capabilities for parameter estimation, visualization and
statistical analysis of model results, and optimization for determination of
management strategies. MMS allows researchers from a variety of disciplines to
work cooperatively in the development, testing and application of linked
modules in an integrated evaluation framework for multidisciplinary problems.
Additional development work for decision support systems addressing surface
water problems has occurred in selected projects supported by the state water
resources institute programs (e.g., Cheng et al., 1993).
In ground water applications, the enormous quantity of site
characterization data at many sites requires that predictive models be interfaced
with effective data base management systems. Decision support systems for
ground water fate and transport evaluations have been developed, notably the
OASIS system of Newell et al. (1990). The USGS has supported similar efforts
through the state water resources institute programs (e.g., Peralta et al., 1992),
and significant work has been done by private software firms to enhance the
front- and back-end capabilities of the USGS MODFLOW program for more
efficient input, output, and parameter estimation. In addition, advanced database
management and visualization capabilities have been incorporated into a
number of USGS ground water modeling studies. However, a complete and
unified USGS effort for ground water assessment, comparable to that of the
MMS program, is not in place.
In the future, the power of decision support systems to allow analysts and
decision makers to synthesize complex data and model problems and visualize
the impact of alternative management strategies will grow with the availability
of new technologies utilizing 3-D color graphics and perhaps even virtual
reality, where a decision maker could travel along with an “insiders view” of a
proposed remediation option. For certain components of a predictive model, in
which traditional approaches to simulation and data interpretation cannot fully
capture important factors and relationships, approaches based on artificial
intelligence and expert systems may be appropriate. Applications in ground
water science include site characterization, interpretation of geophysical logs,
and model selection and calibration (National Research Council, 1990b).
Because these advanced computer technologies are evolving rapidly, the USGS
should ensure that the scientific information produced by the Survey can be
utilized along with these tools.
OPTIMIZATION AND DECISION ANALYSIS

Predictive models allow decision makers to examine the possible impact of
alternative management strategies in a “what if?” manner. Often, however, the
suite of alternatives is too large or complex to effectively explore in an ad hoc
manner in search of a “best” (or simply “good”) strategy. In this case, more
formal methods for strategy selection
are needed as part of the decision support package. These methods generally
fall into the category of optimization or decision analysis tools.
Optimization methods have been widely applied to both surface water and
ground water problems. Applications have evolved from simple linear, single
criteria, deterministic formulations that consider only water quantity, to
nonlinear, multicriteria formulations that consider uncertainty and address
problems of both water quantity and quality (Hipel, 1992). Numerous
formulations have recently been developed to address the design of ground
water remediation, focusing on the optimal placement, timing, and flow rates of
pump-and-treat capture wells (e.g., Gorelick et al., 1984; Wagner and Gorelick,
1987; Chang et al., 1992; Wang and Ahlfeld, 1994). Optimization is also an
important tool for decision support, and research by the USGS has contributed
significantly to its advancement. Optimization packages for both parameter
estimation and management strategy selection are included as part of the MMS
for watershed evaluation, and similar tools can now be interfaced with
MODFLOW. These efforts are extremely valuable and should continue. Such
an initiative also would be of tremendous industrial and regulatory interest.
A second approach to the selection of management strategies, the
technique of decision analysis, is similar in many respects to optimization, but
emphasizes different aspects of the decision problem. In decision analysis, the
emphasis is on the role of uncertainty in affecting the optimal decision, and the
role that information can play in reducing this uncertainty. The methods of
decision analysis have recently been applied to structure models, data
collection, and management decisions for ground water (e.g., Marin et al., 1989;
Reichard and Evans, 1989; James and Freeze, 1993), and sediment remediation
(Dakins et al., 1994). These methods allow iterative evaluation of ongoing data
collection programs in concert with decisions on contaminant control and
remediation. They are thus well suited for packages that integrate data-base
management, modeling, characterization of uncertainty, and visualization of
water flow and water quality problems.
An important limitation in the application of optimization and decision
analysis methods to the management of hazardous materials in the environment
is the inherent time lag in incorporation of state-of-the-art process knowledge
and models. The critical geophysical, chemical, and
biological processes discussed earlier in this chapter are only now being
incorporated into contaminant transport models. A further lag occurs in the
incorporation of these models into optimization or decision analysis
evaluations. For example, virtually all of the optimization and decision analysis
applications to ground water remediation cited earlier were for “pump-and-
treat” applications assuming dissolved phase contaminant transport with simple
adsorption/reaction processes. In this case, the principal source of uncertainty is
assumed to evolve from the stochastic character of the subsurface hydraulic
conductivity. Although this focus has allowed impressive scientific
advancement and methods development, extension of these methods to consider
other important processes—such as multiphase flow and microbially- and
surface-mediated reactions, and the significant uncertainty present in these
processes—is needed to address the many sites where the traditional model and
pump-and-treat approaches are inadequate (National Research Council, 1994b).
To help speed the transition from research to applied decision models, decision
support systems should be designed in a flexible, modular manner, allowing
easy substitution and testing of alternative model formulations (as is the design
for the MMS). Advances in computing technology, which promote such a
flexible, tool-box approach, can thus go hand-in-hand with advances in
fundamental process knowledge in promoting more effective and useful
decision support systems.
An important recent trend in the management of hazardous materials is the
desire to include a broader range of participants in the decision making process.
Greater stakeholder involvement in problem formulation and evaluation, and
decision making is sought for the cleanup and management of contamination on
both private and public lands. Methods for considering evaluation by multiple
stakeholders have evolved in recent years, including techniques that help
facilitate negotiation and conflict resolution (e.g., Ridgley and Rijsberman,
1992; Thiessen and Loucks, 1992). These features can help enhance a decision
support system and allow it to be used as a focal point for evaluation in a group
decision context.
DECISION SUPPORT IN THE USGS HAZARDOUS

MATERIALS SCIENCE PROGRAM
To help delineate the near-term potential for decision support systems to
enhance the hazardous materials science research program of the USGS, a brief
review of the types of decisions supported in this program is provided. In
particular, the range of decision support exhibited in the USGS Federal-State
Cooperative and DOD contamination programs, and whether and how research
from the Core Hydrologic Research and Toxic Substances Hydrology programs
could better interact with these through the aid of decision support systems, are
considered.
The Core Hydrologic Research program and the Toxic Substances
Hydrology program provide the long-term research for theoretical process
understanding and the development of general methods and tools. Decision
support systems fall within the general domain of such tools; system
development efforts thus occur within these more basic research programs.
However, the motivation for developing these tools is based, in part, on their
potential applications in the Federal-State Cooperative and DOD contamination
programs.
The Federal-State Cooperative program has encompassed approximately
2,000 projects since it was formally recognized in 1928. Both surface and
ground water projects are included, with a somewhat greater portion of the
current activity involving ground water problems. Both water flow and quality
problems are addressed, though the latter have been more greatly emphasized in
recent years. Models of one type or another are used in approximately half of
these investigations. Models are used to a greater extent in ground water
studies; studies of surface waters and non-point source pollution are more often
descriptive in nature.
The DOD contamination hydrology program focuses on specific water and
soil quality problems at DOD sites. In most cases, these problems involve
subsurface soil and ground water contamination, often with the need to consider
geochemical processes for metals and organic complexes. The studies are often
conducted as part of ongoing remedial investigations, aimed at determining
whether the proposed remedy is consistent with the hydrogeologic conditions at
the site. Such sites thus provide the need for ongoing data collection for the
purpose of tracking remediation
progress, effectiveness, and compliance; while also providing the opportunity

for post-audit confirmation studies of predictive models. This type of ongoing
evaluation can be greatly served by decision support systems with integrated
data base and modeling capabilities. To address the evolving needs for
advanced process representation, these systems will require flexible
configurations to allow new models and data configurations to be imported as
the need arises.
Decision support systems with data base and modeling capabilities can
play a direct and important role in expediting the implementation and
interpretation of surface water and ground water studies in both the Federal-
State Cooperative and DOD contamination programs. The capability to
accomplish this for surface water evaluation is now in sight, through the work
of the USGS initiative on Watershed Modeling Systems and the Modular
Modeling System. Similar efforts are underway to enhance the capabilities of
USGS ground water models, although a single, unified effort similar to that of
the MMS is not apparent. The committee supports such integrated research, and
encourages efforts to incorporate and apply this work in the evaluation studies
of the hazardous materials science and technology research program. It is clear
that the USGS research programs provide the information and expertise
necessary for the solution of many critical water quality problems at the site and
regional scale. Development of the next generation of decision support
methodologies and platforms will allow these solutions to be identified in a
more efficient, insightful, and generalizable manner.
OPPORTUNITIES FOR THE USGS IN MODELING

The field of modeling continues to be a fruitful area for potential research.
Given current research directions, several areas in particular should provide
significant opportunities within the USGS, including:
• continued development of the MODFLOW family of codes with

particular emphasis on the addition of state-of-the-art capabilities for
mass transport, more modern solvers, and graphical interfaces;
• development of robust, stand alone mass transport codes capable of

modeling the complexities of reactive chemical transport and the
kinetics of microbial processes;
• modeling and parameterization of field parameters in relation to NAPL-
water systems with emphasis on field and laboratory-based studies as
well as modeling-related work;
• validation of contaminant fate and transport models using field
experiments;
• fundamental work in the model investigation of coupled phenomena; and
• development of new approaches for modeling flow and transport in
fractured rock systems.
The area of decision support is a relatively new field that has not been
studied extensively. Opportunities for research exist at the USGS in:
• the linkage of powerful visualization technologies with the design of

remedial systems;
• the creation of decision support “tool-boxes” similar to MMS that
would enable users to rapidly create and test decision support systems;
and
• the integration of model and data base capabilities in decision support
schemes.
CONCLUSIONS 70
6
Conclusions
Effective policies for hazardous materials management must consider the

development of new methods for the disposal of hazardous materials that avoid
unacceptable levels of contamination, as well as methods for dealing with
existing contaminated waters, sediments, and soils that have resulted from past
inadequate water disposal practices. The USGS, as the agency with primary
responsibilities for assessing the nation's land and water resources, has an
important role to play in the overall solution to problems associated with the
disposal of hazardous wastes. But no single agency, including the USGS, can be
charged with answering all of these questions. What is needed is an imegrated,
cooperative research effort by several agencies and institutions with relevant
roles in the area of hazardous materials management.
In considering directions that the various programs within the USGS could
follow to resolve important problems in hazardous materials science and
technology, this study reached several conclusions and presents a set of
recommendations to the USGS. These recommendations can be interpreted as
broad guidelines for implementing a plan to maximize the effectiveness of
USGS work on hazardous materials.
OVERALL PROGRAM FRAMEWORK

USGS programs should be responsive to national priorities for addressing
problems in the area of hazardous waste. In planning these pro-
CONCLUSIONS 71
grams, careful attention needs to be given to select critical problems for study,
and to appreciate the shift in emphasis in the hydrogeological sciences toward
applied problems of a generic nature. Further, there must be a diversification in
scientific personnel that includes theorists, computer modelers, and laboratory
experimentalists in addition to a field-oriented work force.
The USGS should develop a risk-based approach for setting research
priorities within the hazardous materials programs. It is important that the
agency focus its resources for research on hazardous materials in the hydrologic
environment on those issues that have the greatest potential to reduce risks to
both public health and natural resources. By no means straightforward, the
approach must make full use of decision-support tools as well as the
professional judgement of scientists and decision makers from within and
outside the agency. Documents such as Science and Judgement in Risk
Assessment (National Research Council, 1994d) can provide conceptual
guidance that should be of general value in developing the approach. The USGS
recently adopted a new strategic planning process into which this risk-based
approach can be incorporated explicitly and applied consistently. This process
should be useful in ensuring that actions throughout the agency conform with
agency priorities set over the coming years.
USGS COLLABORATION WITH OTHER AGENCIES

The USGS programs in hazardous materials science and technology are
very diverse and are carried out within an organizational structure that has
evolved over time in response to national problems (Appendix A). The USGS
has produced solid scientific results under this structure, and thus there appears
to be no reason to undertake significant reorganization.
During the course of this study, many instances of cooperation were
evident within the WRD (between scientists in the district offices and scientists
in the NRP), within the USGS (between scientists in WRD and scientists in the
Geological Division), and among federal agencies (among scientists in the
USGS and scientists in other agencies and institutions). In the future,
cooperation will become ever more important because it will be needed to
address interdisciplinary problems and because
CONCLUSIONS 72
there are likely to be fewer federal resources available to address these

issues. The USGS should strive to improve program integration and
coordination both within the USGS itself and with other agencies.
In addition, other federal agencies often act as "consumers" of USGS
research. Satisfying the needs of these agencies is likely to assume increased
importance in the future, as the USGS takes on a new role of assessing the
efficacy of remediation schemes and methods in relation to hydrogeological
settings. Providing leadership in the assessment of long-term results of
environmental remediation and the development of modern methods for
waste disposal is a role that appears to be particularly fitting for attention
by the USGS.
SOME CRITICAL ISSUES

The USGS has been very effective at characterizing natural processes that
control the transport, and to some extent the fate, of hazardous materials
released to the environment. The long-term, field-based, mass transport studies
of environmental contaminants have been a successful part of USGS research.
This type of work should be continued, but expansions into critical areas are
essential. First, the USGS should move aggressively to expand the application
of their broad-based expertise in characterizing natural processes to include the
evaluation of the effectiveness of remediation techniques. Most remediation
systems are evaluated only over relatively short periods of time. The USGS
should lead the effort to perform the long-term assessments that are essential to
both technology refinement and for informed policy decisions. For example, the
USGS should undertake work to assess the long-term performance of
ground water remediation schemes, the side effects of remediation, and
optimal monitoring strategies in various hydrogeological settings.
Other critical areas in which the USGS should consider focusing
attention include the issue of translocation of contaminated sediments and
soils due to extreme events (floods) and, in the area of computer modeling,
the refinement of flow visualization techniques and muiticomponent and
compositional hydrogeochemical modeling.
The USGS also must maintain its strong tradition of interdisciplinary
studies. It is critical that the organization provide an integrated
CONCLUSIONS 73
effort in which physical, chemical, and biological scientists fully cooperate

toward mutual goals.
EDUCATIONAL OPPORTUNITIES
The USGS has provided substantial benefits to students through a
variety of informal mechanisms and should strive to increase cooperative
activities with universities. Evidence for USGS impact on graduate education
includes publications stemming from work in the programs related to hazardous
materials that are co-authored by students from a number of universities. Not
only has the USGS contributed to the education of professionals who will help
solve environmental problems now and in the future, but it has in turn
benefitted by association of USGS scientists with other capable scientists at
universities and elsewhere. When appropriate, such cooperative arrangements
should be encouraged. For example, a professor from a university with strong
programs in contaminant hydrology might be “traded” for a USGS scientist for
a year. Specific problems could be addressed by graduate and undergraduate
students with full or partial USGS funding. The existing relationship between
USGS and land-grant universities through the state water resources research
institutes provides one mechanism for implementing increased cooperation.
ISSUES IN PLANNING AND IMPLEMENTATION

This report identifies issues that should be addressed in the context of
future planning and implementation of research programs. As an institutional
imperative, the USGS must look outward to develop research activities that are
relevant to national needs, such as the cleanup of industrial and defense related
industries. Thus, it is recommended that the USGS make even greater efforts to
communicate and explain results of research on hazardous materials to
interested parties, including personnel from other agencies, regulators,
industrial workers, and conconcerned citizens. Several approaches might be
considered by the USGS to achieve this improvement. There may be
opportunities for better part-
CONCLUSIONS 74
nerships with industries, other agencies, and universities in the future. Care
should be taken to maintain long-term follow through with regulators and other
stakeholders after a project has been completed. USGS staff will need to
communicate better the value of their programs to a non-scientific
audience, including Congress, and may need to receive training on how to
make effective presentations to lay audiences.
The USGS should develop decision-support systems to assess
hazardous-materials problems, to assist in the design of remediation
programs, and to develop national policies to prevent problems in the
future. USGS work in this area should be coordinated carefully with other
agencies, for example the Agricultural Research Service, where decision-
support systems for nonpoint pollution from agriculture are being developed.
In respect to research, general priorities should be set with input from
other agencies (DOD, DOE, EPA, and appropriate state agencies, for
example), scientists with backgrounds in environmental risk assessment,
and appropriate non-governmental organizations. Once the priorities are
set and a strategic plan is developed, the plan should be submitted to an
external scientific panel and reviewed for scientific quality. This type of
peer review is needed as part of the process to ensure success of research in
the hazardous materials area. The recommendation for peer review at this
level is the primary recommendation of this report with regard to the
charge to advise on methods for planning for success. The “standard” peer-
review measure of success—the review of articles prepared for publication—
will serve the purpose of evaluating the success of the USGS programs in
hazardous materials science and technology, but only if the strategic direction
of the program is focused at the outset on the most important problems for the
nation. Continued external peer review of USGS priorities, plans, and strategies
related to hazardous materials in the hydrogeologic environment is essential.
REFERENCES 75
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APPENDIX A 90
Appendix A
U.S. Geological Survey Water Resources
Division Plan for Hazardous Materials
Science
INTERRELATIONSHIP OF PROGRAMS
U.S. Geological Survey (USGS) investigations related to hazardous
materials science are conducted primarily through four programs: (1) Core
Hydrologic Research, (2) Toxic Substances Hydrology, (3) Federal-State
Cooperative, and (4) Department of Defense Environmental Contamination.
Together, investigations funded by these programs span a range of effort from
long-term research on controlling processes to site-specific studies designed to
provide near-term options for existing problems. Two programs, Core
Hydrologic Research and Toxic Substances Hydrology, are funded by federal
appropriations to the USGS. The other two programs are funded entirely or
partially by other federal agencies or state and local cooperators. Details about
the planning and decision-making process for each of these programs are
provided in Sections 2 through 5 of this appendix. Section 1 addresses the
interrelationship of the programs.
Activities–Research and Methods Development

Research and methods development projects are funded by the Core
Hydrologic Research and Toxic Substances Hydrology programs. Both of these
programs are line items in the USGS budget. As such, they must meet the goals
and objectives outlined in the annual budget submission to the Congress. Within
these broad goals, there is considerable flexibility
APPENDIX A 91
to adjust the directions of projects funded by these programs to meet emerging

needs. There is also an opportunity to address theoretical problems and
questions that require longer-term research. Core Hydrologic Research provides
partial support for the National Research Program. The Toxic Substances
Hydrology program is conducted by scientists in the National Research
Program and District offices.
Activities–Site-specific Investigations
The Federal-State Cooperative program, also a line item in the USGS
budget, is based within Water Resources Division (WRD) District offices. At
least 50 percent of the funds for projects within this program are provided by
state or local cooperators. Typically, projects funded by this program address
problems such as assessing the presence and distribution of contaminants in
water resources, predicting the probable effects of alternative actions, and
measuring the progress of clean-up operations. Projects must be highly relevant
to the over 1,000 cooperators who help support them. The availability of federal
funds is the controlling factor in the growth of the Federal-State Cooperative
program. Every year there are several million dollars worth of cooperator funds
that are unmatched by federal funds. Thus, federal interest in the project is a key
factor in identifying priority projects for funding.
Projects conducted with funds entirely supplied by other federal agencies,
such as the Department of Defense Environmental Contamination program, are
closely linked to the needs of the funding source. This program is administered
at the district level. Often there is little flexibility within individual projects
which must complete the tasks agreed to within the agreed upon time frame.
However, it has been the USGS experience that, these projects can evolve into
challenging areal hydrologic assessments. There is little opportunity for process-
oriented research within this program, but there is much opportunity to field test
methods and techniques, to demonstrate new study approaches, and to apply the
scientific understanding obtained from the Core Hydrologic Research program
and the Toxic Substances Hydrology program.
Because growth of this program is primarily limited by the availability of
personnel, the USGS has the opportunity to choose offers which are
APPENDIX A 92
most challenging and which will provide opportunities to further the general
understanding of contaminant hydrology.
Program Development and Interaction

The mix of projects within the four programs provides a variety of
activities related to hazardous materials science. The Core Hydrologic Research
program and Toxic Substances Hydrology program provide continuity, long-
term investigations, and the opportunity for development of methods and tools.
At the other end of the spectrum, the Federal-State Cooperative program and
projects funded by other federal agencies keep the USGS in touch with real-
world problems and help to identify emerging issues. The balance of effort
within programs and among programs is periodically adjusted to meet new
challenges and to maintain an overall effort that provides understanding for the
present and the future, as well as the capability for action at specific problem
sites. The success of the USGS Hazardous Materials Science program is judged
by its relevance and usefulness to the scientific community and to decision
makers.
The Core Hydrologic Research program has the longest time horizon; here
exists the opportunity to fund scientific investigations that may have payoff
years into the future. For example, scientists funded by this program were
instrumental in developing the basic understanding of ground water hydrology
that was fundamental for the development and application of ground water flow
and transport models. Today, these models are used world-wide by the USGS
and the academic and consulting communities, in studies of hazardous waste
sites. Other tools developed under the Core Hydrologic Research program that
are currently in widespread use or are emerging technologies include
geochemical models and the use of chloroflourocarbon compounds for age-
dating ground water.
Although there is a component of undirected, long-term research within
the Toxic Substances Hydrology program, most projects are more problem-
oriented and of intermediate duration (4-10 years). The focus on
interdisciplinary research at field sites known to be contaminated has allowed
USGS to produce important understanding of contaminant trans
APPENDIX A 93
port and transformation mechanisms. This understanding and the study

approaches used by the program have been adapted for use within USGS
operational programs. For example, natural biodegradation of organic
contaminants in ground water, as demonstrated at the Bemidji and Galloway
field sites, is starting to be considered as a remediation alternative. Projects
funded by the Federal-State Cooperative program and the Department of
Defense are gathering data related to this process and evaluating their
importance at contaminated ground water sites.
The Federal-State Cooperative program and the Department of Defense
Environmental Contamination program provide an important feedback
mechanism to USGS research and methods development programs. First, it is
through these programs that new research methods are applied to help solve
problems. Second, these operational programs have, over the years, identified
problems that have required increased attention from the research community.
For example, in the 1970's, projects within the Federal-State Cooperative
program and meetings with local cooperators, as well as other sources of
information, helped to identify the emerging problem of organic contaminants
in ground water. The USGS responded to the general problem of ground water
contamination by developing new procedures for sample collection, new
analytical methodology in the laboratory, and new approaches to understanding
ground water transport of organic contaminants. Further, concern about
hazardous contaminants in water resources led to the initiation of the Toxic
Substances Hydrology program.
CORE HYDROLOGIC RESEARCH PROGRAM PLANNING

AND DECISION-MAKING PROCESS
Origin
The Core Hydrologic Research program is an important source of funding
for the National Research Program (NRP), which had its beginnings in the late
1950's when core research was added as a line item to the Congressional
budget. Since that time, the NRP has grown to encompass a broad spectrum of
scientific investigations, and the source of funding for the NRP has expanded to
include several other USGS
APPENDIX A 94
programs and other federal agencies. Because the planning process for Core
Hydrologic Research program funds is included within the overall NRP
planning process, the remainder of this section will focus on the plans and
decision-making process of the NRP.
The NRP uses the sciences of hydrology, mathematics, chemistry, physics,
ecology, biology, geology, and engineering to gain a fundamental
understanding of the processes that affect the availability, movement, and
quality of the nation's water resources. The knowledge gained and methods
developed have great value to WRD's operational program. Results of the
investigations conducted by the NRP are applicable not only to the solution of
current water problems, but also to future issues that may affect the nation's
water resources.
Plans for Program Development

The NRP conducts basic and problem-oriented research in support of the
mission of the USGS. Relevant hydrologic information provided by the USGS
is available today to assist the nation in solving its water problems because of a
conscious decision made in years past to invest in research. The NRP is
designed to encourage pursuit of a diverse agenda of research topics aimed at
providing new knowledge and insights into varied and complex hydrologic
processes that are not well understood. The emphasis of these research activities
changes through time, reflecting the emergence of promising new areas of
inquiry and the demand for new tools and techniques with which to address
water resources issues. For example, the National Water Quality Assessment
program was conceived by NRP researchers, and has now become one of the
largest operational programs in WRD. Recently, a new technique using
chloroflourocarbon compounds to date ground water was developed in the NRP
and is being widely used in the operational program. Knowledge gained and
methods developed in this program apply to all of the hydrologic investigations
of the USGS, to the water-oriented investigations and operations of other
agencies, and to the general scientific community. Through the years, many of
the USGS's major research and resource assessment initiatives related to
existing and emerging national water resources problems had their origins in the
NRP.
APPENDIX A 95
Decision-making Process
The activities of the NRP are divided into six research disciplines: Ground
Water Chemistry; Surface Water Chemistry; Ground Water Hydrology; Surface
Water Hydrology; Geomorphology and Sediment Transport; and Ecology.
Activities in each discipline are conducted by project chiefs, and the general
focus of, and guidance within, a discipline is provided by a Research Adviser
(RA) and Assistant Research Adviser (ARA) for that discipline. Individual
researchers within the NRP operate with a high degree of independence in terms
of choosing a research problem and in carrying out research on that problem.
The results of the research are published in peer-reviewed journals, as USGS
publications, or sometimes both. In this way, the information gained in the
studies is widely disseminated within the agency and to the scientific
community at large. In addition, researchers in the NRP generally spend up to
30 percent of their time consulting with District personnel on specific problems,
the approaches needed to solve those problems, and new methods and
techniques useful to District projects.
Researchers in the NRP are evaluated every three years (or more often if
desired) by a panel of peers. The evaluation, based on material supplied by the
researcher, prepared according to a standard format, considers the researchers
achievements, publications, service to the organization, and other factors.
Promotions and other personnel actions are based on the recommendation of the
peer panel.
Once a year, a meeting of the NRP Research Committee is held. The
committee consists of: Assistant Chief Hydrologist for Research and External
Coordination (ACH/R&EC); Assistant Chief Hydrologist for Program
Coordination and Technical Support; Chief, Office of Hydrologic Research
(OHR); Chief, Office of Ground Water; Chief, Office of Surface Water; Chief,
Office of Water Quality; RAs, and ARAs. At this meeting, the NRP program is
reviewed, strengths and weaknesses are identified, and recommendations are
made for program direction and priority areas for new hires.
In order to continue to foster effective and productive scientific research
programs, managers of the USGS WRD require ongoing assessments of the
quality of research being conducted. An important part of this assessment
procedure is a periodic review of research activities and
APPENDIX A 96
accomplishments within related "subdiscipline" groups (clusters) of WRD

research projects by panels of respected researchers from both inside and
outside of the USGS. The primary purposes of the cluster reviews are to provide
managers with expert opinion concerning WRD research activities and to
provide the research staff with an evaluation of the direction, techniques, and
perceived impact of their research. The goal of the cluster review is to improve
future research within subdiscipline groups (clusters).
Once a year, an NRP budget meeting is held. At this meeting, the ACH/
R&EC; Chief, OHR; Chief, Branch of Regional Research (BRR), Eastern
Region; Chief, BRR, Central Region; Chief, BRR, Western Region; RAs, and
ARAs review each of the projects in the NRP and their requested budgets for
the next fiscal year. Productive projects addressing high priority issues are
treated most favorably. Funding restraints may be used to encourage changes in
less productive projects and those addressing lower priority issues. In this
manner, the budgetary process provides one method of directing reorientation
of the focus and productivity of projects.
USGS TOXIC SUBSTANCES HYDROLOGY PROGRAM

PLANNING AND DECISION-MAKING PROCESS
Origin
The USGS Toxic Substances Hydrology (Toxics) program began in 1983
as an outgrowth of a then-existing program on Subsurface Waste Injection.
From 1983 until 1985, the program addressed only ground water contamination.
In 1986, a surface water component was added. The driving force for the
creation and continuation of the program is the fact that it will take enormous
financial resources to clean up hazardous waste sites in this country and to
reduce contamination from nonpoint sources. The objective of the program is to
provide information that is useful in making decisions about remediation of
existing contaminated areas and the prevention of future contamination.
APPENDIX A 97

Focused field investigations are conducted at sites that are known to be
contaminated. The goal of these intensive investigations is to obtain a better
understanding of the processes that control contaminant transport and
transformation. Obtaining information that is transferable to other sites is a
factor in selecting sites and planning investigations. The goal of the program is
to address major sources and types of contamination of ground water and
surface water. A decision was made early in the program that USGS could
make an important contribution by conducting, long-term research at well-
characterized sites. Thus, assessments of sites continue to be funded as long as
they are productive. The program's budget has been stable for several years;
therefore, new investigations can only begin when ongoing studies are
completed and funds can be redirected.
Original plans for the program were to gain additional insights into
controlling processes by conducting comparison studies of the same
contaminants in different climatic and geographic regions. For example,
gasoline in ground water would be investigated in the humid northeast and in
the and west, and pulp mills discharging to rivers in Florida and in Oregon
would be studied. This overall plan has not been followed because of financial
and human resource limitations. Duplication of studies in different climatic
regions has been judged to be less important than addressing a number of the
most important types and sources of contamination at least once.
In the early years of the program, 14 studies of nonpoint source and ground
water contamination were funded. Seven of these studies were continued
through the late 1980's to allow for more extensive data analysis. The overall
goal of all of these studies was to understand the relationship between ground
water quality and land use and natural factors. In 1989, the program began a
series of studies of the occurrence of agricultural chemicals (pesticides and
nitrate) in water resources of the upper Midwestern cornbelt. These studies have
been highly coordinated with the U.S. Department of Agriculture (USDA) and
the U.S. Environmental Protection Agency (USEPA).
The Toxics program has investigated the following major sources and types of contamination:
Source Contaminants Environment Status
Wood treatment creosote GW, Pensacola, FL finished
APPENDIX A
Sewage disposal nutrients, trace metals GW, Cape Cod, MA ongoing

Crude oil organic chemicals GW, Bemidji, MN ongoing
Gold-ore processing arsenic SW, Whitewood Creek, SD finished
Petrochemical industry organic chemicals SW, Calcasieu River, LA finished
Mining trace metals SW, Arkansas River, CO ongoing
Copper-ore processing copper, trace metals GW & SW, Globe, AZ ongoing
De-greasing operation trichloroethylene GW, Picatinny Arsenal, NJ report writing
Leaking storage tank gasoline GW, Galloway, NJ ongoing
Agriculture and urban land use pesticides, trace metals, organic chemicals SW, San Francisco Bay and tributaries, CA ongoing
Landfill mixture of inorganic and organic contaminants GW & SW, Norman landfill, OK initiated FY 1994
98
APPENDIX A 99
Decisions about the nonpoint source investigations are discussed above.
The most recent focus for that component of the program, the upper Midwest,
was chosen after consultation with USDA and USEPA. New directions within
the field-oriented investigations are established by the selection of new sites for
study of specific types of contaminants. The process for selecting sites for new
focused field investigations is a follows:
1. Regional, District, and research offices are contacted to gain insight

into the sources of contamination, types of contaminants, or
hydrogeologic environments that are in need of investigation by the
Toxics program. The intent is to provide understanding, methods,
and study approaches for use in the USGS operational program.
Because personnel in the USGS operational program have frequent
contact with state agencies and EPA regional offices, they are an
excellent source of information about emerging national issues.
2. A call for site nominations is distributed.
3. An interdisciplinary team of USGS experts is assembled to review
site nomination packages and provide advice about which sites
offer the best opportunities.
4. The research team for the selected site prepares a 3- or 4-year
integrated research plan which will guide activity at the site. The
site-selection team provides some advice about the kinds of issues
that need to be clarified during preparation of the research plan.
5. After the integrated research plan is prepared, it is reviewed by
several members of the site-selection team. Comments and
suggestions are forwarded to the site team. Modifications to the
research plan are made, as necessary.
6. Progress of the site investigations is determined on a continuing
basis through review of publications from the studies. A more
complete review occurs every 2 and one-half years at technical
meetings of the Toxics program. At the end of the 3- or 4-year
research cycle, the site research teams are asked to prepare a plan
for continuation of research. This is reviewed by program
coordinators and technical advisors to deter
APPENDIX A 100
mine relevance, quality of science, and past productivity. Decisions

about closing out projects are based on this technical review.
FEDERAL-STATE COOPERATIVE PROGRAM PLANNING

Origin
The USGS Federal-State Cooperative Program has contributed directly to
water resources knowledge for almost 100 years. The first USGS cooperative
water resources investigation was with the State of Kansas in 1895. In 1905,
Congress appropriated funds specifically for cooperative studies, marking the
official beginning of the program. In 1928, Congress gave formal recognition to
the federal-state partnership and limited the Federal financial contribution for
cooperative water resources studies to no more than 50 percent of the total
funds for each investigation. In 1977, Congress recognized the need for
uniform, current, and reliable information on water use and directed the USGS
to establish a National Water-Use Information Program, which is similar to the
Federal-State Cooperative Program. The data collected and compiled on the
nation's water use complements the USGS data on the availability and quality of
the nation's water resources.
The fundamental characteristic of the Federal-State Cooperative Program
is that local and state agencies provide at least one-half the funds to the USGS
and the USGS does most of the work. The Federal-State Cooperative Program
contributes directly to water resources knowledge by fostering a working
partnership between the federal and state and local governments in the
advancement of earth science, and by compiling a major part of the nation's
hydrologic information. From its earliest days, the program has been
responsible directly for the development of procedures for streamgaging,
concepts of surface water and ground water flow, and analytical techniques for
investigations of water quality.
APPENDIX A 101

In fulfilling its water resources mission, the USGS performs four principal
functions:
• It collects data needed for the continuing determination and evaluation

of the quantity, quality, and use of the nation's water resources.
• It conducts analytical and interpretive appraisals to describe the
occurrence, availability, and physical, chemical, and biological
characteristics of surface and ground water.
• It conducts research in hydraulics, hydrology, and related scientific and
engineering fields.
• It disseminates water data and the results of investigations and research.
The collection of surface water and ground water data on a systematic

basis under the provisions of the Federal-State Cooperative Program is a major
part of the USGS's coordinated water resources activities. The resulting
information provides a continuing record of the quantity, quality, and use of the
nation's water resources. These data provide information necessary for the
determination of water suitability for various uses, identification of trends, and
evaluation of the effects of stresses on the nation's surface and ground water
resources.
Within the Federal-State Cooperative Program, typically about half of the
funds support the collection of hydrologic data; the remaining half support
hydrologic investigations and research. Investigations encompass areas that
range in size from a square mile or less to multistate regions. In these
investigations, USGS scientists bring together information to define,
characterize, and evaluate the areal extent, quality, and availability of the water
resource. Since the early 1970's, there has been an increase in the number of
investigations that have emphasized water quality issues, such as aquifer
contamination, river quality, storm runoff quality, and the effects of acid rain,
coal mining, and agricultural chemicals and practices on the hydrologic system.
All data and results of analytical studies are made available to cooperating
agencies and to the public through published reports and
APPENDIX A 102
through computerized information programs, such as the National Water

Information System (NWIS) and the National Water Data Exchange
(NAWDEX) Program. Abstracts of completed reports are made available
through the USGS Water Resources Scientific Information Center (WRSIC).
Hydrologic data can be accessed by computer terminals at offices in every state.
In many places, the Federal-State Cooperative Program provides the only
source of support for water data collection and investigations required to assess,
on a continuing basis, the status of the nation's water resources. Information
developed in the Federal-State Cooperative Program has relevance to potential
and emerging long-term problems, such as water supply, waste disposal, energy
development, and environmental management and protection. Because common
analytical methods and techniques are used, the information also is relevant to
problems having interstate, regional, national, or international significance. The
program provides the basis required to abide by interstate and international
compacts and federal law and court decrees, and to carry out congressionally
mandated studies, regional and national water resources assessments, and
planning activities.
Program priorities are based on national needs that have been identified by
the President and Administration advisors, by the Congress, by the Department
of the Interior, by other federal agencies, and from information the USGS has
received from cooperating agencies and other interested parties. Issues that are
identified through the National Water Summary preparation process also are
taken into consideration. As a result, the priorities are developed in response to
mutual federal, regional, state, and local requirements.
The USGS and its cooperating agencies work together in a continuing
process that leads to adjustments in the program each year. The number of
requests for scientific and technical assistance continues to grow from state
agencies responsible for ground water protection and for controlling and
mitigating contamination. State offerings typically exceed federal matching
funds each year and reflect the increasing emphasis on water
APPENDIX A 103
quality issues, as well as other concerns regarding the availability, distribution,

and use of the resource.
Each year, about $1.0 million in federal funds from the Federal-State
Cooperative Program allocation are set aside for merit competition. Project
proposals are reviewed by USGS peer panels and those with highest scientific
merit are selected to receive the federal merit funds. The other half of the funds
for these projects are provided by state or local cooperators. This process, which
directs federal matching funds to the best proposals, assures that the Federal-
State Cooperative Program will continue to provide relevant and high-quality
information.
DEPARTMENT OF DEFENSE ENVIRONMENTAL

CONTAMINATION HYDROLOGY PROGRAM–PLANNING
Origin
The USGS Department of Defense (DOD) Environmental Contamination
Hydrology Program became an official WRD program in 1987 when a manager
was named to the program at WRD headquarters. Until that time the program
consisted of a loose network of a few studies throughout the WRD. The
objective of the program is to provide technical expertise to the DOD while
simultaneously providing a forum for furthering WRD's understanding of the
processes related to the fate and transport of environmental contaminants in
ground water, surface water, and aquifer material.

The program is developed by responding to the requests by DOD agencies
to WRD headquarters and District offices. Agreements have been developed
and are in the process of being developed with numerous DOD agencies. These
agreements list WRD's interests and capabilities. DOD partners communicate
directly with WRD District offices identified by the Program Manager as the
appropriate partnering WRD office. The
APPENDIX A 104
program is developed at the District level where studies are undertaken within
the District's capabilities and limitations. Current investigations address the
following aspects of contaminant hydrology:
• Definition of hydrogeologic framework of many terranes.

• Movement of ground water and contaminants in different terranes.
• Ground water flow modeling of different terranes.
• Heavy metals in ground water.
• Isotope geochemistry.
• Surface and borehole geophysics.
• Soil gas and its relation to ground water contamination.
• Determination of aquifer parameters of different terranes.
• Development of relational data base and use of geographic information
systems.
• Bioremediation of contaminants in different hydrogeologic
environments.
• Quality assurance and quality control of laboratory analytical data and
field data.
DOD commands contact the program manager who in turn contacts the
Regional Hydrologist's representative in the affected region. The decision to
undertake a DOD-funded project lies with the District Chief in consultation
with the pertinent Regional Hydrologist. In some cases a DOD partner may
request that WRD undertake a program consisting of many studies located
throughout the country under the condition that WRD agree to work at some or
all of the sites. In these cases the decision on any study remains with the District
Chief in consultation with the Regional Hydrologist. Decisions to undertake
these environmental studies are made when the process of conducting the
investigation provides the WRD with opportunities to further advance its
understanding of the processes related to the fate and transport of environmental
contaminants in ground water, surface water, and aquifer material.
APPENDIX A 105
SUMMARY
In summary, USGS projects in hazardous materials science span a
spectrum of hydrologic investigations. Collectively, the Core Hydrologic
Research program, the Toxic Substances Hydrology program, the Federal-State
Cooperative program, and the Department of Defense Environmental
Contamination program allow the USGS to maintain the capability to undertake
process-oriented research, conduct developmental activities, and address real-
world problems. Each program has a planning and decision-making process that
meets individual program needs as determined by program objectives. Balance
and feedback among programs keep the USGS effort at the cutting-edge of
science and relevant to policy makers and resource managers.
APPENDIX B 106
Appendix B
Biographical Sketches of Committee
Members
GEORGE M. HORNBERGER obtained his Ph.D. from Stanford

University (hydrology) in 1970. He also holds a bachelor's (1965) and a
master's (1967) degree in civil engineering from Drexel University. As a
professor at the University of Virginia, he is currently interested in modeling of
environmental systems with uncertainty, hydrogeochemical response of small
catchments, and transport of bacteria in porous media. Dr. Hornberger is a
member of the National Academy of Engineering.
LISA ALVAREZ-COHEN is an Assistant Professor in the Department of
Civil Engineering at the University of California, Berkeley, where she teaches
classes on Hazardous and Industrial Waste Treatment Process and
Environmental Microbiology. She received her Ph.D. in Environmental
Engineering and Sciences from Stanford University. Dr. Alvarez-Cohen's
research interest include experimental research and modeling of microbial
processes in porous media, bioremediation of contaminated aquifers, innovative
hazardous waste treatment technologies, and application of cometabolic
biotransformation reactions.
KENNEYH R. BRADBURY is a research hydrogeologist/professor with
the Wisconsin Geological and Natural History Survey, University of Wisconsin-
Extension, in Madison, Wisconsin. He received his Ph.D. (hydrogeology, 1982)
from the University of Wisconsin-Madison, his A.M. (geology, 1977) from
Indiana University, and his B.A. (geology, 1974) from Ohio Wesleyan
University. His current research interests
APPENDIX B 107
include ground water flow in fractured media, ground water recharge processes,
wellhead protection, and the hydrogeology of glacial deposits.
CONSTANCE HUNT received her BS in wildlife biology from Arizona
State University, and her MA in public policy from the University of Chicago.
She is a senior program officer with the World Wildlife Fund, where she directs
the freshwater ecosystem conservation program, including projects to promote
restoration of the upper Mississippi River basin, coordination with South
Florida restoration efforts, involvement in national water resources policy, and
international river conservation efforts. Previously, she conducted inter-agency
coordinator projects, wetland evaluations and delineations, permit processing,
and environmental impact analysis while on the staff of the U.S. Environmental
Protection Agency and the U.S. Army Corps of Engineers.
DAWN S. KABACK is a hydrogeochemist who received her Ph.D. in
geological sciences from the University of Colorado in 1977. Presently, she is
Interim Director of the Colorado Center for Environmental Management in
Denver. Until recently, Dr. Kaback managed the ground water research group
(Environmental Sciences Section) at the DOE Savannah River Laboratory in
Aiken, South Carolina. Her work involves aquifer characterization and
development of innovative technologies to improve environmental restoration
of contaminated soils and ground water. Previously, she worked for Conoco in
the R&D department where she had a variety of assignments related to
environmental effects of mining, geochemical exploration, and clastic
diagenesis as applied to petroleum exploration.
DAVID H. MOREAU is director, Water Resources Research Institute of
the University of North Carolina and also professor in the departments of City
and Regional Planning and Environmental Sciences and Engineering. Dr.
Moreau received a B.Sc. (civil engineering, 1960) from Mississippi State
University, a M.Sc. (civil engineering, 1963) from North Carolina State
University, a M.Sc. (engineering, 1964) from Harvard University, and a Ph.D.
(water resources, 1967) from Harvard University. Dr. Moreau has been a
consultant to United Nations Development Program, Water Management
Models for Water Supply; New
APPENDIX B 108
York City, review of water demand projections; and Water for Sanitation and
Health Program (AID), financing of water supply and waste disposal.
FREDERICK G. POHLAND is Professor and Edward R. Weidlein Chair
of environmental engineering, Department of Civil and Environmental
Engineering, University of Pittsburgh. He received his Ph.D. in civil
engineering from Purdue University in 1961. Dr. Pohland research interests
include environmental engineering operations and processes; water and waste
chemistry and microbiology; solid and hazardous waste management; and
environmental impact monitoring assessment and remediation. Dr. Pohland is a
member of the National Academy of Engineering.
FRANK W. SCHWARTZ received his Ph.D. in geology in 1972 from the
University of Illinois. He is currently Ohio Eminent Scholar in Hydrogeology at
Ohio State University. Dr. Schwartz has been an active consultant to
government and private industry since 1972. Most of his work has involved
project management, report review, technical advice, the development and
application of computer models, and field investigations. Dr. Schwartz is a
member of the Water Science and Technology Board.
LEONARD SHABMAN received a Ph.D. in agricultural economics in
1972 from Cornell University. He is a professor at Virginia Polytechnic
Institute, Department of Agricultural Economics. Dr. Shabman has conducted
economic research over a wide range of topics in natural resource and
environmental policy, with emphasis in 6 general areas: coastal resources
management; planning, investment, and financing of water resource
development; flood hazard management; federal and state water planning; water
quality management, and fisheries management.
MITCHELL J. SMALL a professor at the Carnegie Mellon University, in
the Civil and Environmental Engineering and Engineering and Public Policy
Departments. He received his M.S. and Ph.D. from the University of Michigan.
Dr. Small, has interests in mathematical modeling of environmental quality;
statistical methods and uncertainty analysis; human risk perception and decision
making.
APPENDIX B 109
ALAN T. STONE received his B.S. in chemistry from the University of

Maryland-College Park in 1978, his M.S. in 1981 and Ph.D. in 1983 in
environmental engineering from the California Institute of Technology. He is
currently a professor in the Department of Geography and Environmental
Engineering at Johns Hopkins University. His research interests are in the area
of chemical kinetics and mechanisms; reactions at surfaces; abiotic degradation
of organic pollutants; redox reactions; precipitation and dissolution of minerals,
environmental chemistry of soils, sediments, and aquifers.
DAVID A. WOOLHISER received his Ph.D. in Civil Engineering, with
minors in Meteorology and Geophysics, from the University of Wisconsin in
1962. Dr. Woolhiser retired from the USDA Agricultural Research Service in
1991 after a 30 year career and is currently a Faculty Affiliate in civil
engineering at Colorado State University and a hydrologist in Fort Collins,
Colorado. He is known for his work on the hydrology and hydrometerology of
arid and semiarid rangelands, simulation of hydrologic systems, numerical
modeling of surface runoff, erosion and chemical transport, and probabilistic
models of rainfall and runoff. He is a member of the National Academy of
Engineering.

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About this PDF file: This new digital representation of the original work has been recomposed from

Washington, D.C. 1996

Water Science and Technology Board

of Research by the U.S.

Commission on Geosciences, Environment, and Resources

COMMITTEE ON U.S. GEOLOGICAL SURVEY WATER

GEORGE M. HORNBERGER, Chairman, University of Virginia, Charlottesville

National Research Council Staff

WATER SCIENCE AND TECHNOLOGY BOARD

DAVID L. FREYBERG, Chair, Stanford University, Stanford, California

COMMISSION ON GEOSCIENCES, ENVIRONMENT,

M. GORDON WOLMAN, Chair, The Johns Hopkins University, Baltimore,

This report is a product of the Committee on USGS Water Resources

2 OVERVIEW OF THE FEDERAL EFFORT IN HAZARDOUS 8

3 CHARACTERIZATION: PROCESSES AND METHODS FOR 23

State-of-the-Art in the Field 38

5 MATHEMATICAL MODELS AND DECISION SUPPORT 48

A U.S. Geological Survey Water Resources Division Plan for Haz- 90

B Biographical Sketches of Committee Members 106

The research conducted by the WRD on topics related to hazardous

“Delaney Clause”, which prohibited the addition of a known carcinogen into

in 1981, and that prior to RCRA, up to 90 percent of hazardous wastes was

THE EVOLUTION OF RESEARCH IN HYDROLOGY

OVERVIEW OF RELEVANT USGS PROGRAMS

FIGURE 2.1 Expenditures on USGS programs related to hazardous materials:

Funding for the Federal-State Cooperative Program for projects on

FIGURE 2.2 Breakdown of funding by major source of funds: Federal

many projects under the Federal-State Cooperative Program that have a

COMPARISON OF USGS HYDROLOGIC RESEARCH TO

potential to affect the practice of hydrogeology. It is more difficult to support

an overview of how to address this problem. Second, complementary laboratory

FROM PROCESS DISCOVERY TO APPLICATION: THE

ecosystem functioning) and determining practical alternatives for alleviating the

stresses: 1) improvements in the ability to characterize natural environments in

made in knowledge of the degradability of numerous hazardous compounds,

Innovations in characterization technology have been developed to

resistivity, electromagnetics, and seismic sources has been demonstrated as a

understanding of its role in natural biogeochemical processes (Averett et al.,

CRITICAL AREAS OF RESEARCH

OPPORTUNITIES FOR THE USGS

• Hydrological, biological and geochemical processes within fractured

STATE-OF-THE-ART IN THE FIELD

• Emerging Technology. A technology that requires additional

The development and application of many remedial alternatives has

Land treatment Solidification/stabilization

FIGURE 4.1 Technologies applicable to soils and sediments.

aqueous-phase treatment, may provide supplemental alternatives for an

FIGURE 4.2 Technologies applicable to ground waters.

• soil washing, followed by bioremediation, incineration, or solidification/

FIGURE 4.3 Status of treatment technologies at Superfund sites.

FIGURE 4.4 Status of alternative technologies for Superfund Remedial Action.

• dechlorination, followed by soil washing for inorganics;

Nearly 50 emerging, innovative, or established/conventional technologies

CRITICAL AREAS FOR RESEARCH

is the ultimate target for remediation. For example, heterogeneities within

OPPORTUNITIES FOR THE USGS

ground waters, and surface waters, and the application of innovative

be one of the USGS's most valuable assets.

Mathematical models are indispensable tools in ground and surface water

PREDICTIVE FLOW AND TRANSPORT MODELS

of modeling parameters (National Research Council, 1992). The application of

Saturated Flow in Porous Media

Unsaturated Flow in Porous Media