Ekkehard Holzbecher - Environmental Forensics - Principles & Applications-CRC Press (1999)

Library of Congress Cataloging-in-Publication Data
Morrison, Robert D.
Environmental forensics : principles and applications / by Robert
D. Morrison
p. cm.
Includes bibliographical references and index.
ISBN 0-8493-2058-5 (alk. paper)
1. Environmental forensics. 2. Solvents — Environmental aspects.
3. Organochlorine compounds — Environmental aspects. 4. Petroleum
chemicals — Environmental aspects. 5. Hydrocarbons — Environmental
aspects. 6. Groundwater flow. I. Title.
TD193.4.M67 1999
628.5—dc21 99-40624
CIP
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International Standard Book Number 0-8493-2058-5
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Preface
Environmental forensics is the systematic examination of environmental information
used in litigation. The purpose of this book is to provide a working reference for the
practicing environmental attorney or environmental consultant. As a working refer-
ence, the topics and examples selected are common denominator issues encountered
in environmental litigation; as such, this book is not intended to be a treatise on a
particular subject but rather to present information that you will likely encounter.
Whenever possible, expanded mathematical or chemical discussions were relegated
to the Appendices.
Chapters 1 and 2 provide a working overview of information about chlorinated
solvents and petroleum hydrocarbons. The foundational information in Chapters 1
and 2 was selected to assist you in deciding which forensic tools described in Chapter
4 are applicable to your case. Recognize that the forensic tools described in Chapter
4 are rapidly evolving. Whenever possible, contact the proponents of these technolo-
gies directly to ascertain their current capabilities relative to your case. Chapters 3
and 5 provide information on how to identify biased environmental data and sugges-
tions in regard to the applications and review of biased environmental data, as well
as suggestions concerning the evaluation of contaminant transport models. Chapter
6 describes techniques for forensically evaluating settlement and trial exhibits and
animations.
The information in this book is intended to allow you to distinguish between
evidence and opinions based on scientific methods vs. junk science. Regardless of
your position on an allegation, everyone is well served if valid technical information
and interpretations form the basis for an expert witness opinion.
Best wishes for a successful and informed environmental career.
Robert D. Morrison
San Diego, CA
©2000 CRC Press LLC

The Author
Robert Daniel Morrison has a B.S. in Geology, an
M.S. in Environmental Studies, an M.S. in Environ-
mental Engineering, and a Ph.D. in Soil Physics from
the University of Wisconsin at Madison. Dr. Morrison
has been working for 27 years in the environmental
field on issues related to soil and groundwater con-
tamination. He specializes in the forensic review and
interpretation of scientific data used in support of
litigation involving soil and groundwater contamina-
tion. Dr. Morrison has published articles and books
on soil and groundwater contamination topics and has
shared this information via lectures throughout the
world. He is active in reviewing technical papers on forensics techniques and has
served on the editorial boards of Ground Water and Groundwater Monitoring
Review and Remediation and currently serves on the editorial board of The Interna-
tional Journal of Environmental Forensics. Dr. Morrison has worked as an expert
witness and consultant for the U.S. Department of Justice, the Environmental
Protection Agency (EPA), and numerous law firms on cases where environmental
forensics were used to allocate responsibility. In the capacity as an expert witness
and confidential consultant, Dr. Morrison has provided testimony in numerous
cases, some with claims ranging from tens of thousands of dollars to as much as five
billion dollars.

Acknowledgments
Scientists who directly assisted in the preparation of this book include Sherri Komelyan,
Kathleen Calsbeck, Jamie Campos, Kevin Vaughn, and Christian Benitez of R.
Morrison & Associates, Inc. Numerous colleagues and researchers provided assis-
tance in the form of communication and information. Special thanks to Dr. Jim
Bruya, of Friedman & Bruya in Seattle, WA; Dr. James Szecsody, of Battelle
Northwest Laboratories in Hanford, WA; Dr. Blayne Hartman, of TEG in Solano
Beach, CA; David Kaminski, of QED in Ann Arbor, MI; Kevin Beneteau, of Golder
Associates, Calgary, Alberta, Canada; Dr. Barbara Sherwood Lollar, Department of
Geology, University of Toronto, Canada; Dawn Zemo, of Geomatrix in San Fran-
cisco, CA; and Dr. Ramona Aravena, University of Waterloo, Waterloo, Ontario,
Canada.
Special thanks to the wonderful group at CRC Press, especially Becky
McEldowney, who provided creative insight and inspiration, and Debrah Goldfarb.
who provided marketing direction. Special thanks, too, to Sarah Nicely Fortener of
Nicely Creative Services in Geneva, IL, for her wonderful editing of this book.
Special acknowledgement to my wife, Donna, who tolerated my night stalking
and the use of her computer during this effort.

Contents
Chapters 1 through 6
1 An Overview of the History, Chemistry,

and Transport of Chlorinated Solvents
1.1 Introduction
1.2 Chronology and Use of Chlorinated Solvents
1.2.1 Trichloroethylene (TCE)
1.2.2 Tetrachloroethylene (PCE, or Perchloroethylene)
1.2.3 1,1,1-Trichloroethane (1,1,1-TCA,
or Methylchloroform)
1.2.4 Methylene Chloride (Dichloromethane)
1.3 Chemistry and Properties of Chlorinated Solvents
1.3.1 Terminology and Classification
1.3.2 Chemical Structure and Properties
1.3.3 Henry’s Law Constant (KH)
1.3.4 Liquid Density
1.3.5 Solubility
1.3.6 Viscosity
1.3.7 Vapor Pressure and Density
1.3.8 Boiling Point and Latent Heat of Vaporization
1.3.9 Octanol/Water Partition Coefficient (Kow)
1.3.10 Hydrolysis
1.3.11 Sorption
1.3.12 Biodegradation
1.3.12.1 Anaerobic Degradation
1.3.12.2 Aerobic Degradation
1.4 Transport of Chlorinated Solvents through Soil
1.5 Impact of Cosolvency on Transport through Soil
1.6 Transport of Vapors in Soil
1.7 Transport through the Capillary Fringe
1.8 Transport in Groundwater
1.8.1 Darcy’s Law
1.8.2 Porosity (ne)
1.8.3 Permeability (k) and Hydraulic Conductivity (K)
1.8.4 Retardation
1.8.5 Dispersivity

1.8.6 Free Phase Solvent Transport in Groundwater
1.8.7 Transport in Fractures
1.8.8 Transport in Fractured Porous Media
References
2 Chemistry and Transport of Petroleum Hydrocarbons

2.1 Introduction
2.2 Chemistry of Crude Oil
2.3 Chemistry of Refined Products
2.3.1 Gasoline
2.3.2 Diesel
2.4 Chemical Reactions in the Vadose Zone
2.4.1 Henry’s Law Constant (KH)
2.4.2 Liquid Density
2.4.3 Solubility
2.4.4 Viscosity
2.4.5 Vapor Pressure and Vapor Density
2.4.6 Sorption
2.4.7 Retardation
2.4.8 Biodegradation
2.5 Overview of Transport through the Unsaturated (Vadose) Zone
2.5.1 Transport through Soil
2.5.2 Cosolvation and Colloidal Transport
2.5.3 Residual Saturation
2.5.4 Vapor Phase Transport
2.6 Hydrocarbon Interactions at the Capillary Fringe
2.6.1 Hydrocarbon Solubilization from the
Capillary Fringe into Groundwater
2.7 Transport in Groundwater
2.7.1 Rate of Transport
2.7.2 MTBE Transport in Groundwater
2.7.3 Length of a Petroleum Hydrocarbon Plume
2.7.4 Transport in Fractures
References
3 Identification of Biased Environmental Data

3.1 Introduction
3.2 Geologic Characterization
3.2.1 Boring Log Terminology
3.3 Interpretation of Geologic Information
3.4 Soil Collection for Chemical Analyses
3.4.1 Soil Sampling Equipment
3.4.2 Subsampling and Sample Transfer
3.4.3 Soil Compositing

3.5 Groundwater Characterization
3.5.1 Monitoring Well Location
3.5.2 Installation of Groundwater Monitoring Wells
3.5.3 Sampling Plan
3.5.4 Groundwater Purging
3.5.5 Groundwater Sampling
3.5.6 Sampling Equipment and Sequence
3.5.7 Equipment Decontamination
3.5.8 Sample Containers
3.5.9 Sample Filtration, Preservation, and Holding Times
3.5.10 Field Measurements
3.5.11 Field Quality Control Samples
3.6 Soil Vapor Surveys
3.6.1 Interpretation of Soil Vapor Data
3.7 Analytical Methods
3.7.1 Misidentification of Analytes
3.7.2 Laboratory Documentation
3.7.2.1 Chain of Custody
3.7.2.2 Document Control/Control Log
3.7.2.3 Signature List
3.7.2.4 Logbook Cover Sheet
3.7.2.5 Sample Kit Preparation Log
3.7.2.6 Field Logs
3.7.2.7 Sample Receipt Checklist and/or Log
3.7.2.8 Sample Preparation Logbook
3.7.2.9 Sample Analysis Log
3.7.2.10 Instrument Run Log
3.7.2.11 Instrument Maintenance Log
3.7.2.12 Certificates of Analysis
3.7.2.13 Laboratory Certification
3.7.3 Laboratory Quality Control Samples
References
4 Forensic Techniques Used in Environmental Litigation

4.1 Introduction
4.2 Aerial Photography
4.3 Underground Storage Tank Corrosion Models
4.4 Inventory Reconciliation
4.5 Commercial Availability of a Chemical
4.6 Chemicals and Formulations Unique
to a Manufacturing Process or Activity
4.6.1 Polychlorinated Biphenyls
4.7 Petroleum Refinery Throughput Analysis
4.8 Chemical Identification of Petroleum Hydrocarbons

4.8.1 Analytical Strategy
4.8.2 Proprietary Additives: Petroleum Hydrocarbons
4.8.3 Anti-Knock Additives (Alkyl Leads)
4.8.4 Lead Scavengers
4.8.5 Oxygenates
4.8.6 Trace Inorganics
4.8.7 Petroleum Dyes
4.8.8 Octane Rating
4.9 Radioactive Isotope Dating
4.9.1 Dating Groundwater with Isotopes
4.9.2 Isotopic Analysis for Petroleum Hydrocarbons
4.9.3 Lead Isotope Analysis
4.9.4 Lead Isotope Analysis for Gasoline Fingerprinting
4.9.5 Isotope Analysis of Crude Oil and BTEX
4.9.6 Isotope Analysis of Gas Samples
4.9.7 Isotopic Analysis of Chlorinated Solvents
4.10 Chemical and Biological Degradation Models:
Petroleum Hydrocarbons
4.10.1 Weathering and Biomarkers
4.10.2 Biodegradation Models
4.10.3 Pristane/Phytane Ratios
4.10.4 BTEX Ratios
4.10.5 Challenges to BTEX Ratio Methods
4.11 Chemical Degradation Models: Chlorinated Solvents
4.12 Rapid Optical Screening Tool™ Testing
References
5 Contaminant Transport Modeling

5.1 Introduction
5.2 Liquid Transport through Pavement
5.3 Vapor Transport through Pavement
5.4 Contaminant Transport in Soil
5.4.1 Challenges to Contaminant Transport Models for Soil
5.4.2 Colloidal Transport
5.4.3 Preferential Pathways
5.4.4 Cosolvent Transport
5.5 Contaminant Transport in Groundwater
5.5.1 Types of Groundwater Models
5.5.2 Selection of Boundary Conditions,
Grids, and Mass Loading Rates
5.5.3 Software Applicability
5.6 Application of Groundwater Modeling
in Environmental Litigation
5.6.1 Confirmation Models

5.6.2 Reverse Models
5.6.3 Hydrogeologic Variables
5.6.4 Contaminant Properties
5.6.5 Challenges to Reverse Models
5.6.6 Challenges to Phase-Separate Reverse Models
References
6 Forensic Review of Environmental Trial Exhibits

6.1 Introduction
6.2 Exaggerated Vertical and Horizontal Scales
6.3 Selective Data Presentation
6.4 Data Contouring
6.4.1 Manual Contouring
6.4.2 Computer Contouring
6.4.2.1 Inverse Distance Method
6.4.2.2 Kriging
6.4.2.3 Minimum Curvature Method
6.4.2.4 Sheppard’s Method
6.4.2.5 Polynomial Regression
6.4.3 Color-Coded Data
References
Appendices
A Sample Calculation for the Transport of

PCE Vapor through Concrete Pavement
A.1 Introduction
A.2 Sample Calculation
References
B Sample Calculation for the Transport of

PCE Liquid through Concrete via Diffusion
B.1 Introduction
B.2 Sample Calculation
References
C Properties of Alcohol Oxygenates and Ether Oxygenates
D Advective and Partitioning Transport Equations

of Radon for Detecting Diesel in Groundwater
D.1 Introduction
D.2 Derivation
D.3 Conclusions
References

E Chemical and Commercial Synonyms for Selected
Chlorinated Solvents and Aromatic Hydrocarbons
References
F Laboratory Terms and Definitions

Chapters 1 through 6
1 An Overview of the
History, Chemistry,
and Transport of
Chlorinated Solvents
PCE formulated by Faraday in 1821.
1.1 INTRODUCTION
Chlorinated solvents are one of the most frequently encountered contaminants in

environmental investigations (Siegrist, 1993). Trichloroethylene (TCE) and tetra-
chloroethylene (PCE), for example, were detected in 945 groundwater-supplied
drinking systems in an Environmental Protection Agency survey of drinking wells in
the United States. In September 1997, TCE and PCE were detected at 852 and 771,
respectively, of the 1420 National Priority List (NPL) or Superfund sites in the
United States (Butler and Hayes, 1999). As a result of the frequency of detection and
toxicity of chlorinated solvents, millions and often billions of dollars are alleged in
litigation associated with their investigation and remediation.
1.2 CHRONOLOGY AND USE OF

CHLORINATED SOLVENTS
The global production and use of chlorinated solvents began after World War II, with
volumes gradually increasing through the 1950s and 1960s. In the early years of
solvent use, the military was the primary consumer. From 1978 through 1988, the
total production of chlorinated solvents in the United States declined modestly, by
about 11%. After 1988, the decline was more substantial, amounting to about 45%
between 1978 and 1985. The decrease in the demand of chlorinated solvents during
1978 to 1985 reflects the production ban on 1,1,1-trichloroethane (1,1,1-TCA, or
TCA) and Freon-113 (1,1,2-trichloro-1,2,2-trifluoroethane). Another factor in this
decrease was the increased regulations on TCA, tetrachloroethylene (PCE), and

TABLE 1.1
Chlorinated Solvent Uses in the U.S. in 1988
Application TCEa PCEb MCc TCAd Freon-113e Total
Vapor degreasing 47.1 18.1 5.8 106.0 17.7 194.7

Drycleaning — 120.0 — — 2.0 122.0
Intermediate 7.0 80.0 — 22.5 5.3 114.6
Cold cleaning 14.1 6.7 17.2 17.0 40.2 90.2
Electronics 3.2 1.3 16.9 40.8 0.6 78.6
Aerosols — 3.0 20.0 40.8 0.6 64.4
Paint stripping — — 50.0 — — 50.0
Adhesives — — 5.0 26.0 — 31.0
Coatings — 7.0 — 17.2 — 24.2
Flexible foam — — 23.2 — — 23.2
Pharmaceuticals — — 14.4 — — 14.4
Textiles 1.0 2.0 — 7.0 0.5 10.5
Food processing — — 4.2 — — 4.2
Pesticides — — 1.0 3.0 — 4.0
Other — 20.0 49.3 10.5 7.5 87.3
Total demand 72 258 207 298 78 913
Production 82 226 229 328 78 943
a TCE = trichloroethylene.
b PCE = tetrachloroethylene.
c MC = methylene chloride.
d TCA = 1,1,1-trichloroethane.
e Freon-113 = trichlorotrifluoroethane.
methylene chloride (MC). The total global capacity for chlorinated solvents in 1994
was about 1.7 million metric tons, with the U.S. accounting for about 36% of the
total, followed by Western Europe and Japan at 40% and 23%, respectively. Table
1.1 summarizes the consumption of chlorinated solvent use in the U.S. in 1988 for
various industries and applications (IRTA, 1994).
The primary use of chlorinated solvents is vapor degreasing. In vapor degreasing,
solvents are boiled (150 to 250∞F), thereby producing a heated vapor zone within the
degreaser. A single-chamber vapor degreaser contains heating coils at the bottom to
boil the liquid solvent, and cooling coils surround the top to contain the vapor (see
Figure 1.1). Metal parts are lowered into the solvent vapor zone for cleaning, usually
in a metal basket. The warm solvent condenses on the colder parts, dissolving the
contaminants or oil into the solvent. In some instances, a spray wand is manually
used to spray the solvent vapor on the parts in the basket. The vapor zone height is
limited by the cooling coils that condense the solvents and return them to the liquid
at the bottom of the degreaser. The mixture drains to a water/solvent separator, where
the heavier solvent sinks to the bottom and the condensed water and dissolved solvent
are disposed. While many vapor degreasers are more sophisticated, with vacuum

FIGURE 1.1 Single-stage vapor degreaser.
systems, multiple chambers, attached distillation units for removing the soils from
the solvent, ultrasonics, and mechanized basket trays, the general operating principle
is the same.
Cold cleaning is another degreasing technique. Cold cleaning is similar to vapor
degreasing, except that the solvent is maintained at room temperature or is heated to
a temperature below the solvent’s boiling point. Like vapor degreasing, metal parts
are dipped into the liquid solvent, and the contaminants are dissolved and removed
from the metal. Cold cleaning is less effective than vapor degreasing because the
solvent is not boiled clean. The heated solvent used in vapor degreasing is also more
effective in degreasing than the same solvent used at room temperature for the same
purpose. The dominant cold cleaning solvent is 1,1,1-TCA.
Equipment related to vapor degreasers includes distillation or evaporation stills
used to recover solvents. The two types of stills are batch and continuous. In a batch
still (also differential, Raleigh, or pot distillation), a fixed amount of spent solvent is
placed inside a heated evaporation chamber from which the condensed vapor is
withdrawn. Continuous, multistage distillation (also fractional distillation) is used
when there is a need for a high degree of distillation purity, if the amount of spent
solvent to be recovered is large, or when differences in solvent volatility are small.
Continuous distillation is accomplished in a column equipped with trays or packing
materials to facilitate contact between the liquid and vapor phases. Liquid is intro-
duced continuously into the column at the top while the vapor moves upward,
becoming more enriched with the more volatile compounds. The high boiling com-
pounds thereby become concentrated in the liquid.

TABLE 1.2
Solvent Compatibility with Distillation Stills
Boiling Range
Distillation Model/Manufacturer (∞F) Solvents Recycled
SD-15 Acra Electric; Schiller Park, IL N/A TCE, 1,1,1-TCA, PCE

LS-JR Finish Engineering; Erie, PA 100–320 Alcohols, aromatics, chlorinated
solvents, aliphatics, ketones
ER8; Westport, MA <300 Chlorinated solvents
RS-20 Recyclene Products; San Francisco, CA <400 Methylene chloride, acetone,
methanol, 1,1,1-TCA,
n-butyl-acetate, xylene,
mineral spirits, isopropyl
alcohol, Stoddard solvents
Knowledge of the vapor degreaser or solvent still manufacturer is useful in

identifying what solvents are compatible with the equipment. Obtaining the original
operating manual from the manufacturer will provide this information. Table 1.2
summarizes the boiling range and types of solvents that can be recycled for several
distillation stills (California Department of Health Services, 1988).
Chlorinated solvents are used in the electronics manufacturing industry, espe-
cially in the production of semiconductors. Applications include:
• Semiconductor wafer fabrication and assembly

• Printed circuit board fabrication and assembly
• In situ generation of etchants
• Miscellaneous critical electronic applications
Chlorinated solvents used in the semiconductor industry include 1,1,2-trichloro-

1,2,2-trifluoroethane (Freon-113); 1,1,1-trichloroethane (TCA); methylene chloride
(MC); trichloroethene (TCE); and tetrachloroethylene (PCE). Freon-113 and TCA
applications include removal of flux from printed circuit boards after the various
electronic components are soldered to the board. TCA is frequently combined with
alcohol because alcohol is an effective flux remover. TCA and methylene chloride
are also used in the photoresist process. In the early 1990s, all photoresist solutions
were solvent, aqueous, or semi-aqueous solutions. In the photoresist process, dry-
film photoresist is applied to the copper substrate of the electronic board and the
desired circuitry is imprinted by shining a high-intensity light through a photomask.
If a negative photoresist is used, the areas of the film exposed to the light polymerize,
whereas the unexposed areas do not. After the developer carries away the
unpolymerized material, the photoresist is then developed with a solvent such as
TCA, which is followed by the etching step. The remaining photoresist is then
stripped, often with methylene chloride. Table 1.3 lists the composition of formulations

TABLE 1.3
Compounds Associated with the Photoresist Process in Wafer Fabrication
Proprietary Compound Composition
Waycoat photoresist 85% xylene

Microresist developer 95–100% Stoddard solvent
Photoresist developer I 10–30% aromatic hydrocarbons; >60% aliphatic hydrocarbons
Photoresist developer II Mixture of petroleum solvents
Negative photoresist 48% 2-ethoxyethylacetate; 5% n-butyl acetate; 5% xylene.
Positive photoresist 52% 2-ethoxyethylacetate; 6% n-butyl acetate; 6% xylene.
Ultrasonic degreaser Perfluoroisobutylene
Stripper 712D Dodecyl benzene sulfonic acid; 1,2,4-trichlorobenzene, phenols;
pH = 2.4–2.6
Negative photoresist stripper 63% methylene chloride and chlorobenzenes; 23% phenyl sulfonic
J100 (Kodak) acid; 14% phenols and derivatives.
Microstrip 75% chlorinated solvents; orthocresol, dodecylbenzosulfonic acid,
PCE, and dichlorobenzene
Burmar <25% phenol; <25% sulfonic acid; <25% aromatic solvents;
<50% chlorobenzenes
associated with the photoresist process (California Department of Health Services,

1988).
Wafer fabrication is an integral process of semiconductor manufacturing. Poten-
tial contaminants associated with this process include xylene, n-butyl acetate, ammo-
nium fluoride, hydrofluoric acid, sulfuric acid, arsenic, antimony, copper, zinc,
phosphorus, boron, nitric acid, acetic acid, chromic acid, and phosphoric acid.
Dopants used to change the electrical properties of the silicon wafer include anti-
mony, arsenic, boron, and aluminum. In some cases, the chronological use of dopants
provides a means of determining the earliest date that contaminants with these
compounds were introduced into the environment. A diagram of a wafer fabrication
process used since 1986 is shown in Figure 1.2.
While the use and application of chlorinated solvents for semiconductor manu-
facturing has evolved with time, the manufacturing processes remains similar. The
volume of solvents for different electronic applications in the U.S. for 1987 and 1989
is shown on Table 1.4 (California Department of Toxic Substance Control, 1991). As
shown in Table 1.4, about 72,000 metric tons of chlorinated solvents were used in
1987. Freon-113 was widely used in 1987, followed by TCA and methylene chloride.
The use of TCA and PCE during this time frame is believed to be associated with
degreasing applications. Of the electronic board manufacturing activities, solvent use
was highest for board assembly.
In environmental litigation, the most commonly encountered solvents are TCE,
PCE, 1,1,1-TCA, and methylene chloride. Information about the specific applica-
tions and historical production of these solvents is summarized in the following
sections.

FIGURE 1.2 Description of processes for semiconductor wafer fabrication, post-1986.
1.2.1 TRICHLOROETHYLENE (TCE)

Trichloroethylene is used as a metal degreaser and has been available worldwide for
about 50 years. Trichloroethylene was first prepared by Fisher in 1864 during
experiments on the reduction of hexachloroethane with hydrogen (Hardie, 1964).

TABLE 1.4
Use of Chlorinated Solvents in the Electronic Industry in the U.S.
in 1987 and 1989
1987 (1989)
Applications Freon-113 TCA MC TCE PCE
Wafer fabrication 5.4 0.3 (0.5) 1.3 (0.9) 2.2 (3.0) 0.5 (0.7)
Wafer assembly 2.1 (4.9) 1.1 (2.5) 0.5 (0.8) 0.3 (0.5) (0.3)
Developing photoresist 0.8 (3.2) — — —
Stripping photoresist — — 13.8 (5.0) — —
Defluxing boards 25.6 (23.0) 6.6 (8.0) 0.7 (0.6) 0.5 (0.6) 0.5 (0.6)
Critical cleaning 9.2 (8.3) — — — —
In situ etchant generation 0.2 (0.2) 0.2 (0.2) — — —
Note: Figures are in units of thousands of metric tons.
Trichloroethylene production began in Austria and the United Kingdom in 1908;

Germany, in 1910; the U.S., 1925; and Japan, 1935. Trichloroethylene is manufac-
tured by the catalytic oxidation of 1,1,2,2-tetrachloroethane (U.S. patent number
2,951,103) and the catalytic chlorination of acetylene (U.S. patent number 2,938,931).
In the U.S., the Vietnam War accelerated the use of trichloroethylene for aircraft
parts and engine maintenance and production, cleaning rocket hardware, and space
applications and in the automotive industries. The demand for trichloroethylene in
the U.S. peaked in 1968 at about 261,000 metric tons. In 1970, trichloroethylene
accounted for 82% of all of the chlorinated solvents used in vapor degreasing; in
1976, its share had declined to 42%. By 1975, numerous federal, state, and local
regulations in the U.S. existed that restricted the use of TCE due to its being a
suspected carcinogen. In 1975, the National Cancer Institute reported to the National
Institute of Occupational Safety and Health (NIOSH) that PCE and TCE were
“suspect human carcinogens” and that exposure should be minimized. NIOSH recom-
mended that TCA be handled with caution due to its chemical similarity to PCE and
TCE. In 1976, the U.S. exported about 16 million kg, primarily to the Federal
Republic of Germany (3.8 million kg), France (3.4 million kg), Mexico (2.1 million
kg), and Brazil (2 million kg) (U.S. Department of Commerce, 1977).
The demand for trichloroethylene in the U.S. in 1995 was about 128 million
pounds, of which about 16.5 million pounds were imported and about 40 million
pounds exported (Halogenated Solvents Industry Alliance, 1996). While trichloro-
ethylene is an excellent vapor degreaser due to its ability to degrease faster and more
thoroughly than alkaline cleaners, its suspected carcogenicity resulted in many users
switching to TCA and PCE in the 1970s and 1980s. TCA gradually replaced TCE
from 1963 through 1988; as the demand for trichloroethylene decreased, the use of
TCA increased. In February of 1995, the International Agency for Research on
Cancer (IARC) concluded that there was sufficient epidemiological and animal

testing data to classify PCE and TCE as “probable human carcinogens”. The IARC
did not classify 1,1,1-TCA as a human carcinogen. In 1996, the applications of TCE
in the U.S. was about 55% for metal cleaning and degreasing, 41% as a chemical
intermediate, and 4% for miscellaneous applications. Water-based products and
compounds such as n-propyl bromide (EnviroChem) became more common as a
replacement for TCE. In the U.S., trichloroethylene is produced by Dow Chemical
Company and PPG Industries.
Global consumption of trichloroethylene decreased from 224,000 metric tons in
1990 to 214,000 in 1993, but there is expected to be an increase in TCE consumption
as a precursor for HFC-134a production. The annual trichloroethylene consumption
in the U.S. and Japan from 1993 to 1998 was expected to increase about 16% and 6%,
respectively. TCE consumption is expected to decrease in Western Europe by about
2% annually, as decreases in the use of TCE in metal degreasing will offset increases
in HFC-134a precursor consumption.
In Western Europe, trichloroethylene is produced by Elf Atochem (France), Dow
Europe/Switzerland (Germany), EniChem (Spain), ICI Chemicals and Polymers
(United Kingdom) and Solvay/Belgium (France and Italy). In Western Europe,
according to the European Chlorinated Solvent Association (1998), TCE production
from 1993 to 1997 was as follows: 1993 and 1994 (94,000 metric tons), 1995
(103,000 metric tons), 1996 (99,000 metric tons), and 1997 (92,000 metric tons). The
increase in TCE production in 1995 and 1996 is due to the replacement of 1,1,1-
trichloroethane with TCE for vapor degreasing.
1.2.2 TETRACHLOROETHYLENE
(PCE, OR PERCHLOROETHYLENE)
Tetrachloroethylene was first formulated in 1821 (Izzo, 1992). Global demand of
PCE decreased from 513,000 metric tons in 1990 to 338,000 metric tons in 1993. The
use of PCE as a precursor in the production of chlorofluorocarbon-113 (CFC-113)
ceased in 1996 due to its association with ozone depletion. In some countries, PCE
consumption is expected to increase due to its use in manufacturing hydrochloro-
fluorocarbon-123 (HCFC-123) and hydrofluorocarbon-134a (HFC-134a). From 1993
to 1998, PCE consumption in the U.S. and Japan increased about 3% but decreased
about 12% annually in Western Europe.
Tetrachloroethylene has been the chlorinated solvent of choice in the drycleaning
industry since the late 1930s. By the late 1940s or early 1950s, PCE replaced
synthetic solvents such as carbon tetrachloride in the drycleaning industry. Prior to
the 1960s, however, petroleum derivatives were still the dominant solvents in the
drycleaning industry in the U.S., where the demand for PCE increased steadily from
1972 to 1981. PCE usage peaked in 1975 at about 348,000 metric tons. After 1975,
a decline in demand continued until 1994, when the demand for tetrachloroethylene
was about 113,000 metric tons. In the late 1980s, drycleaners consumed 56% of the
PCE in the U.S. In 1990, PCE production in the U.S. was about 383 million pounds,
of which 55 million pounds were exported. In 1990, about 72.1 million pounds were

FIGURE 1.3 PCE demand by the drycleaning industry in the U.S. from 1985 to 1997.
imported into the U.S. (Halogenated Solvents Industry Alliance, 1994). In the U.S.,
PCE is produced by Dow Chemical USA, PPG Industries, and Vulcan Materials
Company. Figure 1.3 summarizes PCE usage in the U.S. by drycleaners from 1985
to 1997 (Halogenated Solvents Industry Alliance, 1998a). In 1990, tetrachloroethyl-
ene use in the U.S. was 50% for drycleaning/textile processing, 25% as a chemical
intermediate, and 15% in metal cleaning and degreasing, with miscellaneous uses
accounting for about 10% (Halogenated Solvents Industry Alliance, 1998a).
In 1992, there were approximately 34,000 drycleaning businesses in the U.S.,
with about 28,000 facilities using PCE. In 1992, the typical commercial drycleaner
processed about 75,000 pounds of clothing annually, which represented about 90%
of the industry. Approximately 25,000 of these commercial drycleaners used PCE
(about 120,000 metric tons annually) (Wolf, 1992).
The three categories of drycleaning machines that use tetrachloroethylene are
• A transfer machine, in which the clothing is washed in one unit and physically
transferred to a dryer for drying. Emissions from the washer and dryer can be
uncontrolled or they can be routed to a control device. Approximately 30% of all
drycleaning machines are transfer units.
• A dry-to-dry vented unit, in which the clothing is washed and dried in the same
cylinder. The PCE emitted from the unit can be uncontrolled or vented to a control
device. Approximately 70% of the retail drycleaners in the U.S. have dry-to-dry units.
• A dry-to-dry closed loop unit, in which the wash and dry cycles occur in the same
unit. Tetrachloroethylene emissions are controlled within the unit with a refriger-
ated condenser.

Most drycleaners (about 90%) remove soil, dust, hair, and lint from the solvent
with cartridges of activated carbon. Distillation units are used to remove oils and
fats from the solvent. After filtration through the activated carbon or tubular filters,
the solvent is heated to between 190 and 250∞F. The PCE is condensed and
recovered, and the remaining sludge can contain up to 50% PCE. Some drycleaners
reclaim the PCE in the sludge in a muck cooker or a cooker/still combination.
In Western Europe, tetrachloroethylene production declined about 4.8% between
1993 and 1997, from 84,000 tons in 1993 to 68,000 tons in 1997, due to the
replacement of obsolete open drycleaning machines with closed systems. From 1988
to 1998, PCE use in the drycleaning industry in Western Europe declined by about
two thirds due to replacement of older equipment with machines with refrigeration
technology that reduced the volume required for operation (Halogenated Solvents
Industry Alliance, 1998). In Western Europe, TCE is produced by Elf Atochem
(France), Dow Europe/Switzerland (Germany), EniChem (Spain), ICI Chemicals
and Polymers (United Kingdom), and Solvay/Belgium (France and Italy) (European
Chlorinated Solvent Association, 1996).
1.2.3 1,1,1-TRICHLOROETHANE (1,1,1-TCA,

OR METHYLCHLOROFORM)
1,1,1-Trichloroethane was created in 1840 by the reaction of chlorine with 1,1-

dichloroethane. TCA was first reported in the U.S. in 1946 (U.S. Tariff Commis-
sion, 1947). In the U.S., it is produced via the chlorination of vinyl chloride derived
from 1,2-dichloroethane, via hydrochlorination of vinylidene chloride derived from
1,2-dichloroethane, or through the thermal chlorination of ethane. In Japan, 1,1,1-
TCA is produced by the chlorination of vinyl chloride.
TCA production and consumption have decreased dramatically due to its ozone
depletion potential in the upper atmosphere. Global consumption from 1990 to 1993
decreased from 665,000 to 349,000 metric tons. On a worldwide basis, production
was reduced to 50% of its 1989 levels throughout 1994 and 1995. Since 1995, TCA
in Europe has been used only as a precursor chemical. Except for its use as a
precursor, worldwide production essentially ceased in 1996.
TCA is the historical solvent of choice in cold cleaning. The demand for
TCA increased substantially over about three decades (1967 to 1994) in the U.S.
In the late 1960s, when the use of TCE came under scrutiny due to its identifi-
cation as an animal carcinogen, TCA was often used as its replacement. The
historical demand for TCA in the U.S. between 1967 and 1994 peaked in 1988 when
about 298,000 metric tons were consumed. TCA usage declined in 1991 due to an
amendment to the Montreal Protocol that called for a complete phase-out of
TCA by 1996 due to its contribution to ozone depletion. In Western Europe,
most manufacturers ceased production by the end of 1995 with the exception of
its use as a chemical intermediate and for some permitted uses for virgin
solvents. By 1994, the U.S. demand for TCA had decreased to about 159,000
metric tons.

1.2.4 METHYLENE CHLORIDE (DICHLOROMETHANE)
Methylene chloride was introduced as a replacement for more flammable solvents
over 60 years ago. Total demand in the U.S. in 1996 was about 285 million pounds,
of which about 20 million pounds were imported and about 130 million pounds
exported (Halogenated Solvents Industry Alliance, 1998b). Globally, methylene
chloride is produced by the following manufacturers:
• Aragonesas and Erkimia (Spain)

• Elf Atochem (France)
• Dow Chemical and Vulcan Materials (U.S.)
• Dow Europe/Switzerland (Germany)
• LIL Europe (Germany)
• ICI Chemical and Polymers (United Kingdom)
• Solvay/Belgium (France and Italy)
Methylene chloride consumption in Western Europe decreased from about 190,000

to 135,000 metric tons from 1985 to 1994 (European Chlorinated Solvent Associa-
tion, 1997).
Methylene chloride is the active ingredient in many paint removers, including
commercial and furniture strippers and home paint removers. It is also used in aircraft
maintenance due to its ability to penetrate, blister, and remove a variety of paint
coatings. In the maintenance of military and commercial aircraft, a methylene
chloride-based product is often specified for surface inspection for damage. Since the
mid-1990s, methylene chloride has replaced 1,1,1-TCA in nonflammable adhesive
formulations, including the fabrication of upholstery foam. TCA is currently the
leading auxiliary blowing agent used to produce slabstock flexible polyurethane
foams in the furniture and bedding industries. In the pharmaceutical industry, meth-
ylene chloride is used as a reaction and recrystallization solvent for extraction, as
well as a carrier for pharmaceutical tablet coatings. In the chemical processing
industry, it is used in the production of cellulose triacetate, which serves as a base for
photographic film. The uses of methylene chloride in the U.S. in 1996 and Western
Europe in 1994 as a percentage of the total consumption are shown on Table 1.5
(European Chlorinated Solvent Association, 1997).
1.3 CHEMISTRY AND PROPERTIES

OF CHLORINATED SOLVENTS
1.3.1 TERMINOLOGY AND CLASSIFICATION

Chlorinated solvents include a wide range of compounds. As such, a common
terminology for describing these compounds is useful. Acronyms used in environ-
mental reports to characterize chlorinated solvents and non-chlorinated compounds
as a function of their specific density include the following terms (Lizette et al.,
1997):

TABLE 1.5
Use of Methylene Chloride in the U.S. and Western Europe
United States Western Europe
Applications (1996) (1994)
Paint stripping 30 19.14

Adhesives 16 —
Aerosols and coatings 11 11.73
Foam manufacturing 10 —
Pharmaceuticals 10 40.71
Chemical processing 9 8.67
Metal cleaning 8 —
Miscellaneous 6 17.92
Note: Figures are percent of total usage.
• NAPL (non-aqueous phase liquid)

• DNAPL (dense non-aqueous phase liquid)
• LNAPL (light non-aqueous phase liquid)
A NAPL is generally immiscible with water. The term “free phase liquid” is used to
describe a NAPL or DNAPL/LNAPL mixture (U.S. EPA, 1992). A DNAPL describes
a chemical with a fluid density greater than 1.01 g/cm3 and a vapor pressure less than
300 torr (a torr is equal to 1/760th of a standard atmosphere or about 1 mmHg).
Examples of DNAPLs include acetic acid, phenol, dichloroethylene, carbon disulfide,
naphthalene, polychlorinated biphenyls, ethylene dichloride, sulfuric acid, parathion,
tetrachloroethylene, trichloroethylene, and methyl bromide. LNAPLs are compounds
with a fluid density less than water (about 1.01 g/cm3) and include mineral spirits #10,
hexane, gasoline, benzene, butyl acetate, turpentine, ether, crude oil, and diethyl sulfide.
Another classification scheme is based on the degree of halogenation and whether
the compound is volatile or semi-volatile. Classes of chlorinated hydrocarbons based
on this scheme are summarized in Table 1.6. Properties of chlorinated solvents
affecting their fate and transport through the subsurface include their chemical
structure, their Henry’s Law constant, liquid density, water solubility, viscosity,
vapor pressure and density, boiling point, latent heat of vaporization, and the octanol
partition coefficient. Reactions that impact the movement and transformation of
solvents in the subsurface and are interrelated with these chemical and physical
properties include hydrolysis, sorption, and biodegradation.
1.3.2 CHEMICAL STRUCTURE AND PROPERTIES

The major chlorinated solvents used in industry are TCE, PCE, 1,1,1-TCA, the
Freons (primarily chlorofluorocarbon-113, or CFC-113), and methylene chloride.
The chemical structures of these solvents are shown on Figure 1.4. Trichloroethylene
(TCE) and perchloroethylene (PCE) have an ethylene or double-bonded carbon

TABLE 1.6
Classification of Chlorinated Solvents Based on Degree of
Halogenation and Volatility
Halogenated Volatiles
Chlorobenzene, 1,2-dichloropropane; 1,1-dichloroethylene; 1,2-dichloroethane;
trans-1,2-dichloroethylene; cis-1,2-dichloroethylene; 1,1,1-trichloroethane;
methylene chloride; 1,1,2-trichloroethane; trichloroethylene (TCE); chloroform;
carbon tetrachloride; 1,1,2,2-tetrachloroethane; tetrachloroethylene (PCE);
ethylene dibromide
Halogenated Semi-Volatiles
1,1-dichlorobenzene; 1,2-dichlorobenzene; Aroclor-1242; Aroclor-1254;
Aroclor-1260; chlordane; dieldrin; 2,3,4,6-tetrachlorophenol; pentachlorophenol
Non-Halogenated Semi-Volatiles
2-methyl naphthalene; o-cresol; p-cresol; 2,3-dimethylphenol; m-cresol; phenol;
naphthalene; benzo(a)anthracene; fluorene; acenaphthene; anthracene;
dibenzo(a,h)anthracene; fluoranthene; pyrene; chrysene; 2,4-dinitrophenol
Miscellaneous
Coal tar, creosote
structure with three and four chlorines, respectively. Methylene chloride is a meth-
ylene chlorideane structure containing two chlorine atoms. Trichloroethane (TCA)
and CFC-113 are ethane derivatives. 1,1,1-TCA has three chlorines, all on one
carbon. CFC-113 is fully halogenated with three chlorines and three fluorine atoms.
Freon is a chlorofluorocarbon because it contains a fluorine atom.
FIGURE 1.4 Chemical structure of PCE, TCE, TCA, Freon-113, and methylene chloride.

TABLE 1.7
Henry’s Law Constant for Selected Chlorinated Solvents
Henry’s Law Constant
Compound (atm-m3/mol)
Trichloroethylene (TCE) 0.00937

Tetrachloroethylene (PCE) 0.0174
Carbon tetrachloride (PCM) 0.0298
Chloroform (TCM) 0.00358
Dichloromethane (DCM) 0.00212
1,2-Dibromomethane (EDB) 0.000680
cis-1,2-Dichloroethylene (1,2-DCE) 0.000374
trans-1,2-Dichloroethylene (1,2-DCE) 0.000916
1,1,1-Trichloroethane (TCA) 0.0167
1.3.3 HENRY’S LAW CONSTANT (KH)

The Henry’s Law constant (KH) (also known as the air-water partition coefficient) is
the ratio of the partial pressure of a compound in air to the concentration of that
compound in water at a given temperature. The Henry’s Law constant is, therefore,
a measure of the propensity of a compound to volatilize when moving through the
soil. As the Henry’s Law value increases, the concentration of the contaminant in the
soil vapor phase increases. Compounds with high Henry’s Law constants (PCE,
Freon-11, Freon-113, and vinyl chloride) are more amenable to soil gas surveys and
remediation via vapor extraction than compounds with low values. Values for
Henry’s Law constants are usually expressed in units of moles per cubic meter for
air to moles per cubic meter for water (atm-m3/mol). As a rule of thumb, compounds
with a Henry’s Law constant greater than 10–3 atm-m3/mol and a molecular weight
less than 200 g/mol are considered volatile (U.S. EPA, 1996). A compound with a
Henry’s Law constant less than about 5 ¥ 10–5 atm-m3/mol is considered soluble and
tends to remain in water (Olson and Davis, 1990).
The Henry’s Law constants for TCE and PCE are 0.00937 and 0.0174 atm-m3/
mol, respectively, and Table 1.7 lists the Henry’s Law constants for selected chlori-
nated solvents (Montgomery, 1992; Pankow and Cherry, 1996).
Values for Henry’s Law constants can also be expressed in dimensionless form as:
KH¢ = KH/(RK) (Eq. 1.1)
where
KH¢ = dimensionless Henry’s Law constant.

KH = Henry’s Law constant (atm-m3/mol).
R = ideal gas constant (8.20575 ¥ 10–5 atm-m3/mol – K).
K = temperature of water (degrees K).

TABLE 1.8
Chemical Formula and Liquid Density for Selected
Chlorinated Solvents at 25∞C
Liquid Density
Chlorinated Solvent Formula (g/cm3)
Trichloroethylene (TCE) CHCl:CCl2 1.46
Tetrachloroethylene (PCE) CCl2CCl2 1.63
1,2-Dibromomethane (EDB)a BrCH2CH2Br 2.18
cis-1,2-Dichloroethylene CH2Cl2 1.28
trans-1,2-Dichloroethylene CH2Cl2 1.26
1,1,1-Trichloroethane (TCA) C2H3Cl3 1.35
Chloroformb CHCl3 1.49
1,2-Dichloropropane CH3CHClCH2Cl 1.16
Dichloromethane (DCM)c CHCl2F 1.34
1,1-Dichloroethane C2H4Cl2 1.17
Carbon tetrachloride (CT) CCl4 1.59d
Chloroethane C2H5Cl 0.90d
1,1,2,2-Tetrachloroethane C2H2Cl4 1.60
1,1,2-Trichloroethane C2H3Cl3 1.44
Vinyl chloride (VC) C2H3Cl 0.91d
Trichlorofluoromethane (Freon-11) CCl3F 1.49
Dichlorofluoromethane (Freon-12) CCl2F2 1.35e
a Also known as ethylene bromide and ethylene dibromide.

b Also known as trichloromethane.
c Also known as tetrachloromethane.
d At 20∞C.
e At 15∞C.
1.3.4 LIQUID DENSITY

The density (also called specific gravity) of a substance is the ratio of its density
relative to distilled water (a mass-to-volume ratio). The density of distilled water at
standard temperature and pressure is about 1.0 g/mL. The density of a substance is
dependent on the temperature at the time of measurement. Most chlorinated solvents
have fluid densities greater than 1 g/cm3.
Compounds with densities greater than 1.0 relative to water (e.g., perchloroeth-
ylene, trichloroethylene, polychlorinated biphenyls, bromoform) have a greater prob-
ability of “sinking” into the groundwater. Chlorinated solvents with fluid densities
greater than water are transported vertically in the vadose zone due to gravity and
capillary forces. Upon entering the groundwater, these DNAPLs are transported as
a function of specific gravity and less by advection (the mass transport of groundwa-
ter) through groundwater. Liquids with densities less than 1.0 (methyl ethyl ketone,
gasoline, diesel, Stoddard solvent, mineral oils) tend to “float” and spread along the
capillary fringe. Table 1.8 lists selected chlorinated solvents, their formulas, and
liquid densities (Montgomery, 1992; Pankow and Cherry, 1996; Ramamoorthy and
Ramamoorthy, 1998).

TABLE 1.9
Generic Categories of Solubility
Generic Category Solubility (mg/L)
Insoluble Less than 1

Slightly soluble 1–100
Soluble 100–10,000
Very soluble Greater than 10,000
The density of a mixture of free phase chlorinated solvents varies as a result of

the selective dissolution (i.e., effective diffusion coefficient) of individual solvents
into soil or rock. Individual compounds of a DNAPL mixture such as a spent solvent
migrating through a fractured clay will selectively dissolve with time into the clay.
The dissolution of the chlorinated solvent into the clay results in a change in the
composition and physical properties of the solvent, including liquid density (Parker
et al., 1994a). In most cases, the specific density of the mixture increases as the higher
density solvents persist longer in the immiscible phase.
1.3.5 SOLUBILITY
The solubility of a compound is the saturated concentration of the compound in water
at a known temperature and pressure. In general, the higher the water solubility, the
more likely it is that the compound will be mobile in the subsurface while being less
accumulative, bioaccumulative, volatile, and persistent. The lower the water solubil-
ity, the greater the probability that it will be immobilized via adsorption and will be
more accumulative or bioaccumulative in organisms. The solubility of many chlori-
nated solvents is high.
The terms “slightly soluble” or “very soluble” are used in environmental reports
or by expert witnesses. These generic categories of solubility at room temperature (20
to 30∞C) are described in Table 1.9 (Kamrin, 1997). Calculated and literature solu-
bilities of selected pure phase chlorinated solvents in water at 25∞C are shown in
Table 1.10 (Huling and Weaver, 1991; Pankow and Cherry, 1996; Ramamoorthy and
Ramamoorthy, 1998).
The effective solubility of a multi-component solvent in water depends on the
composition of the mixture and the respective breakdown products. A constituent’s
solubility within this multi-component mixture may be orders of magnitude lower
than the aqueous solubility of the pure chemical in water (Odencrantz et al., 1992).
The concentration of a dissolved phase solvent at a threshold concentration is
used as evidence of the presence of a DNAPL. In the 1980s, the rule of thumb was
that, if a dissolved concentration of 10% of the saturation for the chlorinated solvent
was detected, the presence of a DNAPL was inferred (Feenstra and Cherry, 1988).
In the early 1990s, research indicated that concentrations 1% or more of a compound’s

TABLE 1.10
Calculated and Literature Solubilities of Chlorinated Solvents
Calculated Solubility Literature Solubility
Compound (mg/L)a (mg/L)
Trichloroethylene (TCE) 1384.9 1100

Tetrachloroethylene (PCE) 236.96 200
1,2-Dibromomethane (EDB) 5017.5 4200
cis-1,2-Dichloroethylene 6995.8 3500
trans-1,2-Dichloroethylene 4389.1 6300
1,1,1-Trichloroethane (TCA) 1309.6 1300
Chloroform (TCM) 8513.5 8000
1,2-Dichloropropane 2968.0 2800
a Knowledge of the vapor pressure and Henry’s Law constant allows calculation of
the solubility according to the following relationship: solubility (mg/L) = (vapor
pressure [torr] ¥ molecular weight of the compound [g/mol])/(760 ¥ Henry’s Law
constant) (Pankow and Cherry, 1996).
solubility constitute a high likelihood of the presence of a DNAPL (Cohen et al.,

1993; U.S. EPA, 1992, 1993). The most recent convention is consistent with this “1%
rule” (Newell and Ross, 1991; Pankow and Cherry, 1996).
1.3.6 VISCOSITY
Viscosity is the property of a substance to offer internal resistance to flow. Kinematic
viscosity is the absolute viscosity of the substance divided by its density. For
example, the absolute viscosity of TCE is 0.57 cSt and its specific density is 1.46, so
its kinematic viscosity is 0.39 cSt. A high-density liquid with a low viscosity has a
low kinematic viscosity; such a fluid flows quickly through a porous medium vs. a
liquid with a higher kinematic viscosity.
Viscosity units encountered in environmental reports include the poise and
stoke. The poise is a measure of absolute viscosity and is equal to gm/sec ¥ cm.
Kinematic viscosity is expressed in stokes, which are equal to gm/sec ¥ cm ¥ density
at a given temperature. A centipoise (cP) and centistoke (cSt) are each equal to
0.01 stoke.
Fluid velocity through porous media is often approximated as a proportional
inverse to the kinematic viscosity. In the vadose zone, TCE may move 2.5 times
faster than water through the same soil (Dragun, 1988). A decrease in viscosity,
therefore, increases the flow rate of a chlorinated solvent through a porous media.
The kinematic viscosities of selected chlorinated solvents are summarized in Table
1.11 (Huling and Weaver, 1991; Montgomery, 1992).

TABLE 1.11
Kinematic Viscosity of Selected Solvents
Chemical Kinematic Viscosity
(cSt)

1,2-Dibromomethane (EDB) 0.79
cis-1,2-Dichloroethylene 0.38
trans-1,2-Dichloroethylene 0.32
Chloroform (TCM) 0.38
1,2-Dichloropropane 0.75
1.3.7 VAPOR PRESSURE AND DENSITY

Volatilization is the phase change of a compound from a liquid or solid to a gas. An
example is the partition of TCE from a shallow or highly fluctuating groundwater
into the soil vapor in the unsaturated zone. Volatilization is not a form of degradation.
Factors affecting the volatility of a compound include:
• Vapor pressure
• Water solubility
• Soil moisture content
• Adsorption
• Wind speed, exposure to sunlight, air temperature, and turbulence (if the product
is released at the ground surface)
• Soil temperature
• Depth below the land surface and time available for volatilization to occur
In general, compounds with vapor pressures exceeding 0.5 to 1 mmHg can exist in
appreciable concentrations in the vapor phase near a free phase solvent. The vapor
pressures and densities of selected chlorinated solvents are summarized in Table 1.12
(Montgomery1992: Pankow and Cherry, 1996; Ramamoorthy and Ramamoorthy, 1998).
1.3.8 BOILING POINT AND LATENT

HEAT OF VAPORIZATION
The boiling point of a chlorinated solvent is important due to its application in vapor
degreasing. Table 1.13 lists the boiling point and latent heat of vaporization for
several common chlorinated solvents (Montgomery, 1992: Ramamoorthy and
Ramamoorthy, 1998). The boiling point of PCE is high, while methylene chloride
and CFC-113 are low. The latent heat of vaporization is one measure of the energy
necessary to maintain the solvent at its boiling point. The higher the latent heat of
vaporization, the higher the energy needed to keep the solvent at its boiling point.

TABLE 1.12
Vapor Pressure and Density of Selected Chlorinated Solvents
Vapor Pressure Vapor Density
Compound (mm at 20∞C) (g/L)
Tetrachloroethylene (PCE) 14.0 6.86

Trichloroethylene (TCE) 57.8 5.37
1,1,1-Trichloroethane (TCA) 90.0 5.45
Methylene chloride 348.9 3.47
Freon-11 687.0 5.61
Freon-13 270.0 7.66
1.3.9 OCTANOL/WATER PARTITION COEFFICIENT (KOW)

The octanol partition coefficient (also called the partition coefficient) is the ratio of
the equilibrium concentration of a chemical in octanol and water. Octanol/water
partition coefficients are unitless. In general, compounds with values greater than
1000 are indicative of a low mobility in the subsurface, nonbiodegradability, and high
sorbativity by soil (Ney, 1995). A low Kow value (<500) suggests a high water solubility,
a high mobility, little to no bioaccumulation, and a susceptibility to degradation.
The octanol/water partition coefficient is an estimate of the hydrophobicity or the
partitioning tendency of a compound from water into organic media such as wax,
lipids, humin, and humic acid. The Kow estimates the organic carbon-water partition
coefficient (Koc) via the following relationship (Karickhoff, 1981):
Koc = 0.41 Kow (Eq. 1.2)
Koc (also known as the sorption or soil/sediment partition coefficient) is the ratio of
the adsorbed chemical per unit weight of organic carbon to the aqueous solute
concentration. This value is used in groundwater modeling to estimate the retardation
of a compound transported in groundwater due to sorption.
TABLE 1.13
Boiling Point and Latent Heat of Vaporization
Boiling Point Latent Heat of Vaporization
Compound (∞F) (Btu/lb)
Tetrachloroethylene (PCE) 250 90

Trichloroethylene (TCE) 188 103
1,1,1-Trichloroethane (TCA) 165 102
Chlorofluorocarbon-113 (CFC-113) 118 63
Methylene chloride (MC) 104 142

1.3.10 HYDROLYSIS
Hydrolysis is the chemical breakdown of substances by water. The rate of breakdown
depends upon the chemical structure of the contaminant, solubility, sunlight, pH, and
oxidation-reduction (redox). Hydrolysis is generally assumed to be a first-order
process (i.e., the time required to reach one-half [t1/2] of its original amount). An
example of hydrolysis is the breakdown of TCA to acetic acid (McCarty, 1994).
Hydrolysis rates vary over a few orders of magnitude, depending on the initial
concentration or procedural differences in the measurement. Tetrachloromethane is
reported to have a hydrolysis half-life of 7 years at a concentration of 7000 mg/L and
7000 years at a concentration of 1 mg/L (Mabey and Mill, 1978). The hydrolysis half-
life of trichloromethane is reported to be 1.25 years and 3500 years at the same
concentrations (Dilling et al., 1975). Hydrolysis rates in the presence of soil may be
faster or slower than those reported in water, depending on the soil and compound-
specific effects of pH, redox, sorption, and surface catalyzed reactions.
1.3.11 SORPTION
Sorption encompasses adsorption, absorption, ion exchange, ion exclusion, retarda-
tion, chemisorption, and dialysis. It is used to denote the uptake of a vapor or liquid
into another material without reference to a specific mechanism (Chiou, 1989).
Absorption (the penetration of substances into the bulk of a solid or liquid) and
adsorption (the surface retention of solid, liquid, or gas molecules by a solid or liquid)
are the most important. Sorption affects distribution of a contaminant between the
solid and liquid phase and the relative retardation of the chemical. The higher the
fraction of the chlorinated solvent sorbed, the less is available for transport deeper
into the soil.
The sorption capacity of a compound is described by its sorption coefficient. The
sorption coefficient is the ratio of an adsorbed chemical per unit weight of organic
carbon to its concentration. It implicitly assumes a reversible process where sorption
and desorption occur at the same rate. The sorption coefficient is usually estimated
via batch isotherm experiments. Several correlations are available for organic com-
pounds that relate the distribution coefficient to the soil organic content as expressed
by the octanol/water partition coefficient (Fetter, 1994).
1.3.12 BIODEGRADATION
Biodegradation is the enzyme-catalyzed transformation of complex compounds (prin-
cipally by bacteria, fungi, and yeast) into simpler substances. Bacteriological or
reductive dechlorination is the principal process resulting in the degradation of
chlorinated solvents in the subsurface (Gao et al., 1995). For most biodegradation
pathways, the final degradation products are carbon dioxide and water. Figure 1.5
depicts reductive dechlorination degradation pathways for PCE, 1,1,1-TCA, and
carbon tetrachloride. Soil contains both anaerobic and aerobic regions, many of

FIGURE 1.5 Degradation pathways of PCE, 1,1,1-TCA, 1,2-DCA, and carbon tetrachloride. (Data from Vogel et al., 1987a,b; McCarty, 1993, 1994;
Pankow and Cherry, 1996.)

which are highly localized. These alternating regions of oxygen-rich and oxygen-
deficient sediments create unique and distinct degradation environments. A common
classification scheme is the biological decay of chlorinated solvents as anaerobic or
aerobic.
1.3.12.1 Anaerobic Degradation

Anaerobic degradation occurs via dehalogenation. A chlorine atom is released during
dehalogenation. Strong reducing conditions with low dissolved oxygen levels must
exist in order for dehalogenation to proceed. Methanogenic (methane-producing)
bacteria facilitate dehalogenation under anaerobic conditions. In anaerobic degrada-
tion, the rate of reductive dehalogenation decreases as more chlorines are removed.
The process is examined via the loss of three chlorine atoms under anaerobic
conditions as follows (Woodbury and Li, 1998):
H+ + HC2Cl3 Æ H2C3Cl2 + Cl– Æ H+ + H2C3Cl2 Æ

(TCE) Æ (DCE) Æ (DCE)
H3C2Cl + Cl– Æ H+ + H3C2Cl Æ H4C2 + Cl– Æ

(vinyl chloride) Æ (vinyl chloride) Æ (ethene)
DCE can exist as the three isomers 1,1-DCE, cis-DCE, and trans-1,2-DCE. Of these
isomers, cis-1,2-DCE is produced in the greatest abundance, at a rate of about 30
times the concentration of trans-1,2-DCE. The decay rate from TCE to cis-1,2-DCE
is also faster than from TCE to trans-1,2-DCE or 1,1-DCE. The decay rate from cis-
1,2-DCE to vinyl chloride (chloroethene), however, is slower than from trans-1,2-
DCE and 1,1-DCE to vinyl chloride. The eventual products of this dechlorination
process beyond vinyl chloride are ethene, ethane, and carbon dioxide. Recent re-
search indicates that under strongly reducing methanogenic conditions, methane is a
significant degradation product of 1,1,1-TCA (Bradley et al., 1999).
1.3.12.2 Aerobic Degradation

Aerobic degradation is believed to be initiated by enzymes called oxygenases (Tsien
et al., 1989). These enzymes initiate degradation after producing a specific organic
compound that serves as a carbon and energy source for the bacteria. Naturally
occurring total organic carbon (TOC) can provide the carbon source.
Research indicates that, unlike anaerobic environments, for aerobic degradation
the more chlorinated the compound, the slower the degradation process. Subsurface
environments conducive to aerobic degradation include highly transmissive aquifers,
the presence of methane-oxidizing bacteria, and chlorinated compounds with a small
number of chlorine atoms.
The rate and ability of microbes to degrade chlorinated hydrocarbons is
dependent on the ability of the subsurface environment to support a healthy
community of microbes. The concentrations of nutrients and oxygen required to

TABLE 1.14
Results of TCA and TCE Degradation in
Anaerobic and Aerobic Environments
Subsurface TCA TCE
Environment Week (mg/L) (mg/L)
Anaerobic 0 570 540

4 420 260
8 580 340
95 73 54
Aerobic 0 600 650
2 440 440
4 540 480
14 430 260
Aerobic 0 600 540
2 580 540
4 620 600
14 650 500
sustain viable microbial communities are highly variable. Some generalizations

concerning biodegradation are that biodegradation may not occur if the concentra-
tion of the compound is very low, although most chlorinated solvents can be
degraded to some extent. An example of the effect of the subsurface environment
on degradation is illustrated by a study of an aviation gasoline plume containing
TCA and TCE. Soil samples spiked with TCE and TCA were analyzed over time
to examine the anaerobic and aerobic degradation rates. Table 1.14 summarizes
these results (Wilson et al., 1994).
The presence of chlorinated solvents at high concentrations may inhibit the
microbial degradation that may otherwise occur (Phelps et al., 1988). These types of
complications, as well as the heterogeneity of the subsurface aerobic and anaerobic
environments, introduce significant uncertainty in the use of degradation rates as
indicators of the timing of a chlorinated solvent release (Alexander, 1985).
1.4 TRANSPORT OF CHLORINATED

SOLVENTS THROUGH SOIL
Chlorinated solvents can enter the subsurface as a dissolved phase, a non-aqueous

phase liquid (NAPL), or a vapor. Non-aqueous phase liquids can exist as a separate
phase within the subsurface and as a dissolved and/or vapor phase plume originating
from the NAPL. Care must be exercised in extrapolating pure phase properties, such
as fluid density, volatility, and viscosity, to a release that is a solvent mixture.

As chlorinated solvents travel through soil, they are distributed in the unsaturated
zone and capillary fringe as residual saturation. Dense non-aqueous phase liquid
residual saturation values range from 2 to 40% of the soil pore space and are
generally higher in poorly sorted soils. The residual saturation of PCE in a Selvilleta
sand, for example, was reported to be 27% (Wilson et al., 1990). A vapor phase halo
exists for some distance and concentration around this residual soil contamination.
In the case of a solvent dissolved in water that is released at the ground surface, the
dissolved phase spreads vertically and horizontally as a function of the soil suction
gradient and gravity. This trend continues until the suction gradient in the upper portion
of the contaminant plume becomes negligible. Gravity eventually constitutes the
only remaining force to move the liquid vertically. If the liquid does not reach the
capillary fringe, the fluid become immobilized as residual saturation around the soil
grains until it is remobilized by infiltrating water or a fluctuating water table.
The movement of a free phase liquid through soil is controlled primarily by
capillarity due to the interfacial tensions present between different fluids (LNAPL/
DNAPL, LNAPL/water, DNAPL/air, etc.) and the size of the soil pore opening. The
moisture content of the soil also influences the ability of the free phase liquid to move
into the open pore space or displace the water occupying this space. In most cases,
water coats the soil grains, thereby restricting the movement of the chlorinated
solvent into the larger pore openings.
The ability of a chlorinated solvent to enter the smaller openings between the soil
grains is a function of the interfacial tensions between the chlorinated solvent and
other liquids (air, water, another DNAPL/LNAPL). The energy or pressure required
for entry into these smaller openings is known as the entry pressure, which is defined
as the capillary pressure at which the free phase solvent becomes continuous at the
macroscopic scale and is capable of flowing through the material. For most soils, the
entry pressure corresponds to water saturation ranges from about 0.8 to 0.95 (Pankow
and Cherry, 1996). The entry pressure is proportional to the interfacial tension
between the free phase liquid and water and is inversely proportional to the opening
between the soil grains.
The entry of a free phase liquid into smaller openings between soil grains is
dependent on the pore opening and interfacial tension(s) between the liquids. Free
phase liquids tend to become immobilized or trapped within finer grained materials.
Conversely, liquids introduced into the subsurface that reduce the interfacial tensions
between the liquids (e.g., surfactants) enhance the movement of the free phase liquid
into these smaller apertures. The primary forces driving free phase liquids through
the vadose zone include (Kueper and McWhorter 1991, 1992):
• Duration and volume of the release

• Density and viscosity of the fluid
• Pressures driving the liquid
• Intrinsic permeability of the soil
• Degree of free product saturation of the soil
• Presence of preferential pathways such as fractured rock or slickensides found in
silt or clayey soils

Highly permeable soil and free product saturation result in higher flow rates. A free
phase liquid can also move laterally along the surface of sloping fine-grained strati-
graphic units. Higher density and lower viscosity fluids also permit higher flow rates.
Given that most chlorinated solvents are more dense than water and have viscosities
lower than water, in a given geologic medium with high free product saturation most
liquid chlorinated solvents migrate at rates comparable to or faster than water.
Most solvent movement occurs when it is connected or continuous. In such cases,
the free products in different pore openings form an immiscible phase continuum
through the various pore throats. Once the solvent release at the surface ceases, the
pressure forces driving the free phase liquid cease and the liquid in the pore openings
becoming disconnected. This liquid then becomes residual free product attached to the
soil particles as disconnected film or as wedges between soil particles. Once movement
of the chlorinated solvent ceases and the free product exists as residual saturation or
ganglia, high hydraulic gradients are required to remobilize the solvent.
1.5 IMPACT OF COSOLVENCY ON

TRANSPORT THROUGH SOIL
Cosolvency is another transport mechanism. Cosolvency (also referred to as

cosolvation) is the enhancement of an otherwise low mobility compound by its
preferential dissolution into an organic solvent. Examples include the remobilization
of a hydrophobic compound such as DDT or PCB by a release of gasoline or oil into
which DDT — 1,1¢-(dichloroethylidene)bis(4-chlorobenzene) — or PCBs (polychlo-
rinated biphenyls) preferentially dissolve into the fuel and are transported to depth
(Morrison and Newell, 1999).
Cosolvation occurs when a mobile phase is formed from multiple solvents that
are miscible (Kargbo, 1994). For soils, cosolvation is shown to increase the mobility
of a compound significantly only at high cosolvent concentrations, usually greater
than about 5% of the solution (Lane and Loehr, 1992; Nkedi-Kizza et al., 1987).
Cosolvation is described by the theoretical solvophobic model, which assumes
that sorption is the result of hydrophobic interactions (Rao et. al, 1985); the model
is log-linear. Deviations in the adsorption coefficient (Kd) from water due to mixed
solvents is estimated by the following equation (Nkedi-Kizza et al., 1985):
ln (Kdm) = ln (Kdw) – (cs cf c) (Eq. 1.3)
where
Kdm = the partition coefficient from mixed solvents.

Kdw = the partition coefficient from water.
c = an empirical constant.
sc = a number that, at a given concentration, is a function only of the solute and the
solvents.
fc = fraction of the cosolvent.

1.6 TRANSPORT OF VAPORS IN SOIL
Volatility is the tendency of a compound to be transported from the liquid to the

vapor phase. Given that most chlorinated solvents are volatile, a vapor phase is often
associated with a NAPL as it moves through the vadose zone. Vapor can partition
into moisture in the vadose zone, thereby creating dissolved phase contamination of
previously uncontaminated soil pore water and/or groundwater.
The primary mechanism for vapor transport in the vadose zone is vapor diffusion
(Thorstenson and Pollock, 1989). Generally, the more volatile the compound, the
greater its diffusion rate. Transport also occurs via advection due to pressure and/or
density gradients. Most chlorinated solvent vapors are denser than air, and large
density gradients may exist near a residual source of chlorinated solvents (i.e., the
vapor next to the free phase liquid may reach saturation). Density gradients can result
in vapor velocities of meters per day. In some cases, density-induced advection is as
significant as vapor diffusion.
The volatility of a chlorinated solvent is described by its vapor pressure and its
Henry’s Law constant. The greater the vapor pressure of a compound, the greater the
diffusion rate. Vapor pressures increase with temperature for pure phase or multi-
component liquids. Henry’s Law constant is used to define both the amount of the
compound in the vapor phase (assumes equilibrium) and the retardation of the
compound according to (Cohen et al. 1993):
Rd = (1 + nw) / [(naKH) + (rbKd)] / (naKH) (Eq. 1.4)
where
nw = water-filled porosity (dimensionless).

na = air-filled porosity (dimensionless).
KH = Henry’s Law constant (dimensionless).
rb = soil bulk density.
Kd = soil/liquid distribution coefficient.
The relative diffusive velocity of a chlorinated solvent in vapor can be estimated

with Equation 1.4. For 1,1,1-TCA, TCE, and methylene chloride using Henry’s Law
constants of 0.599, 0.379, and 0.084, respectively; a soil bulk density of 1.85 g/cm3;
and an air and water porosity of 0.5, the relative diffusive velocities from highest
to lowest are methylene chloride, 1,1,1-TCA, and TCE. Compounds with slower
diffusive velocities such as TCE and PCE (relative to TCA or methylene chloride)
are more useful in identifying soil source areas, while compounds with greater
affinities for the gas phase are more useful as indicators of groundwater contami-
nation.
In field studies of trichloroethylene vapor transport in sand, vapor velocities were
impacted by seasonal temperature variations. In some instances, vapors migrated
several meters within several days of a release (Conant et al., 1996). In another study,
TCE in a sandy soil emitted a vapor plume approximately 7 meters from the source

TABLE 1.15
Chemical Formula and Vapor Density of Selected
Vapor Density
Chlorinated Solvent Formula (g/L)
1,1,2,2-Tetrachloroethane C2H2Cl4 6.86

Tetrachloroethylene (PCE) CCl2CCl2 6.78
Carbon tetrachloride (CT) CCl4 6.29
Trichlorofluoromethane CCl3F 5.61
1,1,1-Trichloroethane (TCA) C2H3Cl3 5.45
1,1,2-Trichloroethane C2H3Cl3 5.45
Trichloroethylene (TCE) CHCl:CCl2 5.37
Dichlorofluoromethane (Freon-12) CCl2F2 4.94
Chloroforma CHCl3 4.88
1,1-Dichloroethane (1,1-DCA) C2H4Cl2 4.04
cis-1,2-Dichloroethylene CH2Cl2 3.96
trans-1,2-Dichloroethylene CH2Cl2 3.96
1,1-Dichloroethylene (1,1-DCE) C2H2Cl2 3.96
Dichloromethane (DCM)b CHCl2F 3.47
Vinyl chloride (VC) C2H3Cl 2.55
a Trichloromethane.
b Methylene chloride or Freon-30.
after 18 days (Hughes et al., 1992). A chlorinated solvent released from a degreaser
at an elevated temperature, for example, can result in a significant volume of the
solvent entering the vapor phase. For TCE, the vapor pressure is about double if the
temperature is at 25 vs. 15∞Celsius.
As vapors migrate through the soil, vapor partitioning into the aqueous and solid
phases occurs which retards the distance and rate of vapor migration from the
source. If the gas permeability of the soil allows the vapors to migrate vertically,
these vapors will eventually reach the capillary fringe, where they can diffuse into
the groundwater. Field studies have demonstrated that a solvent vapor source can
contribute to groundwater contamination (Cherry and Smyth, 1996; Mendoza and
Frind, 1990a,b,c). A rising water table can also provide the mechanism for these
vapors to diffuse into the groundwater (Weeks et al., 1982). The vapor densities of
selected chlorinated solvents are listed in Table 1.15 (Huling and Weaver, 1991;
Montgomery, 1992).
Chlorinated solvents can also volatilize from the water table into the overlying
vadose zone. The vaporization rate of a solvent from groundwater is a function of its
vapor pressure and chemistry. At the Picatinny Arsenal in Morris County, NJ, the
flux of TCE from the water table was estimated to be about 0.1 mg/sec (Martin and
Imbrigiotta, 1994).

TABLE 1.16
Saturated Vapor Concentration of Selected Vapors
Saturated Vapor Concentration
Compound (ppmv) (mg/L)
a
1,1,1-Trichloroethane (C2H3Cl3) 132,000 730
Trichloroethylene (CHCl:CCl2) 77,000 420
Perchloroethylene (CCl2CCl2) 19,000 130
Dichloromethaneb (CH2Cl2) 460,000 1600
a Methyl chloroform.
b Methylene chloride.
If a chlorinated solvent contains one compound, the equilibrium vapor concen-

tration is equal to the vapor pressure of the pure compound. If the liquid is a mixture,
Raoult’s Law can approximate it. Raoult’s Law is a relationship by which the
equilibrium vapor pressure of each constituent is approximated as described by the
following relationship:
c = Xt (P o/RT) (Eq. 1.5)
where
c = equilibrium vapor concentration of the constituent.

Xt = mole fraction of the compound in the source liquid.
Po = pure compound vapor pressure of a particular constituent.
R = universal gas constant.
T = temperature (degrees Kelvin).
The vapor pressure and concentration for TCE as a single compound and as a
component of a three-constituent mixture at 23∞C are 0.09 atm and 500 mg/L, and
0.25 atm and 138 mg/L, respectively.
The presence of chlorinated solvents at concentrations of several percent of their
saturated vapor pressure is indicative of the presence of a free phase liquid. The
saturated vapor pressure of several chlorinated solvents at 20∞C in parts per million
per volume (common soil gas units) and milligrams per liter are summarized in Table
1.16 (Feenstra, 1996). A soil gas concentration of 100 ppm by volume is commonly
considered to be indicative of the presence of free phase liquid.
1.7 TRANSPORT THROUGH

THE CAPILLARY FRINGE
The capillary fringe is the portion of the subsurface located immediately above the
groundwater table through which contaminants move to the underlying groundwater

or through which vapors from contaminated groundwater volatilize and migrate into
the vadose zone. The height of the capillary fringe is dependent on the soil texture;
finer grained materials have a higher capillary fringe than coarse-grained sediments.
A chlorinated solvent can enter the capillary fringe as a dissolved phase or as a
DNAPL or DNAPL/LNAPL mixture. In the case of a dissolved phase, the contami-
nated water enters the capillary fringe and co-mingles with the underlying ground-
water. For a DNAPL/NAPL mixture with a density less than water, vertical trans-
port ceases and the mixture spreads horizontally along the capillary fringe. The
DNAPL/NAPL usually accumulates as a mound on the groundwater surface and
then spreads radially. The center of mass, however, moves downgradient with
respect to the groundwater.
A dense non-aqueous phase liquid entering the capillary fringe must displace
water between the soil pores in order to continue its vertical migration into the
groundwater. The radii between the soil pores in the capillary fringe can cause
significant capillary pressures between the DNAPL and water which hinder further
vertical movement. A misconception concerning DNAPL transport through the
capillary fringe is that a DNAPL preferentially moves into the groundwater via the
capillary fringe as a function of the greater specific density of the DNAPL relative
to water. In many cases, this does occur, although the actual transport process is more
complex. DNAPL transport through the capillary fringe is dependent on several
factors, of which fluid density is only one. The height of a DNAPL required to
penetrate the capillary fringe is described by Hobson’s equation as follows (Ander-
son, 1988; Berg, 1975):
Zc = 2g cos q (1/rt – 1/rp) / Drg (Eq. 1.6)
where
Zc = critical height of the DNAPL required to penetrate the capillary fringe.

2g = interfacial tension between the DNAPL and water.
cos q = contact angle between the fluid boundary and the solid surface of the soil.
(1/rt – 1/rp) = radii of the throat and soil pore, respectively.
Dr = difference in specific densities between the water and chlorinated solvent.
g = acceleration due to gravity.
The practical application of this equation is that for soils with small pores such as silts
and clay, a significant barrier to DNAPL migration through the capillary fringe
exists. For a well-rounded and sorted sediment of diameter D with a rhombohedral
packing, the pore and throat radii, rp and rt, can be estimated from the following
relationships:
rp = 0.212D
rt = 0.077D
As an example, assume a porous soil in a rhombohedral packing and a pore radius

of 0.207D and throat radius of 0.077D, where D is the grain diameter. The critical

TABLE 1.17
Critical Height of PCE To Penetrate the Capillary Fringe
Porous Diameter (D) Critical Height of PCE (Zc)
Media (mm) (cm)
Coarse sand 1.0 13 (5 in)

Fine sand 0.1 130 (4 ft)
Silt 0.01 1300 (43 ft)
Clay 0.001 13,000 (427 ft)
Note: Values used in the calculation of Zc were 0.62 g/cm3, g = 47.5 dyne/cm,
and cos q = 1.
height of PCE necessary to overcome the capillary pressure for four different soil
types is shown in Table 1.17 (Anderson, 1988; Morrison and McGowan, 1993). This
approximation indicates that for a coarse sand, 13 cm (5 in) of DNAPL are required
to accumulate above the capillary fringe until enough pressure is created to allow the
PCE to move into the capillary fringe and underlying groundwater. A DNAPL can,
therefore, be immobilized and accumulate within fine-grained sediments at the
capillary fringe. A similar equation provides the entry pressure for a crack or fracture
in a capillary barrier or rock (Kueper and McWhorter, 1991). The difference is that
the pore/throat radius is replaced by the fracture aperture (Tuck et al., 1998).
A DNAPL residing within the capillary fringe can volatilize and migrate by
diffusion. Gaseous advection due to pressure or density gradients will affect this
transport process. As these vapors migrate, they can partition into the aqueous and
solid phases. These partitioning processes tend to retard the rate and distance of vapor
migration. The vapors may eventually contaminate the groundwater by diffusion
across the capillary fringe and water table at some distance from the DNAPL. Water
infiltrating through the soil and contacting these vapors can result in the dissolution
of the chlorinated solvent into the water which then enters the capillary fringe.
1.8 TRANSPORT IN GROUNDWATER
Chlorinated solvent transport in groundwater occurs as a dissolved or dense non-

aqueous phase liquid from which a dissolved phase “plume” originates. Once a
solubilized chlorinated solvent and water mixture enters groundwater, the same
advective (mass transport) dispersive and molecular diffusion processes used for
estimating groundwater movement apply. In most cases, molecular diffusion (the
transport of a chemical from a region of higher concentration to lower concentration)
is not a significant process. An exception is in the transport of solvents through
subsurface barrier systems; in these instances, transport is by molecular diffusion
(Crooks and Quigley, 1984).

1.8.1 DARCY’S LAW
Darcy’s Law describes groundwater velocity. This law is named after the French
engineer, Henry Darcy, who published a report in 1856 on the water supply for the
city of Dijon, France. In the report, Darcy described a laboratory experiment he
performed to analyze water flow through sand. Darcy concluded that the flow of a
liquid through porous medium is in the direction of, and at a rate proportional to, the
driving force acting on the liquid (the hydraulic gradient) and proportional to the
ability of the conducting medium to transmit the liquid. Naturally occurring hydrau-
lic gradients are typically on the order of 0.01; the units for hydraulic gradient are
dimensionless. Darcy’s Law as expressed in terms of hydraulic head is
Q = –KiA (Eq. 1.7)
where
Q = discharge.
–K = saturated hydraulic conductivity.
i = hydraulic gradient or slope.
A = cross-sectional area.
Environmental reports usually describe the horizontal and vertical velocity of a

contaminant in groundwater. Unlike the calculation of horizontal groundwater veloc-
ity, the vertical velocity is obtained by measuring the water levels in two monitoring
wells or piezometers whose well screens are completed at different depths to obtain
the vertical hydraulic gradient between the two wells. Soil porosity and saturated
hydraulic conductivity are two parameters in Darcy’s Law that are key in estimating
the average groundwater or contaminant velocity. These two input variables are
briefly discussed.
1.8.2 POROSITY (nE)

Porosity is an index (in percent) of the relative open space in a soil or a measure of
the air between soil particles. Porosity is used to calculate the transport of liquid or
vapor in the soil. It is usually expressed as the volume of pore space divided by the
bulk volume multiplied by 100. It can be calculated if the particle density and dry
bulk density of the soil are known.
Soil porosity values range from 30 to 60% of the total soil volume. Porosity is
measured directly in the field or laboratory. Laboratory methods include gas
pycnometry and mercury intrusion. Coarse-textured soils tend to be less porous than
fine-textured soil, although the mean size of individual pores is greater in the former
than the latter. Porosity values are highly variable in clayey soils due to the swelling
and shrinkage associated with changes in moisture content. The term “effective
porosity” is often used interchangeably with the term “porosity” to describe this

volume of interconnected pore space. The term “primary porosity” refers to the
original openings in the soil or rock created when it was formed in its present state,
while “secondary porosity” refers to features such as joints, faults, and openings
along planes of bedding in consolidated rocks having a low primary porosity.
Crystalline rocks such as granite have primary porosities ranging from 0 to 10%.
Typical secondary porosity values range from 0.001 to 1.0%.
Porosity is measured by laboratory drying experiments, laboratory drainage
experiments, in situ unconfined multiple-well pumping tests, in situ single-well
borehole-dilution test, in situ two-well tracer tests, and particle size analysis (Gorelick
et al., 1993). Soil porosity can be estimated if the mean particle diameter for the soil
is known. The mean particle diameter can be estimated from a grain size distribution
chart. The empirical relationship is
q = 0.261 – 0.0385 ln (d) (Eq. 1.8)
where d is the mean particle diameter (cm).
1.8.3 PERMEABILITY (k) AND

HYDRAULIC CONDUCTIVITY (K)
Permeability and hydraulic conductivity describe the ability of a soil to transmit a
fluid. The terms “permeability” (in older texts, coefficient of permeability) and
“hydraulic conductivity” are often used interchangeably; however, they are not the
same. Permeability refers to properties associated with the soil through which a fluid
is migrating. These properties include the distribution of the grain sizes, the spheric-
ity and roundness of the grains, and the nature of their packing. It is not a term that
includes properties of the groundwater flowing through the media.
The Water Resources Division of the U.S. Geological Survey defines hydraulic
conductivity as (Lohman et al., 1979):
A medium has a hydraulic conductivity of unit length per unit time if it will transmit
in unit time a unit volume of groundwater at the prevailing viscosity through a cross-
section of unit area, measured at right angles to the direction of flow, under a hydraulic
gradient of unit change in head through unit length of flow.
Hydraulic conductivity (K) is a constant of proportionality in Darcy’s Law and

is the building block for estimating contaminant transport in groundwater. Hydraulic
conductivity has units of length per time. Common conversions for hydraulic con-
ductivity are summarized in Table 1.18. When using the term “hydraulic conductiv-
ity”, the distinction between saturated hydraulic conductivity and unsaturated hy-
draulic conductivity should be made. Saturated hydraulic conductivity is the
proportionality constant used in Darcy’s Law for saturated flow. Unsaturated hydrau-
lic conductivity is used to express this constant for unsaturated flow (i.e., flow of
liquids in the unsaturated zone). The difference in saturated and unsaturated hydrau-
lic conductivity is that the value for unsaturated hydraulic conductivity varies with

TABLE 1.18
Unit Conversions for Hydraulic Conductivity
1 gal/day/ft2 = 0.0408 m/day = 0.134 ft/day = 4.72 ¥ 10–5 cm/sec
1 ft/day = 0.305 m/day = 7.48 gal/day/ft2 = 3.53 ¥ 10–4 cm/sec
1 cm/sec = 864 m/day = 2835 ft/day = 21,200 gal/day/ft2
1 m/day = 24.5 gal/day/ft2 = 3.28 ft/day = 0.00115 cm/sec
Adapted from Fetter (1994).
the degree of moisture saturation. A lower soil moisture content results in a smaller
unsaturated hydraulic conductivity value. Furthermore, the relationship between
unsaturated hydraulic conductivity and the degree of saturation is nonlinear and
exhibits hysteresis (i.e., non-repeating values).
Hydraulic conductivity is described by the following equation:
K = krwg/mw (Eq. 1.9)
where
k = intrinsic permeability (cm2).

rw = liquid density of water (1.0 g/cm3).
g = gravity constant (980.7 cm/sec2).
mw = dynamic viscosity of water (0.801 millipoiseuille [mPl] = 0.801 centipose [cP]).
and
k = K (mw/rwg) (Eq. 1.10)
For water at 20∞C, the expression (mw/rwg) is equal to 1.02 ¥ 10–5 cm/sec.
Intrinsic permeability is a function of the grain size distribution of the porous
medium and generally decreases from sands to loam to silt to clayey soils. Intrinsic
permeability is expressed in units of square centimeters (cm2) or Darcy (equal to
about 10–8 cm2). To convert cm2 to Darcy, multiply the cm2 value by 108. Intrinsic
permeability can range from about 10–15 to about 10–3 cm2.
Hydraulic conductivity values for saturated zone soils are obtained by direct
measurement from pumping well or slug tests. Hydraulic conductivity can be ap-
proximated if a soil grain distribution curve is available or from approximate func-
tional relationships. Unsaturated hydraulic conductivity values can be determined
with laboratory testing. If laboratory testing is performed for calculating the saturated
or unsaturated hydraulic conductivity value of a soil and the wetting fluid used is
water, recalculate the hydraulic conductivity value for estimating the hydraulic
conductivity value for the contaminant of interest through the same soil.
In the absence of site-specific measurements, hydraulic conductivity values can
be derived using approximate functional relationships based on the grain-size distri-
bution. One of the earliest equations was the Hazen formula (1893) which described

the saturated hydraulic conductivity (K) of a sample as K = Cd10 2 , where d
10 is the
tenth percentile of the grain-size distribution and C is a coefficient that accounts for
the nonuniformity in the grain-size distribution (Hazen, 1893; Pfleider and Moltyaner,
1993). Another relationship is the Kozeny-Carmen equation (Bear, 1979; Indelman
et al., 1999):
K = (rg/m)(q3/(1 – q)2)(d2/180) (Eq. 1.11)
where
K = saturated hydraulic conductivity (cm/sec).
r = water density (kg/m3).
g = acceleration due to gravity (m/sec2).
m = viscosity of water (Newtons/sec/m2).
q = porosity.
d2 = mean particle diameter (cm).
The California Department of Water Resources uses a standard estimate for saturated
hydraulic conductivity of soils based exclusively on grain size. Using this system,
gravel, sand, and sandy clay hydraulic conductivity values are estimated to be about
270, 135, and 10 feet, respectively, per day.
The rate of movement of a compound in groundwater is described by the term
“advection”, which is the average linear groundwater velocity and is the dominant
mechanism by which chemicals move in groundwater. It is described by Darcy’s
Law. The horizontal stratification of sediments results in hydraulic conductivities
that are usually greater in the horizontal direction than in the vertical direction. In
sediments such as glacial till, the preferential flow of contaminants can occur within
small lenses of materials that are more permeable than the majority of sediments in
the aquifer. Since Darcy’s Law is an averaged value for transport in a homogeneous
and isotropic media such as soil, contaminants are transported at greater rates within
these preferential layers than what is estimated with Darcy’s Law.
To estimate the average velocity of a particular contaminant, a variation of
Darcy’s Law is employed and is described by the following expression:
Vc = V/R (Eq. 1.12)
where
Vc = average velocity of a contaminant.
V = average groundwater velocity.
R = retardation coefficient.
1.8.4 RETARDATION
While Darcy’s Law applies to the average linear velocity for groundwater, it is
not contaminant specific. To examine the transport of an individual chemical,

retardation must be considered. In an ideal case, soluble compounds with higher
velocities are observed at the leading edge of a contaminant plume followed by
those soluble components with decreasing velocities. The separation of the
soluble components with distance from the source is explained by the retarda-
tion factor or retardation coefficient (R), which is the ratio of the concentration
of a compound on a solid to the concentration of that compound in solution.
Retardation values are strongly linked to the total organic carbon content of the
media. The retardation values for TCE in soil with organic carbon percentages of
0.01 to 0.02, 0.001 to 0.01, and <0.001 are 4 to 13, 1.3 to 7, and 1 to 1.3,
respectively (Olsen and Davis, 1990). Compounds that sorb strongly to organic
carbon in soils characteristically have low solubilities; compounds with low
tendencies to adsorb onto organic particles have high solubilities. Retardation is
described as:
R = 1 + (rb/q)Kd (Eq. 1.13)
where
rb = bulk density of the soil.

q = porosity (at low soil porosity values, retardation increases, while retardation
decreases as the soil porosity increases).
Kd = distribution coefficient.
The variable bulk density in the retardation equation is the weight of a soil per unit
volume. For most mineral soils, the bulk density ranges from about 1.0 to 1.54 Mg/
m3 (megagrams per cubic meter = grams per cubic centimeter). When the bulk
density is greater than about 1.65 Mg/m3, the soil is compacted; values less than 1.0
indicate a high level of organic matter (Conklin, 1996). For a sandy aquifer, values
for rb/q range from 4 to 6.
Distribution coefficient (Kd) values are obtained from the literature, calculated
from the measured organic carbon content in soil, or measured from laboratory batch
sorption or column transport studies. The most common technique measures the soil
organic content and obtains the soil/organic carbon partition coefficient (Koc) of the
chemical from published tables. Kd is then estimated by the following relationship:
Kd = (Koc)(foc) (Eq. 1.14)
where
Kd = distribution coefficient.
Koc = soil/organic carbon partition coefficient.
foc = organic carbon content of the soil.
Koc values for selected chlorinated solvents are listed in Table 1.19 (Mackay et al.,
1993; Ramamoorthy and Ramamoorthy, 1998).

TABLE 1.19
Soil/Organic Carbon Partition Coefficients for Selected
Soil/Organic Carbon Partition Coefficient
Chemical (mL/g)
Trichloroethylene (TCE) 126

Tetrachloroethylene (PCE) 364
1,2-Dibromomethane 92
cis-1,2-Dichloroethylene 86
trans-1,2-Dichloroethylene 59
1,1,1-Trichloroethane (TCA) 152
Chloroform (TCM) 44
1,2-Dichloropropane 51
Laboratory experiments indicate that values for retardation vary widely, depend-
ing on the chlorinated solvent and the soil. Given the uncertainties associated with
calculating R, a compound with a value of less than 2 is considered to be moving at
a rate similar to groundwater. Values for Kd vary over about 6 orders of magnitude,
while bulk density divided by porosity (rb/q) values vary by a factor less than 10.
Table 1.20 lists values of observed retardation coefficients for chlorinated solvents
and other compounds in various sand and gravel aquifers (MacKay, 1990; Olsen and
Davis, 1990). Predicted retardation values are generally two to five times lower than
measured values (Ball and Roberts, 1991; Curtis et al., 1986; MacKay et al., 1986;
Pankow and Cherry, 1996).
Spatial variations in the composition and ratios of the degradation products of
chlorinated solvents are frequently observed. The presence and distribution of the
breakdown products are explained as a function of the redox potential of the aquifer,
as well as the age of the release. A groundwater plume entering an area with low
dissolved oxygen or an anaerobic environmental can display a unique chemical
signature with more breakdown products than the aerobic portion of the groundwater
plume. An example is the release of TCE into an aerobic aquifer in which the only
breakdown product is cis-1,2-dichloroethylene. An anaerobic zone through which
the aquifer passes results in the accelerated degradation of the TCE and cis-1,2-
dichloroethylene to 1,1-dichloroethylene and vinyl chloride, resulting in a distinctive
chemical signature. This degradation sequence is used in the design of porous
reactive walls as a remediation technology (Benner et al., 1997; Tratnyek et al.,
1997).
The geometry of a chlorinated solvent plume is dependent on whether the release
is from a point or line source, the area of the release, and whether it is transient or
steady state. A line source tends to create a large cross-sectional area through which
the chlorinated hydrocarbons enter the groundwater. A point source usually creates
a tear-shaped plume with the apex of the tear at the point source.

TABLE 1.20
Retardation Values for Selected Chlorinated Solvents
Site Location/Aquifer Material Chlorinated Solvent Retardation Coefficient
Palo Alto, CA/sand and gravel Chloroform (CHCl3) 2.5–3.8

Bromoform (CHBr3) 6
1,1,1-Trichloroethane (C2H3Cl3) 12
Chlorobenzene (C6H5Cl) 33
R. Aare, Switzerland/sand and gravel Perchloroethylene (CCl2CCl2) 5
Gloucester, Ontario/sand and gravel 1,4-Dioxane (C4H8O2) 1.6
Tetrahydrofuran (C4H8O) 2.2
1,2-Dichlorobenzene (C6H4Cl2) 7.6
Carbon tetrachloride (CCl4) 23
Benzene (C6H6) 8.8
Borden, Ontario/sand and gravel Carbon tetrachloride (CCl4) 1.8–2.5
Perchloroethylene (CCl2CCl2) 2.7–5.9
Bromoform (CHBr3) 1.9–2.7
1,2-Dichlorobenzene (C6H4Cl2) 1.2–2.86
Otis Air Force Base, MA/
sand and gravel Trichloroethylene (CHCl:CCl2) 6–9
Perchloroethylene (CCl2CCl2) 1.0
Dichlorobenzene (C6H4Cl2) 1.0–1.1
Rocky Mountain Arsenal, CO/ Trichloroethylene (CHCl:CCl2) 1–2
sand and gravel
1,1,1-Trichloroethane (C2H3Cl3) 1–2
California site/sandy silt Trichloroethylene (CHCl:CCl2) 0.1–3.2
California site/fine sand Trichloroethylene (CHCl:CCl2) 0.01–0.7
California site/clay Trichloroethylene (CHCl:CCl2) 0.02
1.8.5 DISPERSIVITY
Dispersivity is the lateral spreading of a contaminant plume with distance in ground-
water. Dispersivity is three dimensional (i.e., horizontal, vertical, and transverse) and
is dependent on the aquifer characteristics and geometry of the contaminant source
area. In a homogeneous, isotropic porous media, dispersivity occurs due to the
following mechanisms:
• Velocity variations within the space between soil grains

• Variations in travel path lengths
• Variations in velocity directions
• Molecular diffusion
Dispersivity values are obtained by fitting mathematical models to plume data or dye
tracer tests performed in the field. Values for dispersivity increase with distance from
the source, although a relatively stable value (macrodispersivity) should be obtained

at some distance from the source. Dispersivity values are used in a longitudinal,
transverse, and vertical direction relative to the center of mass of a contaminant
plume.
Longitudinal dispersivity values used with solute transport models range from 90
to 300 feet, while horizontal dispersivity values can be as much as 150 feet. There
is little physical evidence for using such large numbers other than groundwater
models are able to simulate contaminant concentrations which compare favorably
with observed values in monitoring wells. In cases where no data exist, the U.S.
Environmental Protection Agency recommends multiplying the length of the plume
by 0.1 to estimate the horizontal dispersivity (Wilson et al., 1981). Other authors use
probabilistic theory to estimate transverse and vertical dispersivity as 0.33 and 0.056
times the plume length, respectively (Gelhar and Axness, 1981; Salhotra et al., 1993).
Field studies of dispersion for sand and gravel aquifers indicate that dispersion
is weak in these types of aquifers (Freyberg, 1986). Similar observations are noted
for aquifers where groundwater flow is relatively uniform with little divergence in
flow direction (Feenstra et al., 1996).
1.8.6 FREE PHASE SOLVENT TRANSPORT

IN GROUNDWATER
A dissolved phase can originate from a free phase solvent that exists as a LNAPL or
DNAPL in an aquifer. The rate at which the dissolved phase is created and the
concentration are estimated from the partition coefficient, solubility data, and infor-
mation on the chemical concentration of the chlorinated solvent (Dracos, 1987;
McKay et al., 1991; Ptacek et al., 1987).
The entry and distribution of a DNAPL into a granular media aquifer are affected
by the density of the DNAPL and the distribution of horizontal zones of lower
permeability materials. The difference in permeability between two zones does not
have to be significant to alter the flow pattern of the DNAPL. Differences between
a coarse sand to a finer sand, for example, may be sufficient to act as a barrier to
vertical migration (Kueper et al., 1989). The entry pressure required for a DNAPL
to penetrate a coarse and fine sand interface can be sufficient to cause the lateral
movement of the DNAPL to a point where the entry pressure is lower and allows the
DNAPL to resume its vertical migration.
The randomness of DNAPL distribution in groundwater is due in part to varia-
tions in soil texture which change the entry pressure of a DNAPL. The accumulation
of dense non-aqueous phase liquids in the saturated zone is considered to be greater
than in the vadose zone (Schwill, 1988). For saturated soils, residual DNAPLs can
occupy 2 to 15% of the total pore space. In the case where a DNAPL pool accumu-
lates, the DNAPL can occupy 40 to 70% of the bulk pore space. The hydraulic
conductivity in these areas is significantly reduced by the presence of the DNAPL.
Whether a dense non-aqueous phase liquid is dispersed in the saturated zone as
ganglia or as a pool has a significant impact on the volume of groundwater needed
to “flush” the DNAPL until completed dissolution is achieved. If the dense non-

aqueous phase liquid is dispersed in pools, the low permeability in the pool limits the
groundwater flux through this zone. The time for remediation based on extraction of
the dissolved phase contamination formed from the DNAPL pool is therefore in-
creased.
A multi-component DNAPL pool will exhibit the preferential dissolution of the
more soluble components followed by those with smaller solubilities. A halo of
chlorinated solvents leaving such a DNAPL pool will often exhibit changes in the
detection and concentration of the individual solvents dissolving from the multi-
component DNAPL pool.
The depth of DNAPL penetration in the saturated zone is dependent on the
volume of DNAPL entering the aquifer and the various entry pressures created by
changes in soil texture. At some point, these forces balance one another and vertical
movement ceases. At sites with numerous layers and low-permeability zones, there
is no means by which to predict the depth of DNAPL penetration. In such environ-
ments, DNAPL pools are more likely to accumulate at the interfaces of these soil
layers, thereby providing an indication of where to sample to locate these DNAPL
pools.
For a DNAPL in groundwater, a dissolved plume is formed via contact by
groundwater with the free phase liquid. The extent and geometry of the dissolved
phase plume is dependent on the geometry of the DNAPL ganglia or pool. The
composition of the dissolved phase plume is similarly dependent on the solubility and
chemistry of the solvent. The ability to identify the distribution of a DNAPL will
continue to be a daunting challenge, even at field-scale research sites (Broholm et al.,
1999).
1.8.7 TRANSPORT IN FRACTURES

Fractured media exist as fractured bedrock, in sandstone aquifers, clay layers, and in
unconsolidated materials. DNAPLs entering these fractures will displace water.
Given that the capillary entry pressure into most fractures is low (on the order of
several centimeters of head), a DNAPL can flow into the fracture system until the
fracture becomes saturated or the dense non-aqueous phase liquid is disconnected
within the fracture system. The ability to be transported throughout a fracture system
is primarily a function of the intersection and continuity of the fractures (De Marsily,
1985).
Fracture aperture is a key parameter in determining the flow and transport
characteristics of DNAPL in fractured media. Typically, fracture apertures are within
1 to 200 mm in width. Free phase solvents have the ability to enter fractures in these
materials because of their high density, low water/solvent interfacial tension, and low
viscosity. In natural fractures, there is usually a large distribution of fracture aper-
tures even within a single fracture. The fracture aperture distribution is controlled by
a number of factors, including the flaws and inclusions in the material and the history
of mechanical, thermal, and chemical stresses on the soil or rock (Atkinson, 1989).
In general, fracture density and apertures decrease with increasing depth. The ability

to estimate the fracture aperture distribution is extremely unpredictable. Direct
methods of detecting and measuring apertures include video imaging inside a well
(Darilek, 1986; Palmer and Sparks, 1991) and geophysical techniques. Geophysical
techniques include seismic reflection, electrical methods relying on the fact that
water-filled fractures have a higher conductivity than unfractured rock and can
mobilize ions in solution, and ground-penetrating radar. Indirect techniques for
measuring the fracture aperture distribution include pumping and tracer injection
tests. These are currently the most accurate means of assessing fracture apertures in
the field.
When a dense non-aqueous phase liquid enters a fracture, the pattern of DNAPL
distribution within the fracture becomes non-uniform. Portions of the fracture
system can be completely free of a dense non-aqueous phase liquid. A conceptual
model should not assume that a DNAPL is uniformly distributed within a fracture
network.
Solvent transport through fractures and their distribution are a function of the
orientation and connection of the fractures. Given that the sizes of the fracture or
apertures vary, DNAPLs can accumulate in horizontal areas of larger openings as
pools which then can become disconnected from other DNAPLs in the smaller sized
fractures. The length of a stable DNAPL pool in a single fracture following a
chlorinated solvent release is a function of the following variables (Kueper et al.,
1992):
• Size of the fracture aperture

• Fracture dip
• Interfacial tension between the DNAPL and fracture wall
• Contact angle of the DNAPL with the surface of the fracture wall
The probability that a dense non-aqueous phase liquid will accumulate in a vertical
fracture is small, given the high capillary pressures that exist in vertical fractures.
Fractured bedrock typically exhibits permeable zones separated vertically by less
permeable zones in which vertical fractures are less frequent. In materials such as
granite, the fracture pattern is usually less ordered and many of the fractures termi-
nate without intersecting other fractures. These fractures then become reservoirs for
DNAPL pools that can serve as long-term (on the order of decades to centuries)
sources of groundwater contamination (Dawson et al., 1997).
Equations describing the entry of a DNAPL into a fracture often reference
whether the DNAPL or water is the wetting or non-wetting phase (Vold and Vold,
1983). These terms refer to the phenomenon by which, in the presence of a solid
surface, one fluid preferentially “wets” the surface. In most cases, water is the
assumed wetting fluid (Kueper et al., 1992).
In order for a fluid to enter an aperture, the capillary pressure at the entrance to
the fracture must exceed the entry pressure of the fracture. The entry pressure of a
fracture is a function of the geometry of the opening that is exposed to the DNAPL.
Once the entry pressure to the opening is exceeded, the DNAPL can flow into the
opening. The entry pressure that is required decreases with increasing aperture

diameter. The maximum depth that a DNAPL achieves in a fractured media is a
function of the
• Aperture size
• Number and type of fracture connections
• Physical properties of the DNAPL
• Height of the column of continuous DNAPL above the fractures at the front of the
DNAPL zone
In some instances, DNAPLs in fracture rock environments have penetrated depths of

hundreds of feet. In some cases, the depths are likely to be greater than 3000 feet
(Pankow and Cherry, 1996).
Current research is inconclusive as to whether or not DNAPL pooling on a clayey
strata results in the desiccation of the clay mineral and the resultant development of
vertical pathways for the DNAPL to travel through the clay. To date, the literature
suggests that this scenario is unlikely.
1.8.8 TRANSPORT IN FRACTURED POROUS MEDIA

The transport of dense non-aqueous phase liquids in fractured porous media, such as
a fractured clay till or sedimentary rock, has been extensively studied (Ge, 1997;
Hinsby et al., 1996). A current conceptual model is that as a DNAPL migrates
through a fracture system, it is unaffected by diffusion, as the penetration is con-
trolled primarily by fracture aperture and DNAPL properties (density, interfacial
tension, and viscosity). Recent modeling indicates that for rough-walled fractures,
the upward flow of groundwater can prevent the downward migration if a sufficient
hydraulic gradient is present (Chown et al., 1997). Once the DNAPL is immobilized,
contaminant diffusion into the porous matrix will commence.
A distinction with DNAPL transport through fractured porous media is that a
portion of the dense non-aqueous phase liquid and dissolved phase plume sorbs and
dissolves into the porous media surrounding the fracture. The contaminant mass that
has diffused into the solid matrix can diffuse back into water in the fracture, thereby
resulting in a long-term source of contamination. In a study of free phase TCE in a
fractured shale, it was estimated that the potential existed for 67% of the original
DNAPL mass to have disappeared through matrix diffusion. This was estimated
based on the 10-year period that the DNAPL could have been in contact with the
porous bedrock (Frappa et al., 1996).
Research indicates that the total mass of a dense non-aqueous phase liquid
present in a fractured system is (Freeze and McWhorter, 1997):
• Distributed in DNAPL in fractures

• Distributed in dissolved phase contamination in the water in the fractures
• Dissolved in the water in the porous bedrock or soil
• Sorbed on the solid material within the bedrock or soil

In general, the loss of dense non-aqueous phase liquids by diffusion into the
porous media is a function of the size of the aperture that the DNAPL occupies. The
diffusion of a DNAPL into porous media in a small fracture results in the DNAPL
disappearing within the aperture most rapidly. As the size of the aperture increases,
the time for DNAPL disappearance within the fracture increases, assuming that the
DNAPL is disconnected from an overlying DNAPL pool.
The significance of DNAPL entry into a fractured subsurface environment is as
follows:
• The ability to intercept DNAPL fractures with a conventional boring program is

low.
• Pumping of liquid from below a DNAPL pool can result in the transport of the
DNAPL to greater depths.
• Matrix diffusion into porous material from a DNAPL-saturated aperture can result
in a dissolved phase source for a significant period of time.
• The transport and distribution of a DNAPL in a fracture system can occur rapidly
compared to a granular aquifer.
• The larger the volume of DNAPL released and the wider the fracture spacing, the
greater the opportunity for DNAPL pools to develop and for the DNAPL to move
a significant distance from the source.
• The introduction of drilling fluids into a DNAPL-contaminated fractured system
can result in pushing the DNAPL away from the borehole.
• Drilling through a DNAPL pool can lead to borehole cross-contamination.
Given these issues, remediation of DNAPL contamination in a fracture system

presents tremendous technical challenges.
REFERENCES
Alexander, M., 1985. Biodegradation of organic chemicals, Environmental Science and Tech-
nology, 18:106–111.
American Society for Testing and Materials (ASTM), 1989. Manual on Vapor Degreasing,
3rd ed., ASTM, Philadelphia, PA.
Anderson, M., 1988. The Dissolution and Transport of Dense Non-Aqueous Phase Liquids in
Saturated Porous Media, Ph.D. thesis in Environmental Science and Engineering, Oregon
Graduate Center, University of Oregon at Portland, p. 260.
Ball W. and P. Roberts, 1991. Long-term sorption of halogenated organic chemicals by aquifer
material. 1. Equilibrium, Environmental Science and Technology, 24:1223–1236.
Bear, J., 1979. Hydraulics of Groundwater, McGraw-Hill, New York, p. 210.
Benner, S., Blowes, D., and C. Ptacek, 1997. A full-scale porous reactive wall for prevention
of acid mine drainage, Groundwater Monitoring Review, Fall:99–108.
Berg, R., 1975. Capillary pressures in stratigraphic traps, Bulletin of the American Association
of Petroleum Geologists, 59(6):935–956.
Bradley, P. and F. Chapelle, 1999. Methane as a product of chloroethene biodegradation under
methanogenic conditions, Environmental Science and Technology, 33(4):653–656.

Broholm, K., Feenstra, S., and J. Cherry, 1999. Solvent release into a sandy aquifer. 1.
Overview of source distribution and dissolution behavior, Environmental Science and
Technology, 33(5):681–690.
Butler, E. and K. Hayes, 1999. Kinetics of the transformation of trichloroethylene and
tetrachloroethylene by iron sulfide, Environmental Science and Technology, 33(12),
2021–2027.
California Department of Health Services, 1988. The Reduction of Solvent Wastes in the
Electronics Industry, Final Report, Waste Reduction Grant Program, Grant No. 86-
T0110, California Toxic Substances Control Division, Alternative Technology and Policy
Development Section, Sacramento, CA, p. 85.
California Department of Toxic Substance Control (DTSC), 1991. Source Reduction of
Chlorinated Solvents: Electronic Products Manufacture, Source Reduction Research
Partnership, Metropolitan Water District of Southern California and the Environmental
Defense Fund, 119 Electronic Electrical (ID#7229), Sacramento, CA, June, p. 32.
Cherry, J. and D. Smyth, 1996. Non-Aqueous Phase Liquids in the Subsurface Environment:
Assessment and Remediation, 1996 Annual Convention and Exposition, November 10–
14, American Society of Civil Engineers, Washington, D.C., p. 22.
Chiou, C., 1989. Theoretical considerations of the partition uptake of nonionic organic
compounds by soil organic matter, in Sawhney, B.L. and K. Brown, (Eds.), Reactions and
Movement of Organic Chemicals in Soils, Soil Science Society of America Special
Publication No. 22, Soil Science Society of America, Madison, WI, pp. 1–19.
Chown, J., Kueper D., and D. McWhorter, 1997. The use of upward hydraulic gradients to
arrest downward DNAPL migration in rock fractures, Ground Water, 35(3):483–491.
Cohen, R., Mercer, J., and J. Matthews, 1993. DNAPL Site Evaluation, CRC Press, Boca
Raton, FL, p. 48 (contract to Dynamic Corporation by EPA under Contact No. 68-C8-
0058).
Conant B., Gillham, R., and C. Mendoza, 1996. Vapor transport of trichloroethylene in the
unsaturated zone: field and numerical modeling investigations, Water Resources Re-
search, 32(1):9–22.
Conklin, R., 1996. Bully for the sand’s physique, Soil and Groundwater Cleanup, Novem-
ber:31–33.
Crooks, V. and R. Quigley, 1984. Saline leachate migration through clay: a comparative
laboratory and field investigation, Canadian Geotechnical Journal, 21:349–362.
Curtis, G., Roberts P., and M. Reinhard, 1986. A natural gradient experiment on solute
transport in a sand aquifer. 4. Sorption of organic solutes and its influence on mobility,
Water Resources Research, 22:2059–2067.
Dawson, H. and P. Roberts, 1997. Influence of viscous, gravitational, and capillary forces on
DNAPL saturation, Ground Water, 35(2):261–269.
De Marsily, G., 1985. Flow and transport in fractured rocks: connectivity and scale effect, in
Hydrology of Rocks of Low Permeability, Memoirs, Vol. XVII, Parts 1 and 2, Interna-
tional Association of Hydrogeologists (IAH), Tucson, AZ, pp. 267–277.
Dilling, W., Tefertiller, N., and G. Kallos, 1975. Evaporation rates and reactivities of meth-
ylene chloride, chloroform, 1,1,1-trichloroethane, trichloroethylene, tetrachloroethylene,
and other chlorinated compounds in dilute aqueous solutions, Environmental Science and
Technology, 9:833–838.
Dracos, T., 1987. Immiscible transport of hydrocarbons infiltrating in unconfined aquifers, in
Vandermeulen, J.H. and S. Hrudey (Eds.), Oil in Freshwater: Chemistry, Biology,
Countermeasure Technology, Pergamon Press, New York, pp. 161–175.

Dragun, J., 1988. The Soil Chemistry of Hazardous Materials, Hazardous Materials Control
Research Institute, Silver Springs, MD, p. 458.
European Chlorinated Solvent Association (ECSA), 1998. European solvent sales in 1997,
Solvents Digest, 17:8.
European Chlorinated Solvent Association (ECSA), 1997. Methylene chloride: an update on
human and environmental effects, Solvents Digest, March:12.
European Chlorinated Solvent Association (ECSA), 1996. Chlorinated solvents in Europe,
Solvents Digest, 9.
Fetter, C., 1994. Contaminant Hydrogeology, 3rd ed., Macmillan, New York, p. 458.
Frappa, R., McManus, M., and B. Parker, 1996. The Use of Non-Conventional Investigative
Methods in the Development of a Conceptual Site Model, paper presented at the 28th Mid-
Atlantic Industrial and Hazardous Waste Conference, July 14–17, Buffalo, NY, p. 8.
Feenstra, S., 1996. Characterization of source zones and plumes: selected topics, in DNAPL
Site Characterization and Remediation, University Consortium Solvents in Groundwater
Research Program, November 18–12, San Francisco, CA.
Feenstra, A. and J. Cherry, 1988. Subsurface contamination by dense non-aqueous phase
liquid (DNAPL) chemicals, in Proceedings of the International Groundwater Sympo-
sium, May 1–4, International Association of Hydrogeologists, Halifax, Nova Scotia, pp.
62–69.
Feenstra, S., Cherry, J., and B. Parker, 1996. Conceptual models for the behavior of dense non-
aqueous phase liquids (DNAPLs) in the subsurface, in Pankow, J. and J. Cherry (Eds.),
Dense Chlorinated Solvents and other DNAPLs in Groundwater, Waterloo Press, Guelph,
Ontario, pp. 53–128.
Freeze, A. and D. McWhorter, 1997. A framework for assessing risk reduction due to DNAPL
mass removal from low-permeability soils, Ground Water, January-February:111–123.
Freyberg, D., 1986. A natural gradient experiment on solute transport in a sand aquifer. 1.
Spatial moments and the advection and dispersion of nonreactive tracers, Water Re-
sources Research, 22(13):2031–2046.
Gao, J., Skeen, R., and B. Hooker, 1995. Effect of temperature on perchloroethylene dechlo-
rination by a methanogenic consortium, in Hinchee, R., Leeson, A., and L. Semprini
(Eds.), Bioremediation of Chlorinated Solvents, Battelle Press, Columbus, OH, pp. 53–
59.
Ge, S., 1997. A governing equation for fluid flow in rough fractures, Water Resources
Research, 33(1), pp. 53–61.
Gelhar, L. and C. Axness, 1981. Stochastic Analysis of Macro-Dispersion in Three Dimension-
ally Heterogeneous Aquifers, Report No. H-8, Hydraulic Research Program, New Mexico
Institute of Mining and Technology, Soccorro, p. 140.
Gorelick, S., Freeze, R., Donohue, D., and J. Keely, 1993. Groundwater Contamination:
Optimal Capture and Containment, Lewis Publishers, Boca Raton, FL, p. 385.
Halogenated Solvents Industry Alliance (HSIA), 1998a. Facts about PERC Drycleaning,
HSIA, Washington, D.C., p. 3.
Halogenated Solvents Industry Alliance (HSIA), 1998b. Methylene chloride, White Paper,
June:12.
Halogenated Solvents Industry Alliance (HSIA), 1996. Trichloroethylene, White Paper, June:8.
Halogenated Solvents Industry Alliance (HSIA), 1994. Perchloroethylene, White Paper, Feb-
ruary:7.
Hardie, D., 1964. Chlorocarbons and chlorohydrocarbons: trichloroethylene, in Kirk, R. and
D. Othmer (Eds.), Encyclopedia of Chemical Technology, 2nd ed., Vol. 5, John Wiley &
Sons, New York, pp. 183–195.

Hazen, A., 1893. Some Physical Properties of Sands and Gravels with Special Reference to
their Use in Infiltration, Annual Report of the Massachusetts Board of Public Health, pp.
541–556.
Hinsby, K., McKay, L., Jorgensen, P., Lenczewski, M., and C. Gerba, 1996. Fracture aperture
measurements and migration of solutes, viruses, and immiscible creosote in a column of
clay rich till, Ground Water, 34(6):1065–1075.
Hughes, B., Gillham, R., and C. Mendoza, 1992. Transport of trichloroethylene vapors in the
unsaturated zone: a field experiment, in Proceedings of the Conference on Subsurface
Contamination by Immiscible Liquids, International Association of Hydrogeologists,
Calgary, Alberta, Balkema, Rotterdam, pp. 81–88.
Huling, S. and J. Weaver, 1991. Dense Nonaqueous Phase Liquids, EPA/540/4-91-002, U.S.
Environmental Protection Agency, Office of Solid Waste and Emergency Response,
Washington, D.C., p. 21.
Indelman, P., Moltyaner, G., and G. Dagan, 1999. Determining the hydraulic conductivity spatial
structure at the Twin Lake site by grain size distribution, Ground Water, 37(2):223–227.
IRTA (Institute for Research and Technical Assistance), 1994. U.S. chlorinated solvent use in
1988 (thousand metric tons) in chlorinated solvents: an overview of their production, use,
and release, in Proving the Technical Case: Soil and Groundwater Contamination
Litigation with Emphasis on Chlorinated Solvent Contamination, November 9–19, San
Jose, CA, Department of Engineering and Professional Development, College of Engi-
neering, University of Wisconsin, Madison, p. 1.
Izzo, V., 1992. Dry Cleaners – A Major Source of PCE in Ground Water, State of California
Central Valley California Regional Water Quality Control Board, Well Investigation
Program, Fresno, CA, p. 23.
Kamrin, M., 1997. Pesticide Profiles: Toxicity, Environmental Impact and Fate, Lewis Pub-
lishers, Boca Raton, FL, p. 676.
Kargbo, D., 1994. Chemical contaminant reactions and assessment of soil cleanup levels for
protection of groundwater, Environmental Geology, 23:105–113.
Karickhoff, S., 1981. Semi-empirical estimation of sorption of hydrophobic pollutants on
natural water sediments, Water Research, 134:241–248.
Kueper, B., Abbot, W., and G. Farquhar, 1989. Experimental observations of multiphase flow
in heterogeneous porous media, Journal of Contaminant Hydrology, 5:83–95.
Kueper, B., Haase, C., and H. King, 1992. Leakage of dense, nonaqueous phase liquids from
waste impoundments constructed in fractured rock and clay: theory and case history,
Canadian Geotechnical Journal, 2:234–244.
Kueper, B. and D. McWhorter, 1991. The behavior of dense, non-aqueous phase liquids in
fractured clay and rock, Ground Water, 29(5):716–728.
Lane, W. and R. Loehr, 1992. Estimating the equilibrium aqueous concentrations of poly-
nuclear aromatic hydrocarbons in complex mixtures, Environmental Science and Tech-
nology, 26(5):983–990.
Lizette, R., Masten, S., Wallace, R., and D. Wiggert, 1997. Experimental investigation of
surfactant-enhanced dissolution of residual NAPL in saturated soil, Ground Water Moni-
toring Review, Fall:89–98.
Lohman, S., Bennett, R., Brown, R., Cooper, H., Drescher, W., Ferris, J., Johnson, A.,
McGuinness, C., Piper, A., Rorabaugh, M., Stallman, R., and C. Theis, 1972. Definitions
of Selected Ground-Water Terms-Revisions and Conceptual Refinements, Water Supply
Paper, U.S. Geology Survey, U.S. Government Printing Office, Washington, D.C., p. 14.
Mabey, W. and T. Mill, 1978. Critical review of hydrolysis of organic compounds in water under
environmental conditions, Journal of Physical and Chemical Reference Data, 7:383–415.

MacKay, D., 1990. Characterization of the distribution and behavior of contaminants in the
subsurface, in Ground Water and Soil Contamination Remediation: Toward Compat-
ible Science, Policy and Public Perception, report on a colloquium sponsored by the
Water Science and Technology Board, National Academy Press, Washington, D.C., pp.
70–90.
MacKay, D., Shiu, W., and K. Ma, 1993. Illustrated Handbook of Physical-Chemical Prop-
erties and Environmental Fate for Organic Chemicals. Vol. III. Volatile Organic Chemi-
cals, Lewis Publishers, Chelsea, MI, p. 916.
MacKay, D., Shiu, W., Maijanen, A., and S. Feenstra, 1991. Dissolution of non-aqueous phase
liquids in groundwater, Journal of Contaminant Hydrology, 8:23–42.
MacKay, D., Freyberg, D., Roberts, P., and J. Cherry, 1986. A natural gradient experiment on
solute transport in a sand aquifer. 1. Approach and overview of plume movement, Water
Resources Research, 22:2017–2029.
Martin, M. and T. Imbrigiotta, 1994. Contamination of groundwater with trichloroethylene at
the Building 24 site at Picatinny Arsenal, New Jersey, in Symposium on Natural Attenu-
ation of Ground Water, Aug. 30–Sept. 1, EPA/600/R-94/162, Office of Research and
Development, U.S. Environmental Protection Agency, Denver, CO, pp. 109–115.
McCarty, P., 1994. An overview of anaerobic transformation of chlorinated solvents, in
Symposium on Natural Attenuation of Ground Water, Aug. 30–Sept. 1, EPA/600/R-94/
162, Office of Research and Development, U.S. Environmental Protection Agency,
Denver CO, pp. 104–108.
McCarty, P., 1993. In situ bioremediation of chlorinated solvents, Biotechnology, 4:323–330.
Mendoza, C. and E. Frind, 1990a. Advective-dispersive transport of dense organic vapors in
the unsaturated zone. 1. Model development, Water Resources Research, 26:379–387.
Mendoza, C. and E. Frind, 1990b. Advective-dispersive transport of dense organic vapors in
the unsaturated zone. 2. Sensitivity analysis, Water Resources Research, 26:388–398.
Mendoza, C. and Frind, 1990c. Modeling of ground-water contamination caused by organic
solvent vapors, Ground Water, 28(2):199–206.
Montgomery, J., 1992. Groundwater Chemicals Field Guide, Lewis Publishers, Chelsea, MI,
p. 271.
Morrison, R. and E. McGowan, 1993. Hydrocarbon transport in soils, National Environmental
Journal, 3(5):52–56.
Morrison, R. and E. Newell, 1999. The cosolvation transport of DDT and toxaphene in xylene
at a pesticide formulation facility, Journal of Soil Contamination, 8(1):63–80.
Newell, C. and R. Ross, 1991. Estimating Potential Occurrence of DNAPL at Superfund Sites,
Quick Reference Guide Sheet, Publ. No. 9355.4-07FS, U.S. Environmental Protection
Agency, Washington, D.C., p. 3.
Ney, R., 1995. Fate and Transport of Organic Chemicals in the Environment. A Practical
Guide, 2nd ed., Government Institutes, Rockford, MD, p. 302.
Nkedi-Kizza, P., Rao, S., and A. Hornsby, 1987. Influence of organic cosolvents on leaching
of hydrophobic organic chemicals in soils, Environmental. Science and. Technology,
21:1107–1111.
Nkedi-Kizza, P., Rao, P., and A. Hornsby, 1985. Influence of organic cosolvents on sorption
of hydrophobic organic chemicals by soils, Environmental. Science and Technology,
19(10):975–979.
Odencrantz, J., Farr, J., and C. Robinson, 1992. Transport model parameter sensitivity for soil
clean-up level determinations using SESOIL and AT123D in the context of the California
leaking underground fuel tank field manual, Journal of Soil Contamination, 1(2):159–
182.

Olson, R. and A. Davis, 1990. Predicting the fate and transport of organic compounds in
groundwater, Hazardous Material Control, 3(3):39–64.
Palmer, I. and D. Sparks, 1991. Measurement of induced fractures by downhole TV camera
in Black Warrior Basin Coalbeds, Journal of Petroleum Technology, 43(3):270.
Pankow, J. and J. Cherry, 1996. Dense Chlorinated Solvents and other DNAPLs in Ground-
water, Waterloo Press, Guelph, Ontario, p. 522.
Parker, B., Gillham, R., and J. Cherry, 1994. Diffusive disappearance of dense, immiscible
phase organic liquids in fractured geologic media, Groundwater, 32(5):805–820.
Pfleiderer, S. and G. Moltyaner, 1993. The use of velocity and conductivity data for the
quantification of heterogeneity: a comparison, Water Resources Research, 29(12):4151–
4156.
Phelps, T., Ringelberg, D., Hedrick, D., Davis, J., Fliermans, C., and D. White, 1988.
Microbial biomass and activities with subsurface environments contamined with chlori-
nated hydrocarbons, Geomicrobiology Journal, 6, 157–170.
Ptacek, C., Cherry, J., and R. Gillham, 1987. Mobility of dissolved petroleum-derived hydro-
carbons in sand aquifers, in Vandermeulen, J.H. and S. Hrudey (Eds.), Oil in Freshwater:
Chemistry, Biology, Countermeasure Technology, Pergamon Press, New York, pp. 195–
216.
Ramamoorthy, S. and S. Ramamoorthy, 1998. Chlorinated Organic Compounds in the Envi-
ronment: Regulatory and Monitoring Assessment, Lewis Publishers, Boca Raton, FL, p.
370.
Rao, P., Hornsby, A., Kilcrase, D., and P. Nkedi-Kizza, 1985. Sorption and transport of
hydrophobic organic chemicals in aqueous and mixed solvent systems: model develop-
ment and preliminary evaluation, Journal of Environmental Quality, 14(3):376–383.
Salhotra, A., Mineart, P., Hansen, S., and T. Allison, 1993. Multimed, the Multimedia Expo-
sure Assessment Model for Evaluating the Land Disposal of Wastes — Model Theory,
EPA 600/R-93/081, U.S. Environmental Protection Agency, Washington, D.C., p. 122.
Schwill, F., 1988. Dense Chlorinated Solvents in Porous and Fractured Media-Model Experi-
ments (J. Pankow, trans.), Lewis Publishers, Boca Raton, FL, p. 146.
Siegrist, R., 1993. VOC measurement in soils: the nature and validity of the process, in
National Symposium on Measuring and Interpreting VOCs in Soils: State of the Art
Research Needs, January 12–14, Las Vegas, NV, p. 10.
Thorstenson, D. and D. Pollock, 1989. Gas transport in unsaturated porous media: the ad-
equacy of Fick’s Law, Review of Geophysics, 27:61–78.
Tratnyek, P., Johnson, T., Scherer, M., and G. Eykholt, 1997. Remediating ground water with
zero-valent metals: chemical considerations in barrier design, Groundwater Monitoring
Review, Fall:108–114.
Tsien, H., Brusseau, G., Hanson, R., and L. Wackett, 1989. Biodegradation of trichloroethyl-
ene by methylosinus trichosporium OB3b, Applied Environmental Microbiology,
55(12):3155–3161.
Tuck, D., Iversen, G., Pirkle, W., and C. Rulison, 1998. Time-dependent interfacial property
effects on DNAPL flow and distribution, in Wickramanayake, G. and R. Hinchee (Eds.),
Nonaqueous Phase Liquids: Remediation of Chlorinated and Recalcitrant Compounds,
Battelle Press, Columbus, OH, pp. 73–78.
U.S. Department of Commerce, 1977. United States Exports, Schedule B Commodity Group-
ings, Schedule B Commodity by Country, FT 410/Dec., U.S. Government Printing Office,
Washington, D.C., pp. 2–85.
U.S. EPA, 1996. Region 9 Preliminary Remediation Goals (PRGs) for 1996, U.S. Environ-
mental Protection Agency, U.S. Government Printing Office, Washington, D.C., p. 22.

U.S. EPA 1993. Evaluation of the Likelihood of DNAPL Presence at NPL Site, EPA/540/R-
93/073, Office of Emergency and Remedial Response, Hazardous Site Control Division,
U.S. Environmental Protection Agency, Washington, D.C., p. 15.
U.S. EPA, 1992. Estimating Potential for Occurrence of DNAPL at Superfund Sites, Publ. No.
9355.4-07FS, Office of Solid Waste and Emergency Response, U.S. Environmental
Protection Agency, U.S. Government Printing Office, Washington, D.C., pp. 9.
U.S. Tariff Commission, 1947. Synthetic Organic Chemicals: United States Production and
Sales, 1946, Rep. No. 159, Second Series, U.S. Government Printing Office, Washington,
D.C., p. 141.
Vogel, T. and P. McCarty, 1987. Abiotic and biotic transformations of 1,1,1-trichloroethane
under methanogenic conditions, Environmental Science and Technology, 21:1208–1213.
Vogel, T., Criddle, C., and P. McCarty, 1987. Transformation of halogenated aliphatic
compounds, Environmental Science and Technology, 21(8):722–736.
Vold, R. and M. Vold, 1983. Colloid and Interface Chemistry, Addison-Wesley, Reading,
MA, p. 694.
Weeks, E., Earp, D., and G. Thompson, 1982. Use of atmospheric fluorocarbons F-11 and F-
12 to determine the diffusion parameters of the unsaturated zone in the southern high
plains of Texas, Water Resources Research, 18:1365–1378.
Wilson, B., Wilson, J., Kampbell, D., Bledsoe, B., and J. Armstrong, 1994. Traverse City:
geochemistry and intrinsic bioremediation of BTX compounds, in Symposium on Natural
Attenuation of Ground Water, EPA/600/R-94/162, U.S. Environmental Protection Agency,
Washington, D.C.
Wilson, J., Conard, L., Mason, S., Peplinski, W., and W. Hagan, 1990. Laboratory Investiga-
tion of Residual Liquid Organics from Spills, Leaks and the Disposal of Hazardous
Wastes in Groundwater, EPA/600/6-90/004, U.S. Environmental Protection Agency,
Washington, D.C.
Wilson, J., Enfield, T., Dunlop, W., Cosby, R., Foster, D., and L. Baskin, 1981. Transport and
fate of selected organic pollutants in a sandy soil, Journal of Environmental Quality,
10:501–506.
Wolf, K., 1992. Case study — pollution prevention in the dry cleaning industry: a small
business challenge for the 1990s, Pollution Prevention Review, Summer:311–330.
Woodbury, A. and H. Li, 1998. The Arnoldi-finite element method for solving transport of
reacting solutes in reacting media, in Wickramanayake, G. and R. Hinchee (Eds.),
Nonaqueous-Phase Liquids Remediation of Chlorinated and Recalcitrant Compounds,
The First International Conference on Remediation of Chlorinated and Recalcitrant
Compounds, May 18–21, Monterey, CA, Battelle Press, Columbus, OH, pp. 97–106.

2 Chemistry and
Transport of Petroleum
Hydrocarbons
3800 B.C. First documented use of asphalt for caulking reed boats
2.1 INTRODUCTION
An understanding of the chemistry and transport of petroleum hydrocarbons provides

the foundation for forensically reviewing information dealing with petroleum hydro-
carbon contamination. This chapter provides basic terminology and concepts asso-
ciated with the transport and fate of crude oil and refined products in the subsurface.
2.2 CHEMISTRY OF CRUDE OIL
There are over one million types of hydrocarbons in crude oil, ranging from light
gases to heavy residues. No two crude oils are identical. Crude oil is defined by Philip
(1998) as…
…extremely complex mixtures of saturated and aromatic hydrocarbons, ranging from

C1 to C100 or higher, plus a wide variety of compounds containing nitrogen, sulfur, and
oxygen. In addition, there is also a fraction called the asphaltene fraction which is
basically insoluble in n-pentane and contains a very complex matrix of high molecular
weight polar compounds.
In most cases, 90 to 98% by weight of crude petroleum consists of hydrocarbons,

while the remaining materials include sulfur, oxygen, nitrogen, and other organic
compounds. Variations in crude oil composition occur due to the nature of the source
of the organic material, the geologic and thermal history, chemical changes that occur
during oil formation and migration, and chemical alteration due to biodegradation,
oxidation, or selective dissolution. Despite wide variations in the chemistry of crude
oil, the elemental compositions fall within a narrow range of elements, as shown on
Table 2.1 (Neumann et al., 1981). Crude oils have normal paraffins (n-paraffins)

TABLE 2.1
Elemental Composition of Crude Oil
Element Composition (%)
Carbon 84–87
Hydrogen 11–14
Sulfur 0–3
Nitrogen 0–1
Oxygen 0–2
ranging from C1 to C40. Although higher carbon numbers exist in crude oils, most
crude oils fall within the C5 to C30 range (Schmidt, 1998).
The predominant hydrocarbon classes that comprise crude oil are straight or branched-
chain alkanes, cycloalkanes, and aromatics. Alkanes (paraffins) are saturated hydrocar-
bons. Linear or normal alkanes (n-alkanes) ranging from C1 to C40 have been
identified in crude oil and usually comprise 15 to 20%. In general, the most abundant
alkanes in crude oil are the low-molecular-weight normal alkanes (C5–10). Normal
alkanes (n-alkanes) are linear chains of carbons linked by single covalent bonds.
Isoalkanes are hydrocarbons containing branched carbon chains. The highest
concentration of isoalkanes in crude oils is in the C6 to C8 range. Crude oil can
contain 10 to 15% isoalkanes.
Cycloalkanes are similar to alkanes except that cycloalkanes consist of rings of
carbon atoms joined by single atomic bonds. Cycloalkanes are abundant in crude oils
and can comprise up to 30 to 40% by weight. The most abundant cycloalkanes (also
called naphthenes) are the single-ring cyclopentanes (C5H10) and cyclohexanes (C6H12).
Steranes and triterpanes are complex cycloalkanes often used as markers to identify
the source and age of crude oil (Hughes and Holba, 1988; Seifert and Moldowan,
1978; Stout et al., 1999).
Aromatic hydrocarbons consist of rings of six carbon atoms that are unsaturated
(i.e., they do not contain the maximum number of bonded hydrogen atoms). Aromat-
ics include the BTEX (benzene, toluene, ethylbenzene, and total xylenes) and poly-
nuclear aromatic compounds (PNAs). Aromatic hydrocarbons contain carbon atoms
linked with double bonds, the simplest being benzene (C6H6). Each hydrogen atom
on the aromatic ring can be replaced with an alkyl group (CH3) which results in
compounds such as toluene with one alkyl group attached to the benzene ring.
Benzene rings can be linked to other benzene rings to form compounds such as
biphenyls or terphenyls. When two or more benzene rings are fused, polynuclear
aromatic hydrocarbons (also known as polycyclic aromatic hydrocarbons, or PAHs)
are formed (see Section 4.10 in Chapter 4). Polycyclic aromatic hydrocarbons are
compounds that originate from crude oil and many pyrolysis processes. Polycyclic
aromatic hydrocarbons are of concern because of their genotoxic properties. Naph-
thalene (C10H8) is a lower molecular weight example and is generally considered to
be a polycyclic aromatic hydrocarbon, although it has only two aromatic rings. Other
non-hydrocarbon components in crude oil include sulfur, oxygen, and nitrogen.

Sulfur is typically the most abundant element and may be present in several forms,
including elemental sulfur, hydrogen sulfide, mercaptanes, and thiophenes (i.e.,
hydrogen molecules with bonded sulfur atoms). The sulfur content in most crude oils
varies from about 0.1–3% for some of the heavier oils to 5–6% for bitumen. Sulfur
does not decompose during the distillation process. The majority of sulfur is, there-
fore, present predominately in the higher molecular weight fractions and becomes
concentrated in the higher weight refined products. The analysis of the sulfur content
of crude and refined products, such as diesel, can be used to provide evidence to
distinguish between multiple sources. The sulfur content of a petroleum hydrocarbon
is determined using standards such as American Society for Testing Materials
(ASTM) D-124, D-1552, and D-4294.
Oxygen reacts with hydrocarbons to form compounds such as phenols, cresols,
and xylenols. Nitrogen can bond with hydrocarbon molecules in crude oil to form
small concentrations of pyrrole, pyridine, and quinoline. Metals are present in crude
oils, although usually in small amounts. Metals can occur as inorganic salts, metallic
soaps, and organometallic compounds. In some instances, sodium arsenite and
arsenic trioxide are added to oil pumping wells to inhibit corrosion (Rohrbach et al.,
1953; Wellman et al., 1999). The presence of arsenic in crude oil may, therefore,
provide a means for identifying the origin of the crude oil.
2.3 CHEMISTRY OF REFINED PRODUCTS
The chemistry of a refined petroleum product is the result of the composition of the
crude oil and the refining process. The term “refined products” refers to those
petroleum hydrocarbons that are blended and to which additive packages are in-
cluded. Examples of refined products include gasoline, aviation fuels, jet fuel, and
the newer formulations of diesel fuels (Harvey, 1998). Major refinery processes that
affect product chemistry are (Speight, 1991):
• Separation of the crude oil into various fractions

• Conversion of marketable portions of the crude oil
• Finishing of the various product streams
Separation and removal of the various portions of crude oil have historically been
accomplished via distillation. The three products created via distillation are naphtha,
middle distillates, and residual hydrocarbons. Naphtha, with a boiling range of 90 to
190∞C, includes gasoline, which is further processed for octane improvement. The
middle distillate fractions are separated into kerosene (light-end) and diesel range
(heavy-end) products The light-end middle distillates (boiling ranges from 150 to
260∞C) include kerosene, mineral spirits, Stoddard solvent, jet fuels, and diesel No. 1.
Stoddard solvent was used extensively in the first half of this century for degreasing
but was replaced by chlorinated solvents such as trichloroethylene due to the poten-
tial fire hazards associated with Stoddard solvent (Stewart et al., 1991). Examples of
heavy-end products are Bunker fuels, heavy fuel oils, and asphalt. Examples of chro-
matograms for mineral oil, Stoddard solvent, and kerosene are shown in Figure 2.1.

FIGURE 2.1 Chromatograms of mineral oil, Stoddard solvent, and kerosene. (From Bruya,
J., Chromatograms, Friedman and Bruya, Seattle, WA, 1999. With permission.)

TABLE 2.2
Distillation Temperature and Carbon Range of Distilled Products
Distillation Temperature
Product (C∞) Carbon Range
Gasoline 30–200 C5–C10/12

Naphtha 100–200 C8–C12
Kerosene and jet fuels 150–250 C11–C13
Diesel and fuel oils 160–400 C13–C17
Heavy fuel oils 315–540 C19–C25
Lubricating oils 425–540 C20–C45
Heavy-end middle distillates with boiling ranges of 190 to 400∞C are processed
to produce diesel fuel No. 2 and heating oils (Kaplan et al., 1995). Table 2.2
summarizes key distilled products, their distillation temperature range, and carbon
range (Galperin, 1997; Schmidt, 1998). While the distillation temperature and Ameri-
can Petroleum Institute (API) gravity of hydrocarbons provide useful information in
the refining process, they can provide corroborative evidence in distinguishing
among multiple sources of fuel releases. API gravity is defined in Equation 2.1 as:
API gravity = 141.5/P – 131.3 (Eq. 2.1)
where P is the specific gravity of the crude oil or refined product at 60∞F. Evidence
used to distinguish among sources of diesel, gasoline + diesel + jet fuel, and gasoline
at a refinery is shown in Figure 2.2 as a function of API gravity. The API gravity of
each of the various fuels stored at the refinery were known, thereby providing a
baseline for comparison.
The use of the distillation temperature of a fuel to distinguish among multiple
sources (degraded gasoline and a gasoline + diesel + jet fuel mixture) is shown on
Figure 2.3. For the free product samples collected from the groundwater table shown
in Figure 2.2, the initial boiling point (IBP) and final boiling point (FBP) of the fuels
were known, thereby allowing correlation of the IBP and FBP of the samples to
specific locations on the refinery.
The evolution of crude oil refining over time has resulted in different products
and blends of refined product. The unit process and the waste streams from these
processing changes are helpful in age-dating a product and/or bracketing a time
frame when certain refinery processes and their associated waste products were
produced. Table 2.3 summarizes some of the key historical changes in petroleum
refining (Gibbs, 1990; Harvey, 1998).
2.3.1 GASOLINE
Gasoline is composed of low-boiling hydrocarbons in the C5 to C10–C12 range that are
ignitable in an internal combustion engine. On a chromatograph, fresh gasoline

FIGURE 2.2 Use of API gravity to distinguish between fuels.
exhibits an asymmetric distribution pattern from the CH1 (methylcyclohexane) to

CH7 (a heptylcyclohexane) range, with the CH2 peak being the most abundant and
the peaks CH2 to CH7 decreasing rapidly in intensity (Galperin, 1997). Gasoline has
a boiling-point distribution from about 120 to 400∞F. As a result of the preferential
partitioning of low-boiling-temperature compounds found in gasoline, the concentra-
tion of the BTEX components can be as high as 1 to 4% for benzene and 3 to 20%
for toluene.
Gasoline blending has changed, in part, to create fuels with different octane ratings.
Examples of gasoline grades are summarized in Table 2.4 (Harvey, 1998). Gasoline
blends often reflect the level of refining. A premium-grade gasoline, for example, is a
FIGURE 2.3 Use of initial (IBP) and final boiling point (FBP) temperatures to identify fuel
types.

TABLE 2.3
Chronology of Key Changes in Petroleum Refining in the U.S.
Date Key Refinery Process
1910 Straight run (distilled) products produced; 65–75 octane rating

1913 Dubbs thermal cracking process introduced
1920 Coking introduced
1923 Lead introduced in gasoline to minimize backfiring
1926 Lead anti-knock additive introduced
1928 Lead scavengers ethylene dibromide and ethylene dichloride introduced
1929 Regular and premium gasoline sold
1936 Fluid catalytic cracking introduced
1938 Alkylation introduced
1940 Reforming introduced
1959 Hydrocracking introduced
1970–74 More olefins added to gasoline
1980 Lead regulations
1990 Advent of environmental regulations of sulfur, aromatics, and oxygenates
more tightly regulated blend than a mid-grade or regular gasoline. Chromatograms

of gasoline grades and blends are shown in Figure 2.4 (Zemo et al., 1993).
Changes in the octane ratings of different gasoline grades include a 65 to 75
octane rating in 1910, an average octane rating of 82 in 1946, and an average octane
rating of 96 in 1968 (Gibbs, 1990). The significance of these different gasoline grades
and octane ratings over time is that it is unlikely that forensic testing can identify a
gasoline grade once it has entered the subsurface. Compounds used to provide higher
octane ratings, however, can be identified on a chromatogram. Examples include iso-
octane, toluene, ethylbenzene, xylenes, and trimethylbenzene. For example, a pre-
mium-grade, 1994 gasoline tends to have a high percentage of iso-octane and
aromatics. The greater the combined percentage of iso-octane and aromatic com-
pounds, such as toluene, the higher the octane and fuel quality and, therefore, the
more likely it is that the product was refined and blended.
TABLE 2.4
Grades of Gasoline
Leaded Gasoline Unleaded Gasoline
Super premium leaded Premium or supreme unleaded

Premium or supreme leaded Mid-grade unleaded
“Super regular” leaded Regular unleaded
Regular leaded
Economy leaded
Regular low lead

FIGURE 2.4 Gasoline chromatograms. (From Zemo, D. and T. Graf, in Proc. of the 1993
Petroleum Hydrocarbons and Organic Chemicals in Ground Water: Prevention, Detection,
and Restoration, November 10–12, Houston, TX, Ground Water Management Book 17,
National Ground Water Association, Dublin, OH, 1993, pp. 39–54. With permission.)
Refined gasoline contains olefins (alkenes and alkynes), while crude oils and
virgin naphthas do not. As a result, olefins are useful for distinguishing between
refined and crude oils. Olefins are products of the catalytic cracking process. Olefins
are identified on chromatograms as a cluster of small peaks to the right of the C6 peak
(Schmidt, 1998). Alkynes (acetylenes) are also not normally found in crude oil.
Another indicator used to distinguish between refined and unrefined products is the

FIGURE 2.5 Chromatograms for diesel fuels No. 1 and No. 2. (From Bruya, J., Chromato-
grams, Friedman and Bruya, Seattle, WA, 1999. With permission.)
presence of methylcyclohexane (MCH). Methylcyclohexane is abundant in unre-

fined gasoline range hydrocarbons and naphthas. In general, the greater the concen-
tration of methylcyclohexane, the less the product has been refined, as well as the
lower the octane rating of the gasoline.
2.3.2 DIESEL
Diesel consists of hydrocarbons in the C11 to C18–27 range. Depending on the grade of
diesel, it contains a high concentration of cycloalkanes and smaller amounts of
aromatic compounds (i.e., BTEX). Diesel tends to have greater concentrations of
polycyclic aromatic hydrocarbons than does gasoline. The changing formulation of
diesel provides opportunities for dating a release. Prior to 1975, diesel was primarily
straight chained, while post-1975 diesel was thermally cracked. This distinction can
be determined analytically with only several milliliters of product, thereby providing
a bracket of time when the product was available. Chromatograms of a diesel fuel No.
1 and No. 2 are shown in Figure 2.5.

TABLE 2.5
Products, Synonyms, and Characteristics of Diesel and Jet Fuels
Product and
Synonym(s) Composition and Characteristics
Diesel No. 1 Similar in composition to a blend of kerosene and diesel No. 2. Diesel No. 1 is
manufactured in cold climates and is also sold in warm climates when a refinery
desires to blend its kerosene with more expensive diesel No. 2. Diesel No. 1 exhibits
an alkylcyclohexane pattern on a mass chromatograph in the range from CH1 to
CH14, with a maximum at CH5.
Diesel No. 2 Automotive diesel. Straight-run or catalytically cracked petroleum distillate with a
typical carbon range of C8–9 to C24–27 and a boiling range of approximately 163 to
382∞C. Includes straight-run kerosene, middle distillate, hydro-desulfurized middle
distillate, and light catalytically and thermally cracked distillates. Formulated for
use in atomizing-type burners. BTEX components can be present in small amounts.
Using gas chromatography/mass spectrometry (GC/MS), diesel No. 2 shows a
range of alkylcyclohexanes from CH1 to CH14, maximizing around the CH9 and
CH10 peaks. Characterized by a smooth n-alkane distribution pattern.
Diesel No. 4 Railroad diesel. A straight-run or cracked petroleum distillate with a typical carbon
range of C11 to C30. Used without preheating in commercial or industrial burners
that can accommodate a higher viscosity diesel such as diesel No. 4.
Diesel No. 5 A fuel comprised primarily of straight-chained hydrocarbons. Diesel No. 5 is a
residual fuel that often requires preheating for handling.
Bunker C (heating A residual fuel used in commercial and industrial heating. Bunker C requires
oil or diesel No. 6) preheating for storage and for burning. Sulfur is often found in higher concentra-
tions than in other diesels, unless they are deliberately extracted. Bunker C is the
primary fuel for steam-powered ships and for onshore power-generation plants and
is primarily a mixture of diesel No. 1 and No. 2 and residual oil. Bunker C is a
distillation residue of crude oil and contains biomarkers such as terpanes and
steranes. Bunker C has a hydrocarbon range from C9 to about C36 and a boiling point
range of about 340 to 1050∞F.
Kerosene A straight-run distillate with hydrocarbons in the C9/10 to C16 range. A light-end
(No. 1 fuel oil) middle distillate used in vaporizing-type burners where the fuel is ignited by contact
with a heated surface or radiation. Consists primarily of paraffins with smaller
amounts of naphthalene and aromatic hydrocarbons. The carbon distribution peaks
around C12 to C13. It is similar in composition to JP-5 and JP-6 jet fuels.
Diesel is available in various grades. Diesel, kerosene, and the lighter distillates
contain various amounts of the BTEX aromatics up to 1500 parts per million (ppm)
(Dunlap and Beckmann, 1988). The composition and characteristics of diesels and
middle distillate products are described in Table 2.5 (Havlicek, 1986; Kaplan et al.,
1995; Kaplan and Galperin, 1996). A petroleum forensic laboratory to needed to
distinguish between fuels that are similar. Figure 2.6 illustrates chromatograms for
jet fuel No. 4 (JP-4) and jet fuel No. 5 (JP-5) to show the chromatographic similarity
of these two fuels (Bruya, 1999).

TABLE 2.5 (cont.)
Products, Synonyms, and Characteristics of Diesel and Jet Fuels
Product and
Synonym(s) Composition and Characteristics
Stoddard solvent Used as a drycleaning solvent and paint thinner and in printing inks, certain
adhesives, and some photocopy toners. It consists primarily of nonanes with smaller
amounts of alkylbenzenes. Synonyms include mineral spirits, light petroleum naph-
tha, drycleaning safety solvent, petroleum solvent, varnoline, and spotting naphtha.
Registered trade names include Texsolve S® and Varsol 1® (ATSDR, 1995). The
boiling range is between 220 and 300∞F. Stoddard solvent exhibits an alkyl-
cyclohexane pattern upon GC/MS in the CH2 to CH9 range, with the distribution
maximizing at CH5.
Petroleum naphtha Naphtha exhibits an alkylcyclohexane pattern in the CH1 to CH6 range that maxi-
mizes at CH3.
Jet fuels:
JP-1 Military-grade distillate with a flash point of 95∞F.
JP-4 (Jet B) Military-grade distillate with a flash point of –10∞F and a boiling range of 48 to
270∞C. Contains about 65% gasoline and 35% light distillates. Most of the
volatile gasoline hydrocarbons are absent, and the iso-octane content is generally
below 1%. On a chromatogram, it looks like a light-kerosene and/or gasoline
blend with a considerable amount of aromatic compounds. Using GC/MS, it
demonstrates a distribution pattern in the CH1 to CH9 range.
JP-5 (Jet A1) A U.S. Navy distillate with a flash point of 95∞F and a boiling range of 150
to 290∞C. JP-5 has a low freezing point and high flash point for use by carrier-
based aircraft for long-range flights. JP-5 has an alkane distribution pattern in
the kerosene range with a maximum around C11. Using GC/MS, a distribution
pattern in the kerosene range (CH1 to CH9) is discernible, with a noticeable
difference in the maximum peak of distribution with CH5 for JP-5 and CH 4 for
Jet A.
JP-6 (Jet A) Military-grade distillate with a flash point of 100∞F. Preferred for short- and
medium-range aircraft flights.
JP-8 A military aircraft fuel with a distribution pattern around C10 or C11. On a GC/MS,
an asymmetric distribution pattern is observable in the CH1 to CH14 range.
2.4 CHEMICAL REACTIONS

IN THE VADOSE ZONE
The physical transport of crude oil and refined products through the subsurface is a
function of product chemistry, the hydraulic conductivity (K) of the soil or rock, and
the presence of a driving mechanism such as rainfall, ponded water, or leakage from
an underground storage tank. An understanding of the relationship between a con-
taminant and the media through which it is transported is used to estimate the relative

FIGURE 2.6 Chromatograms of JP-4 and JP-5. (From Bruya, J., Chromatograms, Friedman
and Bruya, Seattle, WA, 1999. With permission.)
mobility and distribution of the contaminant. Contaminant properties impacting the

mobility of a chemical through the unsaturated zone and saturated zones include its
Henry’s Law constant, vapor pressure, density, solubility, and viscosity. If the
petroleum hydrocarbon has a significant volatile component, vapor transport of the
compound can be important.
The chemical and physical interaction of petroleum hydrocarbons in the subsur-
face is important in understanding the mobility of the compound. Commonly
encountered interactions include sorption, oxidation/reduction processes, chemical
precipitation, ion exchange, hydrolysis, biological mediated reactions, and cosolva-
tion.

2.4.1 HENRY’S LAW CONSTANT (KH)
The Henry’s Law constant (KH), also known as the air/water partition coefficient, is
the ratio of the partial pressure of a compound in air to its concentration in water at
a given temperature. The Henry’s Law constant is, therefore, a measure of the
propensity of a compound to volatilize as it migrates through the soil (see Chapter
1, Section 1.3.3).
As the Henry’s Law value increases, the amount of the contaminant in the soil
vapor phase increases. Compounds with high Henry’s Law constants (e.g., butane,
hexane, and benzene) are more amenable to soil gas surveys and remediation via
vapor extraction than compounds with low values.
For the lower alkanes (methane through hexane), the dimensionless Henry’s Law
constant ranges from about 30 to 70 which means that, in equilibrium, 30 to 70
molecules of these alkanes are present in the soil vapor for every molecule that
dissolves into the groundwater. For the BTEX constituents, the Henry’s Law constant
is about 0.25, which means that one molecule of BTEX exists in the soil vapor for every
four that dissolve into the water. As a result, a soil vapor survey is about 200 times more
likely to detect the lower alkanes than BTEX compounds (Hartman, 1998).
2.4.2 LIQUID DENSITY

The relative density (also called specific gravity) of a substance is defined as the ratio
of the density of the substance to the density of distilled water (a mass-to-volume
ratio). The density of distilled water at a standard temperature and pressure is 1.0 g/
mL. Specific density is a unitless measurement but is dependent on the temperature
of the substance at the time of measurement. Light non-aqueous phase liquids
(LNAPLs) have densities less than 1.0, while dense non-aqueous phase liquids
(DNAPLs) have densities greater than 1.0. Most crude, residual, and used oils are
LNAPLs with densities from about 0.6 to 1.0 g/mL.
A contaminant’s density is important, especially when the contaminant enters the
capillary fringe (that partially saturated area above the groundwater table). Liquids with
densities greater than 1.0 (e.g., coal tar) have a greater probability of “sinking” into
groundwater than do liquids with densities less than 1.0 (gasoline, diesel, Stoddard
solvents, mineral oils), which tend to “float” on the water table. BTEX (benzene,
toluene, ethylbenzene, and xylene) compounds are lighter than water, while polycyclic
aromatic hydrocarbons (PAHs) such as anthracene, chrysene, fluorene, naphthalene,
phenanthrene, and pyrene are heavier than water. The term PAH is synonymous with
polynuclear aromatic hydrocarbons (PNAs). These chemicals are often classified as
carcinogenic — benzo(a)pyrene, benzo(a)anthracene, benzo(b)fluoranthene,
benzo(k)fluoranthene, benzo(g,h,i)perylene, chrysene, dibenzo(a,h)anthracene, and
indeno(1,2,3-c,d)pyrene — and noncarcinogenic — naphthalene, acenaphthylene,
acenaphthene, fluorene, phenanthrene, anthracene, fluoranthene, and pyrene.
Hydrocarbons with a high specific gravity are transported vertically in the
unsaturated zone due to gravity and capillary forces. If the volume of high-specific-
gravity hydrocarbons released is large, the hydrocarbons will be vertically transported

TABLE 2.6
Density of Selected Light and Dense Hydrocarbons
Density (g/cm3)
Hydrocarbon 25∞C 15∞C
Coal tar 1.028 —

Bunker C (No. 6 fuel oil) 0.969 0.974
No. 5 fuel oil 0.917 0.923
Styrene 0.907 —
No. 4 fuel oil 0.898 0.904
Lube oil (gear oil) 0.883 —
Lube oil (crankcase oil, new) 0.878 —
Lube oil (crankcase oil, used) 0.885 —
North Sea crude 0.8–0.88 —
Benzene 0.874 —
10W40 engine oil 0.866 —
Toluene 0.865 —
Kerosene 0.849 0.839
No. 2 fuel oil 0.840 0 866
Light heating oil 0.82–0.86 —
Marine diesel 0.862 —
Diesel fuel — 0.827
Mineral spirits 0.793 —
Soltrol 0.789 —
Jet fuel 0.77–0.84 —
JP-4 0.755 —
JP-5 0.788 0.844
JP-7 0.779 —
JP-8 0.840 —
JP-A 0.775 —
JP-B 0.757 —
Gasoline 0.720 0.729
Naphtha (petroleum ether) 0.640 —
through the soil and groundwater due to density. This phenomenon is known as
density flow. Upon entering the groundwater, these hydrocarbons migrate as a
function of specific gravity and less by advection (the mass transport of groundwa-
ter). Table 2.6 lists the densities of several light and dense hydrocarbons (API, 1989,
1994, 1995; Dragun, 1988).
2.4.3 SOLUBILITY
The solubility of a compound is the saturated concentration of the compound in water
at a known temperature and pressure. The more soluble the compound, the greater
the fraction that dissolves into the soil pore water or groundwater. BTEX compounds

TABLE 2.7
Highly Soluble Components of Gasoline
Compound Percent in Gasoline by Weight
Benzene 1.94
Toluene 4.73
Ethylbenzene 2.0
o-Xylene 2.27
p-Xylene 1.72
m-Xylene 5.66
2-Butene 0.315a
2-Pentene 0.435a
Butane 3.83
1,2,4-Trimethylbenzene 3.26
Pentane 3.11
a Average of cis- and trans-.
are so frequently encountered in groundwater in part due to their high solubility.

Benzene, for example, was detected 23% of the time at 888 Superfund sites based on
a total of 466 chemicals tested for, as of October 1986. Toluene and xylene were detected
27% and 13% of the time, respectively. Toluene was the second most frequently
encountered contaminant, second only to trichloroethylene (TCE; 1100 mg/L at
20∞C) (Siegrist, 1993). Table 2.7 lists those highly soluble compounds in an API PS-
6 unleaded gasoline along with their estimated percent by weight (API, 1985, 1994).
Compounds with high water solubilities tend to desorb from soils, are less likely
to volatilize from water, and are susceptible to biodegradation. Compounds with low
solubilities tend to sorb onto soils and volatilize more readily from water and are
more likely to enter the groundwater. The water solubility of a compound varies with
pH, the presence of inorganic salts, and the presence of organic carbon. Solubilities
of pure phase compounds in water at three temperatures are summarized in Table 2.8
(Havlicek, 1986; Polak and Lu, 1973; Rossi and Thomas, 1981).
BTEX solubility in water is dependent on the nature of the multi-component
mixture, such as gasoline, diesel, or crude oil. The solubility of a constituent within
a multi-component mixture may be orders of magnitude lower than the aqueous
solubility of the pure chemical constituent in water (Odencrantz et al., 1992). The
weight percent and mole fraction of the BTEX components as functions of the
mixture are also important. Table 2.9 presents the calculated effective solubility of
BTEX compounds in gasoline, diesel, and a California crude oil (API, 1985; Metcalf
and Eddy, 1993).
2.4.4 VISCOSITY
Viscosity is the property of a substance to offer internal resistance to flow. An ideal
fluid is one that is devoid of viscosity. A similar but different term is “kinematic

TABLE 2.8
Solubility of BTEX Compounds and MTBE
Solubility at 0∞C Solubility at 20∞C Solubility at 25∞C
Compound (ppm) (ppm) (ppm)
Benzene (C6H6) — 1780 1760

Toluene (C6H5CH3) 724 515 573
Ethylbenzene (C6H5CH2CH3) 197 153 177
m-Xylene (C6H4(CH3)2) 196 158 146–173
o-Xylene (C6H4(CH3)2) 142 152 213
p-Xylene (C6H4(CH3)2) — — 180–200
MTBE ((CH3)3C(OCH3)) — — 48,000
viscosity” which is the viscosity of the substance divided by its density. The viscosity
of a liquid usually increases with decreasing temperature, though in some complex
mixtures there is a discontinuity in the temperature/viscosity relationship. These
discontinuities occur where there is a large change in viscosity over a very narrow
temperature range. The simplest and most widely used determination of viscosity is
American Society for Testing Materials (ASTM) Standard Method D-445 as de-
scribed in Equation 2.2.
m = p r4P/8Nl (Eq. 2.2)
where
m = quantity discharged in units of time.

r = tube radius.
P = pressure difference between the ends of a capillary tube.
N = coefficient of viscosity.
l = tube length.
TABLE 2.9
Effective Solubility of BTEX Components in Gasoline,
Diesel, and Crude Oil
Effective Solubility (ppm)
Compounds Gasoline Diesel California Crude Oil
Benzene 44.39 8.83 0.70

Toluene 26.54 3.25 1.54
o-Xylene 3.26 1.39 0.25
m-Xylene 8.45 1.44 0.26
p-Xylene 3.25 1.82 0.32
Ethylbenzene 2.87 0.55 0.74

TABLE 2.10
Kinematic Viscosity of Refined Products
Product Kinematic Viscosity at 10∞C Kinematic Viscosity at 100∞ C
(cSt)a (cSt)a
Gasoline 0.61–0.85 <0.40

Diesel 2.7b —
Kerosene 2.3b —
JP-4 1.1–1.8 0.47–0.64
No. 1 fuel oil 2.2–4.2 0.7–1.0
No. 2 fuel oil 3.0–8.0 0.85–1.3
No. 4 fuel oil 30–100 2.5–4.8
No. 5 light fuel oil 130–400 5.5–8.0
No. 5 heavy fuel oil 500–1200 9.0–13
No. 6 fuel oil 1500–30,000 15–50
a One centistoke (cSt) = 1 ¥ 106 m2/sec.

b Measured at 15∞C.
While diesel and gasoline viscosities are similar, crude oil has a wide range of
viscosities. For example, the viscosity of a Prudhoe Bay crude oil in Alaska is 73.5
Saybolt units, while a Kern River crude oil from Bakersfield, CA, is greater than
6000 Saybolt units. The viscosity of refined petroleum products varies from about
0.25 to more than 50,000 cPa at 15∞C. An approximate correlation between specific
gravity and viscosity for refined products is described in Equation 2.3.
hro = 8.28rro(9.5) (Eq. 2.3)
where
hro = ratio of the kinematic viscosity to water.
rro = specific gravity of the refined produced.
As a basis of comparison, the kinematic viscosity for water at 20∞C is 0.01 cm2/sec,
while benzene has a kinematic viscosity of 0.00721 cm2/sec. Pure benzene flows
about 40% faster than water through identical porous media.
The kinematic viscosity is called dynamic or intrinsic viscosity. Infiltration
velocities are often approximated as a proportionality that is inverse to the kinematic
viscosity. For example, a crude oil can migrate 3 to 35 times slower through soil than
water (Dragun, 1988).
The kinematic viscosity of a hydrocarbon is affected by temperature. For crude
oil, this effect can be several orders of magnitude. Table 2.10 summarizes the
kinematic viscosity of selected heavy fuel oils for two temperatures (API, 1989,
1994; Dragun, 1988). A decrease in viscosity increases the flow rate of a hydrocarbon
through a porous media. During the natural weathering of petroleum products,
viscosity tends to increase sharply.

2.4.5 VAPOR PRESSURE AND VAPOR DENSITY
Volatilization is the phase change of a compound from a liquid or solid to a gaseous
phase; it is associated with the vapor pressure of the compound. In general, com-
pounds with vapor pressures exceeding 0.5 to 1 millimeter of mercury (mmHg) can
exist in appreciable concentrations as vapor near a free phase product. Hydrocarbons
that volatilize quickly include butane, pentane, hexane, heptane, and octane. The
aromatic BTEX and methyl ethyl benzenes and trimethylbenzenes also volatilize
quickly but at a rate less than the butanes, pentanes, hexanes, heptanes, and octanes.
The loss of BTEX compounds in a sequential order relative to vapor pressure is often
observed in the analytical data at hydrocarbon-impacted sites.
Vapor density is the density of a compound relative to air (e.g., 29 g/mol). Most
petroleum hydrocarbons have densities 3 to 4 times greater than air. The vapor
density is estimated by dividing the molecular weight of a compound by the molecu-
lar weight of air. The molecular weight of benzene is 78 g/mol; therefore, dividing
78 by 29 yields a vapor density for benzene of 2.5. The vapor density for gasoline
is about 3.3. The significance of vapor density is that petroleum hydrocarbon vapors
can migrate through porous soils in the unsaturated zone as a function of vapor
density (Hartman, 1998).
2.4.6 SORPTION
Sorption is the uptake of a vapor or liquid into another material without reference to
a specific mechanism (Chiou, 1989). Sorption encompasses the processes of adsorp-
tion, absorption, ion exchange, ion exclusion, retardation, chemisorption, and dialy-
sis. Of these processes, absorption (the penetration of substances into the bulk of a
solid or liquid) and adsorption (the surface retention of a solid, liquid, or gas
molecules by a solid or liquid) are the most important. This phenomenon results in
a contaminant’s distribution between the solid and liquid phase and relative retarda-
tion of the chemical. The higher the fraction of the contaminant that is sorbed, the less
is available for transport.
The sorption capacity of a compound is described by the term “sorption coeffi-
cient”. The sorption coefficient is the ratio of an adsorbed chemical per unit weight
of organic carbon to the concentration of the contaminant. It implicitly assumes a
reversible process — that is, sorption and desorption occur at the same rate.
2.4.7 RETARDATION
Retardation is the lowering of the average velocity of a contaminant mass relative
to the average (advective) groundwater velocity. Compounds that sorb strongly to
organic carbon material in soils characteristically have low solubilities; compounds
with low tendencies to adsorb onto organic particles have high solubilities. The
affinity of a compound to be sorbed by organic or mineral matter is called the
retardation factor (R). The retardation factor or coefficient is the ratio of the

concentration of a compound on a solid to the concentration of that compound in
solution.
Laboratory experiments indicate that values for retardation vary widely, depend-
ing on the type of soil and contaminant. Given the uncertainties associated with
calculating R, compounds with values less than 2 can be considered to be moving at
a rate similar to groundwater. Distribution coefficient values can be obtained from
the literature, calculated from the measured organic carbon content in soil, or
measured from laboratory batch sorption or column transport studies. The most
common technique is to measure the organic content of the soil and obtain the soil/
organic carbon partition coefficient (Koc) of the chemical from published tables.
Retardation directly impacts the rate at which a hydrocarbon or components of
a hydrocarbon will move in the subsurface. For example, non-BTEX compounds that
are relatively mobile in water (based on their retardation coefficients) include 1,2,4-
trimethylbenzene, naphthalene, 2-methylnaphthalene, cyclohexane, n-hexane, 2,3-
dimethylbutane, and 2,2-dimethylpentane. Compounds that are relatively less mobile
in water values include benzo(a)anthracene, benzo(a)pyrene, 5-methylchrysene, 1-
methylphenanthrene, and dibenzothiophene.
2.4.8 BIODEGRADATION
Biodegradation is the biological transformation of complex substances into simpler
substances by bacteria, fungi, and yeasts. Hydrocarbon biodegradation is accom-
plished primarily by bacteria. Over 200 soil microbial species have been identified
that can assimilate hydrocarbon substrates. Some of these microbes include Pseudomo-
nas, Flavobacterium, Micrococcus, Mycobacterium, Nocardia, and Acinetobacter
(Bowlen and Kosson, 1995; Manahan, 1984).
For most biodegradation pathways, the final degradation products are carbon
dioxide and water, a process called mineralization. It is possible that the final
mineralization products are not achieved and that the degradation results in relatively
stable aromatic hydrocarbons. While a multitude of degradation reactions can occur,
common transformations occur stepwise from end carbons, producing alcohols,
aldehydes, and fatty acids in sequence.
The rate and ability of microbes to degrade hydrocarbons is dependent on the
ability of the subsurface environment to support a healthy community of microbes.
Conditions that influence the rates of hydrocarbon degradation include soil tempera-
ture, soil porosity, soil moisture content, the oxygen content of the particle spaces,
the nutrient content, and fuel type (Kaplan et al., 1995).
The concentrations of nutrients and oxygen required to sustain viable microbial
communities are highly variable. In general, a 1:20 ratio of available inorganic
nitrogen to the petroleum hydrocarbon and a 1:100 ratio of available phosphate to
petroleum hydrocarbons are necessary to support biological degradation of petro-
leum hydrocarbons.
Some generalizations concerning biodegradation are that biodegradation may not
occur if the concentration of the compound is very low and that most organic

compounds will degrade to some extent. Current research suggests that benzene is
not degraded under denitrifying conditions and that toluene, xylene, and ethylbenzene
degradation are slow (Kao and Borden, 1997). At the Eglin Air Force Base site, the
preferential removal of toluene and ortho-xylene from the BTEX components closest
to the spill was observed. Ethylbenzene and meta- and para-xylene degradation in-
creased after the toluene and ortho-xylene were depleted (Wilson et al., 1994). It was
also calculated that for the BTEX components within the groundwater approximately
1.0 mg of methane was produced for each 1.3 mg of BTEX destroyed. In general, if
the concentration of petroleum hydrocarbons or heavy metal concentrations are in
excess of 25,000 or 2500 ppm, respectively, then the environment is considered
inhibitory or toxic to aerobic bacteria. Biodegradation commences as soon as the
petroleum hydrocarbon is released into the subsurface, with the lower molecular
weight alkanes degraded first, followed by the higher molecular weight compounds.
The temperature of the surrounding soil or groundwater also impacts degradation
rates. Some of the fastest bioattenuation rates of BTEX compounds observed by the
Environmental Protection Agency’s Robert S. Kerr Environmental Research Labo-
ratory in Ada, OK, have been in cases where groundwater temperatures are high (24
to 28∞C).
Biodegradation rates are influenced by the molecular structure of the hydrocar-
bon. Straight-chained saturated hydrocarbons are degraded more readily than aro-
matics (BTEX compounds), which are subsequently degraded more readily than
alicyclics and highly branched aliphatic hydrocarbons. As a result of these hydrocar-
bon degradation sequences, alicyclics and highly branched aliphatics accumulate in
the soil, while the more biodegradable of the compounds in the original product are
not present. In general, the weathering of gasoline, diesel, and Bunker C fuel
proceeds in the following temporal sequence (Galperin, 1997):
1. Abundant normal alkanes

2. Light-end normal alkanes
3. Middle-range normal alkanes, olefins, benzene, and toluene
4. More than 90% removal of the alkanes
5. Alkylcyclohexane and alkybenzenes
6. Isorepnoids and C0-naphthalene reduction
7. C1-naphthalenes, benziothiophene, alkylbenzothiophenes, and C2-naphthalenes
8. Phenanthrenes, dibenzothiophenes, and other polynuclear aromatic hydrocarbons
9. Tricyclic terpane enrichment, selective removal of regular steranes, reduction of
C31–C35 homohopanes
10. Increased abundance of tricyclic terpanes, diasteranes, and aromatic steranes
The biodegradation of specific petroleum fractions in a fuel has been proposed

as a means to age-date a hydrocarbon (Kaplan et al., 1995; Morrison, 1997; Raymond
et al., 1976). The basis of this approach is reliance on the biodegradation half-life of
hydrocarbon compounds in the soil or groundwater. The estimated half-life is the
time required for one half of the compound to biodegrade. The rate of biodegradation
is usually expressed in units of g/m2 day–1, g/m3 year–1, mg/day per bacterial cell,
percent of oil removed after a known number of days or weeks, or g/m3 day–1. A

TABLE 2.11
Biodegradation Half-Lives of BTEX and PAH Compounds
Biodegradation Half-Life (hr)a
Compound Soil Groundwater
Benzene (C6H6) 120–384 240–17,280

Toluene (C6H5CH3) 96–528 168–672
Ethylbenzene (C6H5C2H5) 72–240 144–5472
o-, m-, p-Xylene (C6H4(CH3)2) 168–672 336–8640
Acenaphthene (C12H10) 299–2448 590–4896
Anthracene (C14H10) 1200–11040 2400–22,080
Benzo(a)pyrene (C20H12) 1368–12,720 2736–25,440
Chrysene (C18H12) 8904–24,000 17,808–48,000
Fluoranthene (C10H10) 3360–10,560 6720–21,120
Fluorene (C13H10) 768–1440 1536–2880
Naphthalene (C10H8) 398–1152 24–6192
Phenanthrene (C14H10) 384–4800 768–9600
Pyrene (C16H10) 5040–45,600 10,080–91,200
a Measured at 25∞C.
summary of the half-lives of selected BTEX and polynuclear aromatic hydrocarbon

(PAH) compounds is provided in Table 2.11 (API, 1985; Howard et al., 1991).
2.5 OVERVIEW OF TRANSPORT THROUGH

THE UNSATURATED (VADOSE) ZONE
The unsaturated zone is that portion of the subsurface situated between the ground
surface and first water-bearing formation. Surface releases of hydrocarbons usually
transit this zone prior to entering the groundwater. Physical parameters used to
describe soils and used in petroleum transport calculations include porosity, perme-
ability, hydraulic conductivity, and gas permeability.
The transport of petroleum hydrocarbons through soil can change the hydraulic
conductivity of the native soil, if the hydrocarbons are the primary wetting fluid (as
opposed to water). This can occur with a massive release in which the hydrocarbons
displace the water between the soil grains. It is a physical process and is reversible;
if water subsequently displaces the petroleum hydrocarbons, the hydraulic conduc-
tivity will significantly decrease. These changes usually occur due to the permeation
by nonpolar organics with clay. Typically, these changes are related to the following
mechanisms: dehydration, swelling, flocculation, and macroscopic cracking (Ander-
son et al., 1985; Daniel et al., 1986).
Unsaturated hydraulic conductivity values for the vadose zone are obtained in the
field or laboratory by measuring the hydraulic conductivity of a soil under saturated

conditions and then allowing the water to drain from the soil. The resulting graph that
plots the percent moisture vs. soil suction is called a soil moisture characteristic curve.
A dry soil exhibits greater soil suction than a wet soil. A soil characteristic curve enables
calculation of the hydraulic conductivity as a function of soil moisture content.
2.5.1 TRANSPORT THROUGH SOIL

The fundamental principles governing advective (mass) transport of water in soil
generally apply to those for hydrocarbon transport (i.e., gravity and capillarity).
Hydrocarbons move through the soil under a three-phase flow condition, displacing
air and water. Variations in soil permeability result in a deviation from the gravita-
tionally dominated vertical flow; as the hydrocarbon encounters layers of slightly less
permeable materials or materials with smaller pores, it will tend to flow mostly in the
horizontal direction until it encounters a path of less resistance. This conceptual model
is more complex, however, because other transport and transformation processes occur.
If a large volume of gasoline or diesel is released at or near the surface, it initially
tends to infiltrate vertically through the soil. If the volume of release is sufficient to
overcome the residual soil-retention capacity, the migration of the hydrocarbon will
continue until the fluid reaches the capillary fringe, where it accumulates (Bossert and
Bartha, 1984). As the hydrocarbon is transported through the soil, it may encounter less
permeable soils that create a boundary condition; this may result in lateral spreading
until a more permeable horizon is encountered for the hydrocarbon to move vertically.
On a soil particle scale, petroleum hydrocarbon distribution in soil is dependent
on the pore size between the soil grains and the pore pressures of the air, water, and
hydrocarbons occupying these pore spaces. If the hydrocarbon completely saturates
the soil and displaces water in the soil, maximum lateral and vertical spreading will
occur. Gasoline components will also preferentially dissolve from the bulk hydrocar-
bon and migrate at different velocities through the soil (as well as the groundwater).
This phenomenon is called chromatographic separation, which is often observed in
the separation of more mobile compounds such as methyl-tertiary-butyl-ether (MTBE)
moving ahead of the center of mass of a hydrocarbon in groundwater.
2.5.2 COSOLVATION AND COLLOIDAL TRANSPORT

Cosolvation (also referred to as cosolvency) is the enhancement of an otherwise low
mobility compound by its preferential dissolution into an organic solvent. Cosolvation
occurs when a mobile phase is formed from multiple solvents that are miscible in
each other (Kargbo, 1994). The addition of a cosolvent decreases the retardation and
sorption coefficient of hydrophobic organic compounds such as polycyclic aromatic
hydrocarbon compounds. For soils, cosolvation is shown to increase mobility signifi-
cantly only at high cosolvent concentrations, usually greater than about 5% of the
solution (Nkedi-Kizza et al., 1987). Cosolvation has been demonstrated to enhance
the solubilization of sparingly soluble compounds in the pharmaceutical literature
and in soil research (Lane and Loehr, 1992).

TABLE 2.12
Residual Saturation (mg/kg) of Refined Products in Soil
Soil Type Gasoline No. 2 Fuel Oil Lube Oil No. 6 Fuel Oil
Coarse gravel — 800 1600 —

Gravel to coarse sand — 1600 3200 —
Coarse to medium sand — 2800 5600 —
Medium to fine sand 2000 4800 9600 60,000
Fine sand to silt — 8000 16,000 —
Another example illustrating cosolvation is the detection of the polynuclear

aromatic (PNA) naphthalene and a solvent, such as methanol, at depth. The solubility
of naphthalene in various solvents is as follows: 30 mg/L in water, 77 g/L in ethanol
and methanol, 285 g/L in benzene and toluene, and 500 mg/L in chloroform and carbon
tetrachloride. The presence of methanol and naphthalene at depth would, therefore,
suggest the preferential transport of naphthalene to depth via cosolvation with
methanol. Another example is the release of oxygenated fuels into soil containing
PAHs. The theoretical sorption of a PAH coefficient decreases exponentially as the
fraction of the organic solvent increases (Chen et al., 1977); therefore, the presence of
an oxygenate such as MTBE in the fuel can enhance the transport of PAHs, as well as
benzene, toluene, ethylbenzene, and xylene present in the soil due to cosolvency effects.
2.5.3 RESIDUAL SATURATION

Residual saturation is defined as the fraction of total soil space filled with a liquid due
to capillary forces. As hydrocarbons migrate through soil, a small amount of the total
hydrocarbon mass remains attached to these soil particles via sorption. The hydro-
carbon retained by the soil particles is known as residual or immobile saturation. The
percentage of residual saturation remaining in a soil is dependent on soil moisture
content, soil porosity, and soil texture. The residual saturation for light oil and
gasoline is about 1% of the total soil porosity; for diesel and light fuel oil, 15%; and
for lubricating and heavy fuel oil, about 2%. Residual saturation estimates are
routinely used to estimate the volume of recoverable hydrocarbon in the soil. Re-
sidual saturation values are measured directly by collecting a representative soil
sample and saturating it with the petroleum hydrocarbon of concern, followed by
allowing the soil to drain for several days and then measuring the volume of
hydrocarbon retained by the soil.
The viscosity of a fuel affects its residual saturation. As the viscosity decreases,
the residual saturation concentration decreases (Hoag and Marley, 1986). Theoretical
studies suggest that the residual saturation increases proportionally to the fourth root
of the product’s viscosity. Table 2.12 lists the residual saturation of petroleum
products in soils (Dragun, 1988). Residual saturation is significant because it remains
as a source of contamination via water infiltrating through the soil column coming

into contact with the residual hydrocarbons. Seasonal changes in groundwater level
can resolubilize residual hydrocarbons into the groundwater, a fact that is reflected
in downgradient monitoring wells as a seasonal trend of high and low concentrations
of BTEX concentrations coinciding with the fluctuating water table.
Residual saturation contamination of soils by hydrocarbons can occur in soil
downgradient of a spill that may be on an adjacent property. This situation occurs
when free product on the water table comes into contact with otherwise clean soils
above it due to a rising water table. When the groundwater drops, the previously
clean soil contains a certain percentage of residual saturation. Previously uncontami-
nated soils now become a source for further contamination. This phenomenon is
important to consider when examining soil gas survey data as indicators of the source
of contamination, especially with shallow groundwater. Soils with residual hydrocar-
bon downgradient of the original spill may volatilize, resulting in the appearance of
a release and/or masking of the original source of the contamination.
2.5.4 VAPOR PHASE TRANSPORT

The volatile component of hydrocarbons (BTEX compounds) often partition into
their gaseous state and are present in the subsurface along with the liquid phase
hydrocarbons. The term “volatile hydrocarbons” refers to those compounds with
vapor pressures greater than 1 mmHg or 0.001 atm. The transport of these gases is
about 100 times faster in soils than in the groundwater and is described in Equation
2.4 by a general form of Darcy’s Law as:
v = –k/m(—P + rg) (Eq. 2.4)
where
v = velocity of laminar air flow through the soil.

k = intrinsic permeability.
m = viscosity.
P = pressure head difference.
r = fluid density.
g = acceleration due to gravity.
The transport of gas occurs due to several transport mechanisms, including

diffusion, convection, and gravity-driven flow; the effective porosity of the soil and
the contaminant’s vapor density are also important. Other factors include air tem-
perature and, for near-surface soil, barometric pressure. In general, molecular diffu-
sion is the dominant transport for the gas phase.
The driving force of convective flow is the gradient of the total gas pressure
which results in the movement of air mass from an area of higher pressure to an area
of lower pressure. In the case of diffusion, the driving force is the partial pressure
gradient of each gaseous component in a gas mixture. It is believed that in most cases
diffusion is the dominant transport mechanism.

TABLE 2.13
Vapor Densities of Gases Relative to Air
Gases Lighter than Air Gases Heavier than Air
Hydrogen Gasoline
Ammonia Chlorine
Acetylene Alcohol
Methane N-gas Acetone
Ethylene Ethylene dibromide
Helium Propane
Gravity-driven flow is the tendency of the vapor to move within the vadose zone
as a function of density. The presence of relatively high concentrations of volatile
compounds detected at the bottom of coarse-grained sediments is an example of this
transport mechanism.
The importance of effective porosity for liquids is identical to that for gas; open
space in the soil must be available for the gas to migrate. In sandy soils, as much as
25% of the volume is air; in loamy soils, it is generally between 15 and 20%; and in
clayey soils, the volume of air space is usually below 10% of the total volume.
As vapor density increases, the potential for the gas to move vertically through
the soil column increases. Vapors move through the soil as a function of the
concentration gradient of the contaminant via diffusion as described by Fick’s Law.
The movement is therefore away from areas of high concentration to areas of
low concentration. Another mechanism is temperature; a temperature gradient in the
soil creates a driving force with volatile compounds moving from areas of high to
low soil temperature. Pressure fluctuations due to barometric pressure changes and
wind across the soil surface can also impact the movement and dispersion of soil
gas in shallow soils (Rolston, 1986). The vapor density of a substance is the
mass of vapor per unit volume. Gases that are heavier and lighter than air are listed
in Table 2.13.
A related characteristic is vapor pressure, which is the pressure exerted by the gas
of a substance in equilibrium conditions. Vapor pressure provides a qualitative rate
at which a compound volatilizes from soil. Table 2.14 is a list of vapor densities and
pressures for commonly encountered hydrocarbons (API, 1994; Luhrs and Stewart,
1992). Soil gas surveys using this property to locate sources of soil and groundwater
contamination commonly report the results as parts per billion per volume (ppbv). A
useful conversion is that 250 ppbv is equal to about 1 mg/L in the vapor phase.
While organic contaminants are absorbed onto organic matter, research has
shown that volatile organic compounds in a gas phase can also sorb onto dry soils.
Mineral matter in dry soils, for example, can adsorb TCE from the vapor phase
(Peterson et al., 1988). Research comparing the uptake of volatile compounds onto
wet vs. dry soil shows that vapor uptake on dry soils is greater than for wet soils.
These findings also indicate that vapor uptake is suppressed by the presence of water

TABLE 2.14
Vapor Densities and Pressures for BTEX and MTBE
Vapor Density Vapor Pressure Temperature
Compound (g/L) (mmHg) (∞C)
Benzene 3.19 76 20
Toluene 3.77 22 20
Ethylbenzene 4.34 12 30
o-Xylene 4.34 6.6 25
m-Xylene 4.34 8.3 25
p-Xylene 4.34 8.8 25
MTBE — 245 25
(Chiou and Shoup, 1985; Ong and Lion, 1991a,b; Poe et al., 1988; Rhue et al., 1988).
In general, soils with a high clay content and large surface area adsorb a greater
amount of a chemical.
Once volatilized, the vapor is transported through the soil by advection and
diffusion. The vapor will move primarily in the horizontal direction, controlled by the
slope of the water table and by geologic media (i.e., gas permeability of the media)
and temperature gradients. Given that residual hydrocarbons can release volatiles for
long periods of time depending on their initial molecular arrangement, soil tempera-
ture, moisture content, and biodegradation, a long-term soil vapor source is often
present.
Products of hydrocarbon degradation are used to identify the location of soil or
groundwater contamination using concentrations of gases, such as carbon dioxide or
methane, as indicators of microbial activity. Elevated concentrations of methane gas,
for example, have been shown to demonstrate that hydrocarbons are reduced by a
wide range of anaerobic processes that can produce vapor phase products (Barcelona
et al., 1996).
2.6 HYDROCARBON INTERACTIONS

AT THE CAPILLARY FRINGE
Vertical migration ceases when a hydrocarbon encounters water-saturated pores (i.e.,

the capillary zone or perched layer), because most petroleum hydrocarbons and refined
products are less dense than water. As the volume of floating product increases,
saturation at the capillary fringe becomes sufficient for lateral spreading to occur. A
mound above the water table will occur along with a corresponding depression in the
water table. The amount of collapse depends on the hydrocarbon density. As the
specific gravities of gasoline and light hydrocarbons are approximately 0.7 to 0.8,

about 70 to 80% of the hydrocarbons will reside below the depth of the original water
table.
Spreading occurs along the groundwater surface as a result of the natural ground-
water gradient. This hydrocarbon lens will spread laterally until equilibrium is
achieved between the lens thickness and the capillary pressure. The balance of forces
results in a thick layer in fine-grained sediments and a thinner layer in coarse
sediments (Ryan and Dhir, 1993). The center of the hydrocarbon mass will move
downgradient with respect to groundwater.
The velocity of the floating product can be estimated via Equation 2.5 (ES&T,
1996; Parker and Leonard, 1990):
nN = (fNrroKh/hrofe)—Zaw (Eq. 2.5)
where
nN = velocity of the leading edge of the gasoline on the water table.

fN = mobility factor defined as oil mobility divided by the free oil specific volume.
rro = specific gravity of the gasoline.
Kh = horizontal saturated hydraulic conductivity to water.
hro = the gasoline-to-water viscosity ratio.
fe = effective or “drainable” soil porosity.
—Zaw = the air/water table gradient (same as the water table gradient, which may
underestimate the gasoline velocity if the travel distance is large and/or the
product thickness is low).
A phenomenon known as thin film spreading occurs within the capillary fringe
and groundwater interface. This hydrocarbon film will be one to two soil pore
diameters thick. This layer spreads laterally along the interface of the capillary fringe
and upper two pore volumes. The hydrocarbon will initially spread over a larger area
than the bulk of the hydrocarbons in contact with the capillary fringe. Solubilization
of hydrocarbon components from this thin film also occurs; compounds with low oil/
water partition coefficients will tend to diffuse outward and transfer into the aqueous
phase, leaving the heavier weight hydrocarbons.
The hydrocarbon residing in the capillary fringe will volatilize into the soil air
(Gierke et al., 1990; Miller et al., 1990; Powers et al., 1991; Wilkins et al., 1995).
Volatile components within the LNAPL will evaporate and diffuse upward, while the
higher molecular weight compounds will remain in the LNAPL pool. The rate of
vapor loss from a LNAPL pool residing at the capillary fringe is described by Fick’s
Law of diffusion (see Section 2.5.4) or can be measured directly. For the latter case,
a soil gas survey above the LNAPL can be used to extrapolate the initial slope of the
concentration vs. height to zero concentration to estimate the effective diffusion
length. When direct measurements are unavailable, the one-dimensional conserva-
tive mass transfer (kaa) due to diffusion described by Fick’s Law is described by
Equation 2.6.

kaa = Daaof4/3S10/3
a Ha/La (Eq. 2.6)
where
Daao = diffusion coefficient in free air for species a.

f4/3 = soil porosity.
S10/3
a = the fraction of pore volume with air (90% or less for coarse-sand soils to 10%
or greater for fine-textured soils).
Ha = Henry’s Law constant.
La = effective diffusion coefficient.
Upon entering the capillary fringe, sufficient hydraulic pressure can exist to cause the
hydrocarbon to move hydraulically upgradient. This upgradient distance is minimal,
however, when compared to the downgradient distance. As the hydrocarbon lens
moves laterally, water in the capillary fringe impedes its movement. In the upper
section of the capillary fringe where small amounts of water are present, the hydro-
carbons tend to migrate laterally. In the lower section of the capillary fringe where
relatively large amounts of water are present, the bulk hydrocarbons will also migrate
laterally but at negligible rates as compared to hydrocarbons in the upper portions of
the capillary fringe.
2.6.1 HYDROCARBON SOLUBILIZATION FROM THE

CAPILLARY FRINGE INTO GROUNDWATER
The solubilization of compounds from a free phase product residing at the capillary
fringe into groundwater results in dissolved components that are compositionally
different than the non-aqueous phase hydrocarbon. For non-oxygenated gasoline,
the most soluble components are benzene, toluene, xylene, and ethylbenzene.
Benzene concentrations in groundwater, for example, are enriched up to ten
times more than their concentration in gasoline. While some unleaded gasoline
contains 49% of the aromatic compounds, water in contact with this gasoline has
been found to contain 95% of these compounds after 30 minutes of mixing (Coleman
et al., 1984).
For crude oils, solubility is partially dependent on the API gravity of the
crude oil. Crude oil with a high API is light (less dense than water), while a low
API crude is heavy. The solubility of the crude oil in contact with groundwater
increases with higher API gravities because high-API crude oils tend to be rich in
low-molecular-weight compounds with high solubilities. Numerous expressions are
available to estimate the rate of dissolution of compounds into the groundwater and
they may be represented as from water washing through the free phase hydrocar-
bon and into the groundwater and via solubilization by groundwater in contact with
the NAPL. An example of the latter approach is described in Equation 2.7 (Pfannkuch,
1984):
Ssa = kov(Csa – Cma) (Eq. 2.7)

where
ko = a dimensionless NAPL mass transfer coefficient defined as ko = Av/L, where

Av is the vertical dispersivity of the aquifer and L is the effective aquifer thickness.
v = groundwater velocity.
Csa = the dissolved concentration in equilibrium with the NAPL in the groundwater.
Cma = actual concentration in the groundwater in the mobile region.
Equation 2.7 requires that the initial mass fraction of the various compounds of interest
be known or approximated. A useful application of this information is to estimate the
concentration of the BTEX components under the NAPL as additional data points for
creating an iso-contour map for dissolved contaminants. It is not uncommon for
groundwater under a gasoline or diesel layer not to be sampled and tested.
2.7 TRANSPORT IN GROUNDWATER
Petroleum hydrocarbons entering groundwater are transported as free and dissolved

phases. The free phase components are normally thickest at the point at which the
hydrocarbon enters the groundwater. The rate of dissolution from the free phase can
be estimated from estimating the partition coefficient from solubility data and from
information on the chemical concentration of the compound.
Most hydrocarbon fractions are immiscible with water. Some components in
hydrocarbons, however, are soluble (i.e., benzene, toluene, ethylbenzene, and total
xylenes) as well as additives such as MTBE. This property provides a useful means
for characterizing hydrocarbons and understanding whether BTEX concentrations
represent near-saturation conditions. Once the soluble fraction of the hydrocarbon
has entered the groundwater, its movement is controlled by the same advective and
dispersive processes used for estimating the mass transport of groundwater.
2.7.1 RATE OF TRANSPORT

Advection describes the mass movement of a chemical in groundwater and is the
dominant mechanism by which chemicals move in groundwater. The primary input
variable affecting advective transport is hydraulic conductivity. The use of hydraulic
conductivity in one form of Darcy’s Law is described by Equation 2.8:
v = [K (h1 – h1)/l]/ne (Eq. 2.8)
where
v = groundwater velocity (units of length over time).

K = hydraulic conductivity (gal/day/ft2, m or cm/sec).
(h1 – h1)/l] = groundwater gradient (dimensionless).
ne = effective porosity (percentage).

TABLE 2.15
Saturated Hydraulic Conductivity
Values for Soils
Soil Hydraulic Conductivity
Texture (cm/sec)
Gravel 102–10–1
Sand 1–10–4
Silty sand 10 –10–5
–1
Silt 10–3–10–7
Glacial till 10–4–10–12
Clay 10–7–10–11
Hydraulic conductivity is a function of the porous medium through which the fluid
is moving and of the fluid. Table 2.15 lists ranges of hydraulic conductivity for
several soils (Driscoll, 1986; Freeze and Cherry, 1979).
The horizontal stratification of sediments results in hydraulic conductivity values
that are usually greater horizontally than vertically. In sediments such as till, prefer-
ential flow of contaminants occurs within small lenses of materials that are more
permeable than the majority of sediments in the aquifer. Since Darcy’s Law is an
averaged value for transport, contaminants can be transported at greater rates within
these preferential layers than what is estimated with Darcy’s Law.
While Darcy’s Law applies to the averaged linear velocity of groundwater, it is
not contaminant specific. To examine the transport of an individual chemical,
retardation must be considered. In an ideal case, soluble components with higher
velocities precede components with decreased velocities at the leading edge of a
contaminant plume. The apparent velocity of BTEX components is affected by the
retardation of the specific compound within the aquifer. For example, the retarda-
tion of benzene within a sand and gravel aquifer at a site in Glouchester, Ontario,
was 8.8; this means that if groundwater flow is 8 feet per day and the benzene
retardation coefficient is 8.8, then the rate of benzene transport is about 0.9 feet per
day (MacKay, 1990).
2.7.2 MTBE TRANSPORT IN GROUNDWATER

Methyl-tertiary-butyl-ether (MTBE) is an oxygenate added to gasoline to increase
both the octane ratio of gasoline and combustion efficiency. MTBE lowers the
atmospheric ozone and carbon monoxide concentrations as required by the Clean Air
Act. In 1992, the U.S. Environmental Protection Agency (EPA) mandated that
oxygenated compounds such as MTBE containing at least 2.7% oxygen by weight
should be added to gasoline. This additive has gained considerable attention in recent
years due to its being a primary contaminant of concern with gasoline releases.
Analytical methods used to test for MTBE are EPA Methods 8020 and 8240/8260.

For drinking waters, EPA Method 524 is used. Another method is a modified ASTM
Method D4815, which tests samples for methanol, ethanol, ethyl-tertiary-butyl-ether
(ETBE), and tertiary-methyl-ether (TAME), as well as MTBE.
The separation of MTBE ((CH3)3C(OCH3)) from the gasoline plume is often
detected along the downgradient edge, followed in time by detection of the BTEX
components (Squillace et al.,1996). MTBE can comprise as much as 11% by volume
of gasoline and is more soluble than benzene; as a result, it tends to be more mobile
than the other soluble gasoline components. A breakdown product of MTBE, tert-
butanol (TBA; tert-butyl alcohol or 2-methyl-2-propanol), is possible, although
additional confirmation research is required (Barker et al., 1996). Tert-butyl alcohol
is a significant degradation product, as it has been identified as a carcinogen in
laboratory animals (Cirvello et al., 1995).
One field study measured a 14% loss of MTBE after 476 days of monitoring,
while another investigation reported aerobic biodegradation of MTBE based on
MTBE losses and oxygen consumption (Horan and Brown, 1995). In general, MTBE
does not readily degrade in the subsurface, and the primary attenuation mechanism
is dispersion. MTBE can decrease the retardation of the BTEX components, as they
are more soluble in ether than in water. As a result, when MTBE is present in a
contaminant plume, the BTEX components are often found in higher concentrations
(Garrett et al., 1986).
The physical and chemical characteristics of MTBE are significantly different
than other compounds found in gasoline. MTBE has a low affinity for organic
carbon; as a result, retardation due to the presence of soil organic matter is minimal.
Testing of the retardation of MTBE in the Borden aquifer in Canada resulted in a
retardation factor of 1.0. The solubility of MTBE (43,000 mg/L) is about 25 times
greater than for benzene (1780 mg/L). The biodegradability of MTBE relative to
aromatic compounds (BTEX) is substantially lower. MTBE will also preferentially
leach from gasoline because it has a high affinity for water, which is why MTBE is
found at the leading edge of a gasoline plume, followed by benzene (assuming a
single spill and chromatographic separation of the components in the groundwater).
The ratio of the MTBE plume in groundwater relative to benzene depends on the
concentrations used to define the leading edge of the gasoline plume and the contami-
nant residency (Rempel and Escalante, 1996). A review of 32 sites found the MTBE
to benzene plume-length relationship to be 1.5 to 2.0 after a few years of contaminant
residency (Davidson, 1995). Another factor in MTBE dissolution from gasoline is
due to the natural attenuation of the BTEX components relative to MTBE. In
groundwater, research has found that toluene had the highest attenuation rate, fol-
lowed by xylene, benzene, and ethylbenzene. While attenuation rates for xylene,
benzene, and ethylbenzene are not significant, toluene is significantly greater (Borden
et al., 1995; Buscheck et al., 1996).
The vertical distribution of MTBE in a gasoline plume usually results in the
MTBE being present at a greater depth than the gasoline. The longer distance of the
MTBE plume relative to the gasoline plume allows the MTBE to be distributed
vertically over a greater distance. The longer MTBE plume can also be driven deeper
into the aquifer due to infiltration events.

The shape of a MTBE hydrocarbon plume also depends on whether the release
originates from a point or line source and if it is transient vs. steady state. For
underground storage tanks, it is estimated that 65% of all releases originate from the
product lines, 25% are from the tanks, and the remaining sources are from causes
such as overfilling or spillage. Releases from each of these types of sources will
therefore result in a different type of plume geometry in the subsurface. A line source
creates a large area into which the hydrocarbons are entering the groundwater, while
a point source release creates more of a tear-shaped plume with the apex of the tear
at the point source. The temporal nature of the release will also impact the geometry
of the contaminant plume. A transient release creates a “pulse” or discrete mass of
contaminant that flows advectively with the groundwater; a steady-state release tends
to create a more continuous plume.
Dispersivity also affects the geometry of an MTBE plume. Dispersivity is the
three-dimensional spreading of a contaminant plume in groundwater; it is primarily
dependent on the aquifer characteristics and the geometry of the contaminant source
area. Dispersivity values are obtained by fitting mathematical models to plume data
or from measured values obtained from dye tracer tests performed in the field. Values
for dispersivity increase with distance from the source, although a relatively stable
value (macro-dispersivity) should be obtained at some distance from the source.
Dispersivity values are used in a longitudinal, transverse, and vertical direction
relative to the center of mass of a contaminant plume. In general, the horizontal
dispersivity is about ten times greater than the vertical transverse dispersivity (Davis,
1986). (See Chapter 1, Section 1.8.5, for further details.)
2.7.3 LENGTH OF A PETROLEUM HYDROCARBON PLUME

Recent examination of hydrocarbon plumes has resulted in the finding that plumes
rarely exceed 260 feet in length (Rice et al., 1995). These observations, in turn,
provide evidence for consideration and/or adoption of natural attenuation strategies
(see ASTM Standard Guide for Remediation by Natural Attenuation at Petroleum
Release Sites, ASTM, 1996). Lawrence Livermore National Laboratory conducted a
study of hydrocarbon plumes in groundwater for the California State Water Re-
sources Control Board to support revision of the Leaking Underground Fuel Tank
corrective action process; hydrocarbon plume lengths in groundwater were summa-
rized in this study. These results are similar to the findings of a study by Chevron of
119 sites in California. The results of both studies are summarized in Table 2.16
(Buschek et al., 1996; Rice et al., 1996).
These studies also classified hydrocarbon plumes in terms of the change in plume
geometry for benzene. The plumes were described as “shrinking”, “no significant
trend”, and “increasing”. Table 2.17 lists the result of this classification in percentage
of the total sites (Buschek et al., 1996). A recent examination of the Lawrence
Livermore data indicated that benzene plume lengths defined by the 1-ppm concen-
tration contour were less than 200 ft for 90% of the 1092 sites and less than 75 ft for
70% of the leaking underground storage tanks sites (McNab and Dooher, 1999).

TABLE 2.16
Length of Hydrocarbon Plumes in Groundwater
Plume Length Lawrence Livermore Chevron
(L) (% of 271 sites) (% of 62 sites)
L < 100 ft 50 47
100 ft < L < 260 ft 40 40
L > 260 ft 10 13
Analytical solutions for groundwater transport and attenuation of hydrocarbons

used to estimate the length of hydrocarbon plumes are similar in the Lawrence
Livermore and Chevron findings (Domenico, 1987). Similarities between modeled
and observed plume lengths include the finding that BTEX plumes may be relatively
short (< 300 ft). Longer plumes might be expected when groundwater velocity is high
(> 0.1 ft/day) and when attenuation rates are relatively low. Modeling results of
hydrocarbon plumes also suggest that BTEX plumes may reach stable or steady-state
conditions within 3 to 7 years (McCallister, 1996). These correlations suggest that,
in cases where monitoring data are available to verify plume attenuation rates and
groundwater velocities are known, groundwater modeling may be used to estimate
plume lengths reliably. This information can assist in identifying optimum locations
for additional monitoring wells.
2.7.4 TRANSPORT IN FRACTURES

Fractures such as joints, faults, or bedding plane separations can occur in a variety
of geologic media. The release of hydrocarbons into a fracture system is significant
in that the velocities can be greater than for an unconsolidated media, and the
distribution of the hydrocarbons within the fracture system becomes difficult to
define.
TABLE 2.17
Changes in Hydrocarbon Plume Geometry
Change in Lawrence Livermore Chevron
Plume Geometry (% of 271 sites) (% of 62 sites)
Shrinking 59 51
No significant trend 33 40
Increasing 8 9a
a Insufficient data for 10 or 11 sites.

The flow of hydrocarbons that have entered a fracture network is controlled by
a number of factors, including the fracture aperture (i.e., the distance between the
fracture walls), fracture density (i.e., spacing between the fractures), and fracture
length and orientation. While fracture spacing, length, and orientation control the
degree of interconnection of the fracture network and can be mapped, fracture
aperture is usually not measurable in the field. The inability to measure fracture
apertures is primarily due to their size (10 to 100 mm) and the interferences caused
from drilling or excavation stress relief. As a result, aperture values are usually
estimated using the “cubic law” (Snow, 1969), which is based on the relationship
between hydraulic gradient and the discharge for a viscous fluid flowing between two
parallel smooth surfaces. In reality, apertures can vary greatly in size and wall
roughness, but these are not easily measured.
The transport of a dissolved phase hydrocarbon in a fractured porous medium
occurs by advection through the fractures, advection into the fracture wall matrix,
and diffusion into the fracture walls (assuming that the material is porous). In most
cases, advection into the wall is negligible; diffusion controls solute transport from
rapidly moving liquid through the fractures into the relatively immobile pore water
of the wall matrix.
The process of matrix diffusion can theoretically retard the overall migration of
a hydrocarbon by several orders of magnitude relative to transport within the fracture
system. For example, modeling simulations showed that in a scenario which included
matrix diffusion, chloride migrating through a 25-mm aperture fracture in a glacial
clay would take about 50 years to reach the underlying aquifer present at a depth of
10 m (Sudicky and McLaren, 1992). For the same modeling scenario but with no
matrix diffusion, the solute would reach the aquifer within about half a day.
For non-aqueous phase liquids (NAPLs) moving vertically through a fracture
system, the transport will be rapid after the release; diffusion will have little impact,
as the aperture size and hydrocarbon properties (density, interfacial tension, and
viscosity) will impact the rate of flow (Kueper and McWhorter, 1991). Once the
hydrocarbon becomes immobilized within the fracture system, diffusion into the
porous matrix will occur. The diffusion of the hydrocarbon into the porous matrix
significantly complicates the remediation of the hydrocarbons present within the
porous media.
REFERENCES
API, 1995. Petroleum Contaminated Low Permeability Soil: Hydrocarbon Distribution Pro-
cesses, Exposure Pathways and In Situ Remediation Technologies, API No. 4361, Ameri-
can Petroleum Institute, Washington, D.C., pp. A1–A34.
API, 1994. Transport and Fate of Non-BTEX Petroleum, API No. 4593, American Petroleum
Institute, Washington, D.C., p. 85.
API, 1989. A Guide to the Assessment and Remediation of Underground Petroleum Releases,
2nd ed., API No. 1628, American Petroleum Institute, Washington, D.C., p. 81.

API, 1985. Literature Survey: Hydrocarbon Solubilities and Attenuation Mechanisms, API
No. 4414, American Petroleum Institute, Washington, D.C., p. 101.
ASTM, 1996. Standard Guide for Remediation by Natural Attenuation at Petroleum Release
Sites (draft), American Society for Testing Materials, Philadelphia, PA, p. 16.
ATSDR, 1995. Toxicological Profile for Stoddard Solvent, Agency for Toxic Substances and
Disease Registry, Public Health Service, U.S. Department of Health and Human Services,
Atlanta, GA, p. 3.
Barcelona, M. and R. Morrison, 1988. Sample collection, handling and storage: water, soils,
and aquifer solids, in Proc. of Groundwater Quality Methodology Workshop, November
13, Cooperative States Research Service, Arlington, VA, p. 13.
Barcelona, M., Fang, J., and C. West, 1996. Monitoring in situ bioremediation of fuel
hydrocarbons: the use of chemical and biochemical markers, in 1996 Proc. of the
Petroleum Hydrocarbons and Organic Chemicals in Ground Water: Prevention, Detec-
tion, and Remediation Conference, November 13–15, National Ground Water Associa-
tion, Houston, TX, pp. 511–523.
Barker, J., Schirmer, M., and C. Hubbard, 1996. The longer term fate of MTBE in the Borden
aquifer, in Proc. of the 1996 Petroleum Hydrocarbons and Organic Chemicals in Ground-
water: Prevention, Detection, and Remediation Conference, November 13–15, National
Ground Water Association, Houston, TX, pp. 5–14.
Borden, R., Gomez, A., and M. Becker, 1995. Geochemical indicators of intrinsic bioremediation,
Ground Water, 33(2):180–189.
Bruya, J., 1999. Chromatograms, Friedman and Bruya, Seattle, WA.
Buschek, T., Wickland, D., and D. Kuehne, 1996. Multiple lines of evidence to demonstrate
natural attenuation of petroleum hydrocarbons, in Proc. of the 1996 Petroleum Hydrocar-
bons and Organic Chemicals in Groundwater: Prevention, Detection, and Remediation
Conference, November 13–15, National Ground Water Association, Houston, TX, pp.
445–459.
California Environmental Protection Agency, 1996. Draft Policy for Cleanup of Petroleum
Discharge: October 29 letter from Harry Schueller to Regional Water Quality Control
Board Executive Officers, State Water Resources Control Board Resolution No. 1021b,
p. 4.
Chen, C., Rao, S., and J. Delfino, 1977. Cosolvent Effects on the Dissolution of Polynuclear
Aromatic Hydrocarbons Due to Spills of Oxygenated Fuel in the Subsurface Environ-
ment, presented at the 213th Annual Meeting of the American Chemical Society, Divi-
sion of Environmental Chemistry, April 13–17, San Francisco, CA, Preprints of Extended
Abstracts, 37(1):387–389.
Chiou, C., 1989. Theoretical considerations of the partition uptake of nonionic organic
compounds by soil organic matter, in Sawhney, B.L. and K. Brown, (Eds.), Reactions and
Movement of Organic Chemicals in Soils, Soil Science Society of America, Madison, WI,
pp. 1–19.
Chiou, C. and T. Shoup, 1985. Soil sorption of organic vapors and effects of humidity on sorptive
mechanism and capacity, Environmental Science and Technology, 19:1196–1200.
Cirvellol, J., Radovsky, A., Heath, J., Farnell, D., and C. Lindamood, 1995. Toxicity and
carcinogenicity of t-butyl alcohol in rats and mice following chronic exposure in drinking
water, Toxicology and Industrial Health, 11(2):151–166.
Coleman, W., Munch, J., Stricher, R., Ringhand, H., and F. Kopfler, 1984. The identification
and measurement of components in gasoline, kerosene, and No. 2 fuel oil that partition
into the aqueous phase after mixing, Archives of Environmental Contamination and
Toxicology, 13:171–178.

Corey, A., 1986. Air permeability, in Klute, A. (Ed.), Methods of Soil Analysis. Part I. Physical
and Mineralogical Methods, 2nd ed., American Society of Agronomy, Madison, WI, pp.
1121–1136.
Daniel, D., Anderson, D., and S. Boynton, 1986. Fixed wall versus flexible wall permeaters,
in Hydraulic Barriers in Soils and Rocks, ASTM STP 874, American Society for Testing
Materials, Philadelphia, PA, pp. 107–126.
Danielson, R., and P. Sutherland, 1986. Porosity, in Klute, A. (Ed.), Methods of Soil Analysis.
Part I. Physical and Mineralogical Methods, 2nd ed., American Society of Agronomy,
Madison, WI, p. 443–461.
Davidson, J., 1995. Fate and transport of MTBE: the latest data, in 1995 Proc. of the Petroleum
Hydrocarbons and Organic Chemicals in Ground Water: Prevention, Detection, and
Remediation Conference, National Ground Water Association, Dublin, OH, pp. 285–301.
Davis, A., 1986. Deterministic modeling of dispersion in heterogeneous permeable media,
Ground Water, 24(5):609–615.
Domenico, P., 1987. An analytical model for multidimensional transport of a decaying
contaminant species, Journal of Hydrology, 91:49–58.
Dragun, J., 1988. The Soil Chemistry of Hazardous Materials, Hazardous Materials Control
Research Institute, Silver Springs, MD, p. 458.
Driscoll, F., 1986. Groundwater and Wells, Johnson Division, St. Paul, MN, p. 1089.
Dunlap, L. and D. Beckmann, 1988. Soluble hydrocarbon analysis from kerosene/diesel type
hydrocarbons, in Proc. of the Association of Ground Water Scientists and Engineers and
the American Petroleum Institute (API) Conference on Petroleum Hydrocarbons and
Organic Chemicals in Ground Water, National Ground Water Association, Houston, TX,
pp. 37–45.
ES&T, 1996. ARMOS User Guide: A Real Multiphase Organic Simulator for Free Phase
Hydrocarbons Migration and Recovery, Environmental Systems & Technologies, 2608
Sheffield Drive, Blacksburg, VA.
aqueous phase liquids (DNAPLs) in the subsurface, in Pankow, J. and J. Cherry (Eds.),
Dense Chlorinated Solvents and other DNAPLs in Groundwater, Waterloo Press, Guelph,
Ontario, pp. 53–128.
Freeze, A., and J. Cherry, 1979. Groundwater, Prentice-Hall, Englewood Cliffs, NJ, p. 604.
Freyberg, D., 1986. A natural gradient experiment on solute transport in a sand aquifer. 1.
Spatial moments and the advection and dispersion of nonreactive tracers, Water Re-
sources Research, 22(13):2031–2046.
Galperin, Y., 1997. Application of Forensic Geochemical Methods for Hydrocarbon Fuels
Fingerprinting and Age Dating. Section 2. Hydrocarbon Pattern Recognition and Dat-
ing, University of Wisconsin College of Engineering, Madison, WI, p. 41.
Garrett, P., Moreau, M., and J. Lowry, 1986. Methyl tertiary butyl ether as a ground water
contaminant, in Proc. of the Petroleum Hydrocarbons and Organic Chemicals in Ground
Water Conference, National Water Well Association and American Petroleum Institute,
Washington, D.C., pp. 227–238.
Gibbs, L., 1990. Gasoline Additives: When and Why?, Technical Paper 902104, Society of
Automotive Engineers, Warrendale, PA, p. 24.
Gierke, J., Hutzler, N., and J. Crittenden. 1990. Modeling the movement of volatile organic
chemicals in unsaturated soils, Water Resources Research, 26(7):1529–1547.
Hartman, B., 1998. Applications and interpretations of soil vapor data, in Petroleum Hydro-
carbons: Legal and Technical Considerations, Argent Communications Group, Foresthill,
CA, p. 81–110.

Harvey, E., 1988. Changes in the composition of gasoline and blended products, in Proc. of
the Environmental Forensics: Determining Liability through Applied Science Confer-
ence, International Business Communications (IBC), Southborough, MA, p. 15.
Havlicek, S., 1986. Characteristics of Fuels and Fuel Spills, marketing publication, Coast to
Coast Analytical Services, Santa Barbara, CA, p. 14.
Hill, D. and J. Parlange, 1972. Wetting front instability in layered soils, Soil Science Society
of America Proceedings, 36:697–702.
Hoag, G. and M. Marley, 1986. Gasoline residual saturation in unsaturated uniform aquifer
materials, Journal of Environmental Engineering, 112(3):586–604.
Horan, C. and E. Brown, 1995. Biodegradation and inhibitory effects of methyl-tertiary-butyl
ether (MTBE) added to microbial consortia, in Proc. of the 10th Annual Conference on
Hazardous Waste Research, Kansas State University, Manhattan, pp. 11–19.
Howard, P., Boethling, R., Jarvis, W., Meylan, W., and E. Michalenko (Eds.), 1991. Handbook
of Environmental Degradation Rates, Lewis Publishers, Chelsea, MI, p. 725.
Hughes, W. and A. Holba, 1988. Relationship between crude oil quality and biomarker
patterns, Organic Geochemistry, 13:15–30.
Johnson, P., Kemblowski, M., and J. Colthart, 1990. Quantitative analysis for the cleanup of
hydrocarbon contaminated soils by in situ soil venting, Ground Water, 28(3):413–429.
Kao, C. and R. Borden, 1997. Site-specific variability in BTEX biodegradation under denitri-
fying conditions, Ground Water, 35(2):305–311.
Kaplan, I., 1995. Hydrocarbon and Tracers in Crude Oil and Refined Products for Identifi-
cation, Characterization, and Litigation, Engineering and Professional Development
Extension Program, National Institute on Hydrocarbon Fingerprinting, University of
Wisconsin, Madison, p. 18.
Kaplan, I. and Y. Galperin, 1996. How to recognize a hydrocarbon fuel in the environment and
estimate its age of release, in Bois, T. and B. Luther (Eds.), Groundwater and Soil
Contamination: Technical Preparation and Litigation Management, John Wiley & Sons,
New York, pp. 145–199.
Kaplan, I., Alimi, M., Galperin, Y., Lee, R., and S. Lu, 1995. Pattern of Chemical Changes in
Fugitive Hydrocarbon Fuels in the Environment, SPE 29754, presented at Society of
Petroleum Engineers, SPE/EPA Exploration and Production Environmental Conference,
Houston, TX, March 27–29, 1995.
Kargbo, D., 1994. Chemical contaminant reactions and assessment of soil cleanup levels for
protection of groundwater, Environmental Geology, 23:105–113.
Kimball., B., 1983. Canopy gas exchange: gas exchange with soil, in Taylor, H.M. et al. (Eds.),
Limitations to Efficient Water Use in Crop Production, American Society of Agronomy,
Madison, WI, pp. 215–226.
Kueper, B. and D. McWhorter, 1991. The behavior of dense, non-aqueous phase liquids in
fractured clay and rock, Ground Water, 29:716–728.
Lane, W. and R. Loehr, 1992. Estimating the equilibrium aqueous concentrations of poly-
nuclear aromatic hydrocarbons in complex mixtures, Environmental Science and Tech-
nology, 26(5):983–990.
Luhrs, R. and N. Stewart, 1992. Graphical evaluation of gasoline contaminated water: a
powerful new approach, in Proc. of the Focus Conference on Eastern Regional Ground
Water Issues, October 13–15, National Ground Water Association, Newton, MA, p. 15.
MacKay, D, 1990. Characterization of the distribution and behavior of contaminants in the
subsurface, in Ground Water and Soil Contamination Remediation: Toward Compatible
Science, Policy and Public Perception, report on a colloquium sponsored by the Water
Science and Technology Board, National Academy Press, Washington, D.C., pp. 70–90.

Manahan, S., 1984. Environmental Chemistry, 4th ed., PWS Publishers, Boston, MA, p. 612
McAllister, P., 1996. Application of screening model approaches for evaluation of BTEX
natural attenuation in groundwater, in 1996 Proc. of the Petroleum Hydrocarbons and
Organic Chemicals in Ground Water: Prevention, Detection, and Remediation Confer-
ence, National Ground Water Association, Dublin, OH, pp. 481–494.
McNab, W. and B. Dooher, 1999. Discussion of papers, Ground Water, 37(2):167–168.
Metcalf and Eddy, Inc., 1993. Chemical and Physical Characteristics of Crude Oil, Gasoline,
and Diesel Fuel: A Comparative Study, Western States Petroleum Association, Glendale,
CA, p. 33.
Miller, C., Poirier-McNeil, M., and A. Mayer, 1990. Dissolution of trapped non-aqueous phase
liquids; mass transfer characteristics, Water Resources Research, 26(11):2783–2796.
Morrison, R., 1997. Forensic techniques for establishing the origin and timing of a contami-
nant release, Environmental Claims Journal, 9(2):105–122.
Neilsen, J. and S. Hansen, 1992. Fate and Transport of Creosote Compounds in a Sand Aquifer
at CFB Borden, Ontario, Canada, Master’s thesis, Technical University of Denmark,
Lyngby.
Neuman, S. and G. Chen, 1996. On instability during immiscible displacement in fractures and
porous media, Water Resources Research, 32(6):1891–1894.
Neumann, H., Paczynska-Lahme, B., and D. Severin, 1981. Composition and Properties of
Petroleum, Halstead Press, New York, p. 561.
Nkedi-Kizza, P., Rao, S., and A. Hornsby, 1987. Influence of organic cosolvents on leaching
of hydrophobic organic chemicals in soils, Environmental Science and Technology,
21:1107–1111.
Odencrantz., J., Farr., J., and C. Robinson, 1992. Transport model parameter sensitivity for soil
clean-up level determinations using SESOIL and AT123D in the context of the California
leaking underground fuel tank field manual, Journal of Soil Contamination, 1(2):159–
182.
Ong., S. and L. Lion, 1991a. Mechanisms for trichloroethylene vapor sorption onto soil
minerals, Journal of Environmental Quality, 20:180–188.
Ong., S. and L. Lion, 1991b. Trichloroethylene vapor sorption onto soil minerals, Soil Science
Society of America Journal, 55:1559–1568.
Parker, J. and R. Lenhard, 1990. Vertical integration of three phase flow equations for analysis
of light hydrocarbon plume movement, Transport in Porous Media, 23:2187–2196.
Perry, R. and C. Chilton, 1973. Chemical Engineers’ Handbook, 3rd ed., McGraw-Hill, New
York.
Peterson, J. et al., 1988. Influence of vapor phase sorption and diffusion on the fate of
trichloroethylene in an unsaturated aquifer system, Environmental Science and Technol-
ogy, 22:571–578.
Pfannukuch, H., 1984. Determination of the contaminant source strength from mass exchange
processes at the petroleum/ground water interface in shallow aquifer aquifers, in Proc. of
the NWWA/API Conference on Petroleum Hydrocarbons and Organic Chemicals in
Ground Water Prevention, Detection, and Restoration, Session II, November 5–7, Na-
tional Water Well Association, Dublin, OH, p. 111–130.
Philip, P., 1988. Forensic geochemistry: who was responsible for the spill?, in Proc. of
Environmental Forensics: Determining Liability through Applied Science Conference,
September 24–25, International Business Communications (IBC), Southborough, MA.
Poe, S., Valasaraj, K., Thibodeaux, L., and C. Springer, 1988. Equilibrium vapor phase
adsorption of volatile organic chemicals on dry soils, Journal of Hazardous Matter,
19:17–32.

Polak, J. and B. Lu, 1973. Mutual solubilities of hydrocarbon and water at 0 and 25∞C,
Canadian Journal of Chemistry, 51:4018–4023.
Powers, S., Loureiro, C., Abriola, L., and W. Weber, 1991. Theoretical study of the signifi-
cance of nonequilibrium dissolution of nonaqueous phase liquids in subsurface systems,
Water Resources Research, 27(5):363–377.
Raymond, R., Hudson, J., and V. Jaminson, 1976. Oil degradation in soil, Applied and
Environmental Microbiology, 31(4):522–535.
Rempel, R. and F. Escalante, 1996. Comparison of Dissolved MTBE vs. Benzene Plumes at
Seven Unocal Sites in California, abstract from Association for the Environmental Health
of Soils Annual Conference, October 1996, University of Massachusetts, Amherst.
Rhue, R., Rao, P., and R. Smith, 1988. Vapor phase adsorption of alkylbenzenes and water on
soils and clays, Chemosphere, 17:727–741.
Rice, D., Grose, R., Michaelson, J., Dooher, B., MacQueen, D., Cullen, S., Kastenberg, W.,
Everett, K., and M. Marino, 1995. California Leaking Underground Fuel Tank (LUFT)
Historical Case Analysis, UCRL-AR-122207, Environmental Protection Department,
Lawrence Livermore National Laboratory, Berkeley, CA; submitted to the California
State Water Resources Control Board.
Rohrbach, G. et al., 1953. Corrosion inhibitors for oil wells, U.S. Patents 2,635,996–2,636,000,
April 21.
Rolston, D., 1986. Gas flux, in Klute, A. (Ed.), Methods of Soil Analysis. Part I. Physical and
Mineralogical Methods, 2nd ed., American Society of Agronomy, Madison, WI, pp.
1103–119.
Rossi, S. and W. Thomas, 1981. Solubility behavior of three aromatic hydrocarbons in distilled
water and natural seawater, Environmental Science and Technology, 15:715–716.
Ryan, R. and V. Dhir, 1993. The effect of soil-particle size on hydrocarbon entrapment near
a dynamic water table, Journal of Soil Contamination, 2(1):59–92.
sure Assessment Model for Evaluating the Land Disposal of Wastes: Model Theory, EPA
600/R-93/081, U.S. Environmental Protection Agency, Washington, D.C., p. 122.
Schmidt, G., 1998. The effect of petroleum weathering on pattern recognition and dating, in
Proc. of Environmental Forensics: Determining Liability through Applied Science Con-
ference, September 24–25, International Business Communications (IBC), Southborough,
MA, p. 11.
Seifert, W. and J. Moldowan, 1978. Application of steranes, triterpanes and monoaromatics to
the maturation, migration and source of crude oils, Geochimica et Cosmochimica Acta,
42:77–95.
Sellers, K. and C. Fan, 1991. Soil vapor extraction: air permeability testing and estimation
methods, in Proc. of the 17th RREL Hazardous Waste Research Symposium, EPA/600/
991/002, U.S. Environmental Agency, Washington, D.C.
Siegrist, R., 1993. VOC measurement in soils: the nature and validity of the process, in
National Symposium on Measuring and Interpreting VOCs in Soils: State of the Art
Research Needs, American Petroleum Institute and the University of Wisconsin at
Madison Extension Engineering Program, January 12–14, U.S. Environmental Protection
Agency, Washington, D.C., p. 9.
Snow, D., 1969. Anisotropic permeability of fractured media, Water Resources Research,
29:716–728.
Squillace, P., Zogorski, J., Wilber, W., and C. Price, 1996. Preliminary assessment of the
occurrences and possible sources of MTBE in groundwater in the United States, 1993–
1994, Environmental Science and Technology, 30:1721–1730.

Stout, S. et al., 1999. Biomarkers — underutilized components in the forensic toolkit, Soil and
Groundwater Cleanup, June/July, 58–59.
Sudicky, E. and R. McLaren, 1992. The Laplace transform Galerkin techniques for large scale
simulation of mass transport in discretely fractured porous formations, Water Resources
Research, 28(2):499–514.
Tanner, C. and R. Wengel, 1957. An air permeameter for field and laboratory use, Soil Science
Society of America Proceedings, 21(6):663–664.
U.S. Environmental Protection Agency, 1986. Hazardous waste management system: land
disposal restrictions, Federal Register, 15(9):1649.
U.S. Geological Survey, 1979. Ground-water hydraulics, Geological Survey Professional
Paper, 708:70.
Wellman, D., Reid, D., and A. Ulery, 1999. Elevated soil arsenic levels at a former crude oil
storage facility: assessment, remediation, and possible sources, Journal of Soil Contami-
nation, 8(3), 329–341.
Wilkins, M., Abriola, L., and K. Pennell, 1995. An experimental investigation of rate-limited
nonaqueous phase liquid volatilization in unsaturated porous media: steady state mass
transfer, Water Resources Research, 31(9):2159–2172.
Wilson, J., Pfeffer, F., Weaver, J., Kampbell, D., Wiedemeier, T., Hansen, J., and R. Miller,
1994. Intrinsic bioremediation of JP-4 jet fuel, in Symposium on Natural Attenuation of
Ground Water, EPA/600R-94/162, U.S. Environmental Protection Agency, Washington,
D.C., pp. 60–67.
10:501–506.
Zemo, D. and T. Graf, 1993. The importance and benefit of fingerprint characterization in site
investigation and remediation focusing on petroleum hydrocarbons, in 1993 Proc. of the
Petroleum Hydrocarbons and Organic Chemicals in Ground Water: Prevention, Detec-
tion, and Restoration, November 10–12, National Ground Water Association, Dublin,
OH, p. 39–54.

3 Identification of Biased
Environmental Data
Coincidence, error, studied ignorance, or junk science?
3.1 INTRODUCTION
An expert opinion is worth no more than the factual data upon which it is based. The
critical review of environmental data is therefore essential for judging the reliability
of the factual information. Environmental data relied upon to form an opinion should
be of a sufficient known quality to withstand the scientific and legal challenges
relative to the purpose of the data collection.
In most instances, only a small percentage (about 10 to 15%) of the data in an
environmental investigation contains elements susceptible to bias. These elements
are usually associated with the geologic investigation and sample collection, analyti-
cal testing, and interpretation of the horizontal and vertical extent of soil and
groundwater contamination.
An important task in the forensic review of environmental data is the determina-
tion of whether a pattern of bias (systematic error) exists. This bias can be due to
factually incorrect information, errors, or intentional manipulation. Figure 3.1 illus-
trates bias and data variability (random error) based on a sample population whose
true concentration is about 20 parts per million (ppm). As depicted in Figure 3.1, data
can be biased negatively or positively. Three specific types of biases and/or errors are
defined as follows:
1. Positive bias: In a data sufficiency context, a positive bias arises when a test
incorrectly indicates contamination or an increase in contamination when there is
none.
2. Negative bias: In a data sufficiency context, a negative bias occurs when monitor-
ing fails to detect contamination or an increase in the concentration of a hazardous
material.
3. Erratic data: Erratic data are anomalous values which make it statistically impos-
sible to develop meaningful trends and/or correlations.
These biases result from investigative, sampling, analytical, and statistical errors.
Ultimately, expert witness opinions based on incorrect information can result.

FIGURE 3.1 Graphical representation of sample bias and variability. (From Mishalanie, E.,
in Proc. of the National Environmental Forensic Conference: Chlorinated Solvents and
Petroleum Hydrocarbons, August 27–28, College of Engineering and Engineering Profes-
sional Development, University of Wisconsin, Madison, 1998, p. 27. With permission.)
3.2 GEOLOGIC CHARACTERIZATION
The geologic characterization component of a site investigation provides insight

regarding contaminant distribution and transport. Components of a geologic inves-
tigation usually include:
• Drilling and logging of the boreholes and/or trenches

• Soil retrieval for textural classification and/or physical testing
• Soil sampling for chemical analysis
The first step is to acquire and review the original field borings and/or trench logs.
Compare the information on the field logs and final logs in the report for consistency.
If geologic cross-sections or fence diagrams are included in the report, examine them
for consistency with the field log/trench descriptions.
When reviewing boring logs, examine their placement relative to historical
information, especially areas of known or suspected contamination. This review
often provides insight as to whether additional borings and/or sampling are neces-
sary. Given that site access agreements among multiple parties are usually required
in order to perform additional sampling, the sooner the data sufficiency of the

TABLE 3.1
Soil Classification Schemes
Particle Size Classification Classification Scheme Used
Very fine sand to silt U.S. Department of Agriculture

Very fine sand to coarse silt Canada Soil Survey Committee
Fine sand International Soil Science Society
Fine sand to fines (silt and clay) American Society of Testing Materials
Fine sand to fines (silt and clay) German Standards
Fine sand to silt British Standards Institute
geologic information is identified, the sooner the site access agreements and sam-
pling can proceed. The sufficiency of existing geologic information can be deter-
mined via the following steps:
• Ascertain whether the drilling method employed allows an accurate description of

the subsurface.
• Determine whether the number of soil borings are sufficient to characterize the
geologic environment relative to litigation allegations.
• Decide whether the borings are sufficiently deep to characterize the geology of
interest.
• Decide whether the borings are spatially located so as not to preclude developing
useful information for geologic characterization.
The drilling technology impacts the geologist’s ability to describe the soil and/or
geologic setting. Reliance solely on mixed drill cuttings from air or mud rotary
drilling, for example, precludes the ability to provide detailed descriptions of strati-
graphic changes. Continuous hollow stem augering and/or most push technologies
that retrieve an in situ soil sample provide this level of detail.
3.2.1 BORING LOG TERMINOLOGY

Soil descriptions on a boring log are based on visual observations of drill cuttings or
from physical testing (e.g., sieve analysis and hydrometer tests). The review of soil
textural descriptions requires that a uniform soil classification scheme be used or that
different classifications are standardized (ASTM, 1993). The use of multiple soil
classification schemes is not uncommon where numerous environmental consultants
have performed geologic investigations at the site.
An illustration of the importance of a common classification scheme is a soil
described as a silt based on the results of a grain size analysis. The particle size of
the soil lies between 0.1 and 0.02 mm. Based on these grain size results, multiple
particle size classifications are possible, as shown in Table 3.1 (Gee et al., 1986;
Hillel, 1982; Wilson et al., 1998). According to the International Soil Science Society
classification, the soil is a fine sand. Other schemes classify the soil as ranging from

FIGURE 3.2 Unified Soil Classification System, grain size chart, and well construction
symbols used on boring logs.
a silt to a fine sand. All are correct for their respective classification schemes.
Without adjusting these interpretations to a common standard, however, subsequent
geologic interpretations and associated diagrams can perpetuate this nonstandardized
bias. In the United States, the Unified Soil Classification System developed by the
Corps of Engineers (U.S. Corps of Engineers, 1960) is the most commonly used
system (Figure 3.2).

Soil color is usually recorded on a boring log. If a standardized color scheme is
not used, the correlation value of this information should be considered qualitative.
The most common color standard is the Munsell Soil Color Chart, which contains
196 different standard color chips (Kollmorgen Corp., 1975). The Munsell system is
arranged by the following characteristics:
• Hue is the color of the soil relative to red, yellow, green, blue, and purple.
• Value indicates the lightness of the soil (0 for black and 10 for absolute white).
• Chroma is the strength of the color (0, for neutral grays, to 20). For absolute
achromatic colors (pure grays, white, and black) with zero chroma and no hue, the
letter N (neutral) is used in place of the hue designation.
A notation such as 5YR 5/6 on a boring log indicates use of the Munsell system. In
“5YR”, 5 is the middle of the color value between yellow and red color hue (YR).
The notation “5/6” is the chroma value between 5 and 6.
Boring logs often contain soil terminology used by non-geologists (drillers or
soil scientists). A driller’s log may qualitatively describe a soil as light or heavy. A
sandy soil that is loose and well aerated is called light, while a clayey soil that tends
to absorb and retain fluid when wet is termed heavy. If there is doubt about the
meaning of such terms, ask the author of the boring log.
When soil samples are collected at random depth intervals, ascertain whether
there is an attempt to avoid collecting soil samples with a higher or lower probability
of detecting contamination. An example is the consistent sampling of coarse sands
and the avoidance of sample collection in finer grained materials (silty or clayey
soils) through which a contaminant with a high sorption capacity has infiltrated.
Conversely, soil samples collected at the interface of coarse, overlying, fine-grained
sediments (i.e., a sand overlying a clay) can result in an overestimation of the
concentration, volume, and (by extension) remediation costs for the contaminated
soil. An extension of this manipulation is the use of small sample volumes for
chemical analysis which biases the chemical results due to the soil particle size not
being representative. This technique assumes that the association of a chemical in the
soil is uniquely associated with a particular particle size.
A proposed approach to quantify this potential particle size bias is to examine the
sample size required for analysis relative to the particle size distribution of the soil
sample. This method identifies the potential bias due to the grain size distribution
between soil samples collected from similar soil textures. Ramsey (1996) defines this
potential bias due to the particle size representativeness as:
S = (22.5d3/ms)1/2 (Eq. 3.1)

where
S = sample mass.
22.5 = sampling constant, which is an approximation and is applicable to many, but
not all, hazardous waste materials.
d3 = maximum particle diameter.
ms = sample mass in grams.

FIGURE 3.3 Boring log with organic vapor analysis measurements.
In most cases, the larger the sample volume, the smaller the potential particle size
bias. If a soil sample is homogenized or sieved by the laboratory and a particular
particle size fraction is selected for extraction, a similar chemical bias can be
introduced. Examination of laboratory documentation will provide this information.
If a contaminant is migrating through the soil via unsaturated flow, it can
preferentially circumvent a coarse-grained layer. As a result, systematic sampling of
these coarse-grained sediments underestimates the extent of contamination. Con-
versely, sampling consistently at the interface of a coarse and fine-grained sediment
through which a contaminant has traveled in an unsaturated state provides the
greatest opportunity of detecting a contaminant. Plate 3.1* illustrates a field experi-
ment where dye moving through a medium-grained glacial sand in an unsaturated
state preferentially migrates around the coarse-grained sediment.
* Plate 3.1 appears behind page 242.

FIGURE 3.4 Boring log with field measurements (OVA and HNu™).
Soil lithology descriptions, field measurements, and sampling locations re-

corded on a boring log can provide insight regarding the intentional manipulation
of sampling locations for the purpose of biasing the chemical results. Figure 3.3 is
a portion of a boring log containing field organic vapor analysis (OVA) and HNu™
measurements. The presence of a distinct layer of contamination between 45 and 50
ft is suggested by the HNu™ readings of 200 ppm; if samples were not collected for
chemical testing between this interval, this could suggest intentional biasing. This
type of analysis is also useful for targeting subsequent evidentiary sampling. Figure
3.4 is a field boring log example that illustrates the presence of a volatile compound
at about 5 ft (OVA = 1000 ppm) that was not sampled. Samples in Figure 3.4 with
non-detect and near OVA and HNu™ detection levels at 10 and 20 feet, however,
were sampled. In this instance, the decision not to sample at 5 feet precludes the
confirmation of a potential surface release indicated by the OVA reading of 1000
ppm.

FIGURE 3.5 Boring log with PID, FID, and IR readings.
Field measurements used to screen soil sampling locations are qualitative and
sensitive to the compound detected and instrument calibration, but do not rely on
field measurements beyond this qualitative, field-screening purpose. Figure 3.5 is a
field log in which photoionization (PID), flame ionization (FID), and infrared (IR)
detectors were used. Values for the three instruments for the same soil ranged from
0 to 841 ppm.
3.3 INTERPRETATION OF
GEOLOGIC INFORMATION
Information on a boring log is used to create geologic cross-sections or fence

diagrams. Significant latitude is available in the extrapolation of boring log descriptions

to create these diagrams. These interpretations are important when low permeability
horizons, relative to vapor or liquid contaminant transport, are incorporated in the
geologic cross-sections or fence diagrams.
Geologic diagrams are created via manual interpretation (Figure 3.6) or interpo-
lation by computer software. Areas of inquiry (A through D) on Figure 3.6 are framed
and labeled. If the purpose of the cross-section is to represent the presence of a
continuous layer of clayey soils that retards contaminant transport, potential areas for
differing interpretation are possible as described in the following text.
A. A contact between artificial fill (speckled fill) and a silt and clay (white space) is
present midpoint between Boring 1 and MW-1. This interpretation extends the silt/
clay layer into an area where no data are available but which may be a logical
assumption.
B. The contact between the silty and clayey sand (dotted fill) and the silts and clays
(white space) is interpreted to occur at a point that is not midpoint between MW-
1 and MW-B1. This interpretation is inconsistent with the midpoint methodology
used in A.
C. The extent of the silty and clayey sand (dotted fill) is interpreted to extend halfway
between Boring 2 and VE-2 in one direction but only a short distance in the
opposite direction between Boring 2 and VE-5. This interpretation creates a signifi-
cant horizon of predominately silt and clays between C and D. Another interpre-
tation is to create a contact between framed areas C and D. This alternative
interpretation creates a thin layer of silt and clays that are less of an impediment to
the vertical transport of contaminants. This interpretation is also inconsistent with
examples A and B, where the soil contact between two wells is interpreted as the
midway point. Furthermore, there is no boring located between Boring 2 and VE-4
to indicate the presence of a clay layer.
D. The contact between the gravels at the bottom of VE-5 is extended toward Boring
2, where it is not encountered. This is inconsistent with the method used in A and
B.
E. The geologic interpretation between Boring 2 and VE-4 deviates from the pattern
observed in frames A to C in that the contact between the silty and clayey sands
in Boring 2 and gravels in VE-4 is not interpreted as occurring midpoint. The silty
and clayey soils in VE-4 are portrayed as extending just short of Boring 2, although
there are no intervening data to confirm this interpretation.
Examine the horizontal and vertical scales used in cross-sections. In Figure 3.6, the
vertical scale is 0.4¥ of the horizontal scale. If the scale is not 1:1, the viewer’s
perception may be significantly skewed. The preparation of an alternate geologic
cross-section that is scaled and presented as a rebuttal exhibit may be appropriate.
A variation to the Figure 3.6 manual interpretation of the geologic data is assignment
of numerical values that represent different soil properties. Computer software then
spatially extrapolates between these values. Computer interpretations and their por-
trayal in cross-sections, isopach maps, or fence diagrams can produce highly errone-
ous interpretations. When reviewing a computer-generated geologic diagram em-
ploying this technique, you will need to:

FIGURE 3.6 Example of manually created geologic cross-section.

• Obtain a copy of the tables and/or spreadsheets used to assign numerical values to
different soil and geologic materials.
• Evaluate whether a consistent numerical value is used for identical soil and/or
geologic descriptions.
• Determine how the computer software deals with and assigns geologic descriptions
to two numbers (e.g., rounded up or down).
• Identify whether multiple measurements of a geologic or soil property are statisti-
cally manipulated to skew the interpolation and resulting graphical portrayal of this
property; for example, combining measurements over some vertical distance and
taking the average or arithmetric log of the data can mask the presence of a geologic
or soil property of interest.
3.4 SOIL COLLECTION FOR

CHEMICAL ANALYSES
Significant opportunity exists for introducing bias during the collection of soil
samples. Sampling procedures susceptible to chemical bias (especially volatile or-
ganics) include the following:
• Improper selection of sampling equipment relative to the analyses to be performed
• Subsampling and sample transfer
• Sample compositing
• Extended holding times
3.4.1 SOIL SAMPLING EQUIPMENT

A variety of soil sampling equipment is available with different levels of potential
chemical bias (ASTM, 1997a,b). Split-spoon sampling is probably the most commonly
used method. Split-spoon barrel samplers are not recommended if there is poor sample
recovery (e.g., the metal or brass rings are not completely filled with soil) due to the
potential loss of compounds by volatilization into the headspace of the partially filled
brass tubes. Confirmation that the brass tubes are decontaminated prior to use is
required. Pre-cleaned rings or tubes can be purchased with decontamination certifi-
cation. Recycled tubes can be cleaned at a laboratory with the requisite number of rinsate
samples and testing. In the field, the sampling barrel is attached to the drive rod of the
drill rig and is driven into the soil with soil filling the sampling barrel. The barrel is
then retrieved at the surface and broken open, and the soil in the brass or steel rings
is sealed or transferred into another container. The exposed end of the soil in each
ring should be quickly covered and sealed in the field using an inert film, such as TEF-
fluorocarbon sheets that are then covered with plastic or threaded metal caps. The use
of electrical tape for sealing the plastic end caps on the brass rings is discouraged (see
Figure 3.7). Permeation of toluene from the adhesives in these tapes through the plastic
end caps can occur, resulting in a false bias. In order to confirm the origin of the
toluene from the adhesive, it is the author’s experience that subsequent samples from
the same location are required but without the tape used in the initial sampling.

FIGURE 3.7 Improper use of electrical tape to seal brass tubes containing soil samples.

FIGURE 3.8 Example of subsampling of soils in the field.
3.4.2 SUBSAMPLING AND SAMPLE TRANSFER

Subsampling is the process of “repackaging” a sample into another container. Vola-
tile organic compound losses occur primarily during the soil transfer from a split-
spoon sampler into a 40-mL glass vial, an 8-oz glass jar, or plastic bag, through
volatilization. The amount lost is dependent on the vapor pressure of the compound,
the amount of headspace in the sample container, the ambient temperature, and the
amount of sample disturbance (Hewitt et al., 1992). Figure 3.8 illustrates soil
subsampling from one partially filled brass ring into a second ring so that no
headspace is present. If the subsampled soil in the second brass ring is tested for
volatile organic compounds, losses can be as much as 100% of the actual value
(Siegrist, 1993).
Figure 3.9 summarizes data from soil samples contaminated with TCE collected
with different subsampling procedures and/or containers (Siegrist and Jenssen, 1990).
The primary mechanism for loss was due to volatilization during collection, sample
storage, and handling. The initial concentration of the spiked soil sample was 4.7 ppm.
The soil sampling location coupled with an understanding regarding volatile
losses that occur during soil subsampling can be used to manipulate test results.
Consider excavated soil from an underground gasoline tank removal that is stock-
piled for several days. The ultimate disposal decision for this soil by the regulatory
authority is predicated on the sample results from the stockpile detecting compounds
below a specific action level (Plate 3.2*). BTEX results from a soil sample collected
from the crust of the pile has a higher probability of a lower concentration than a
sample collected from within the interior of the soil pile. A decision based on the
former location can result in the non-detect BTEX results. The stockpiled soil is then
approved for placement into the excavation. At some future time (e.g., a Phase II

FIGURE 3.9 Loss of TCE from different sampling containers. (Adapted from Siegrist, S. and
P. Jenssen, Environmental Science and Technology, 24(9), 1387–1392, 1990.)
property transfer), soil in the former tank excavation is sampled, the samples are
above a regulatory action limit, and remediation is required. This is a common
scenario, especially with aboveground ex situ remediation, that can be avoided by the
selection of appropriate sampling locations and an adequate number of confirmation
samples.
When designing a soil sampling program for volatile organic compound analy-
sis, minimize the number (if any) of subsampling and/or sample transfer steps.
Current soil sampling procedures specify that samples analyzed for volatile organic
compounds should be shipped to the laboratory in containers filled to capacity (i.e.,
no headspace) and stored at 4∞C for no more than 14 days. An option for improving
sample integrity is to use glass jars containing methanol. Given that volatile com-
pounds are more soluble in methanol than water, the longer contact time between
the methanol and soil results in excellent extraction efficiency. In addition, extrac-
tion of the volatile compounds from the soil is performed with a larger subsample
than used in some methods (e.g., 100 g vs. 5 g, or, if placed directly into the purge
vessel, 1 g for gas chromatography/mass spectrometry [GC/MS] analysis). Thus, a
more representative determination of the volatile compounds present results. The
methanol container is usually a wide-mouth, 8-oz jar with TFE-fluorocarbon-lined
lids. Analytical-grade methanol (100 mL) is added to the jar, into which the soil is
placed to a predetermined level followed by immediate sealing of the jar. Michigan,
New Mexico, Massachusetts, and Wisconsin currently require this procedure for
soils analyzed for volatile organic compounds. Considerations in using this tech-
nique include investigating whether sample shipment by a commercial carrier is
restricted. Coordination with the laboratory is also required if the laboratory pre-
pares the methanol-filled containers prior to sampling.

When reviewing test results obtained from soil samples using this technique, be
aware that methanol has a high affinity for many organic compounds. Once a
methanol bottle used to prepare the 8-oz jars is opened, organic compounds can be
rapidly adsorbed into the methanol, thereby resulting in cross-contamination. Labo-
ratories also purchase methanol with contaminant levels exceeding method detection
limits (Hartman, 1998a). Testing the methanol using the same method selected for
the soil samples prior to filling the jars allows quantification of this potential bias. A
potential reduction in analytical sensitivity may also occur if a gas chromatograph/
Hall detector is used.
3.4.3 SOIL COMPOSITING

Composite samples consist of multiple samples collected at various sampling loca-
tions and/or points in time. The constituent information for the individual samples is
lost, although it may be indirectly observed through the composite measurement.
Composite sampling reduces concentration variability, thereby narrowing the confi-
dence interval of the population as contrasted with grab samples that maximize
concentration variability.
When analyzed, composite samples produce a global average value. Compositing
can result in loss of information via sample dilution, especially at near-detection
levels, as well as the possibility of adverse physical, chemical, and biological
interactions resulting from the mixing process (Lancaster et al., 1988). Samples
analyzed for volatile organic compounds should not be composited (ASTM, 1997d).
Compositing can mask information otherwise useful for dating a contaminant re-
lease. Figure 3.10 illustrates this concept; discrete samples collected from borehole
SB2 allow the correction of historical water levels to a known release date to confirm
the release of diesel into the groundwater after 1982. Composite sampling would not
provide the depth of discrete information necessary for this interpretation. Compositing,
however, has value as a field screening technique for rapidly identifying whether
contamination is detectable or providing a precise estimate of the mean concentration
of a waste analyte in soil or groundwater.
Composite sampling is routinely encountered in soil confirmation sampling. This
application has merit due to the expected contiguous and non-randomness of the
contamination, along with the assumed quantity of non-detects associated with the
testing. In general, individual samples selected for compositing should be of a similar
mass, although proportional sampling may be appropriate. An example of propor-
tional sampling is the collection of soil cores from contaminated soil overlying an
impermeable zone (ASTM, 1997c). Soil cores of different length can provide an
averaged contaminant concentration value of the overlying soil, regardless of core
length.
The collection time for a single composite sample should not exceed 24 hr. If
longer sampling periods are necessary, the collection of a series of composite
samples is recommended (ASTM, 1996). If composite samples are collected without
the opportunity to resample, a novel application using the inverse theory technique

FIGURE 3.10 Use of discrete soil sample results and historical groundwater level data to
confirm the release of diesel into the groundwater after 1992.
of linear regularization may provide concentration estimates at the individual sample

level (Lancaster and McNulty, 1998).
The use of field screening technologies rather than composite sampling can
provide a cost-efficient option to compositing. X-ray fluorescence, for example, can
quickly screen a soil sample for a particular element or target compound, thereby
providing the basis to identify a discrete number of samples for testing (see Table
3.10). This approach is conducive to evidentiary sampling, because a large number
of samples can be tested in the field in a short period of time.
3.5 GROUNDWATER CHARACTERIZATION
The hydraulic properties of an aquifer are commonly estimated or measured as part

of a groundwater characterization investigation. The determination of how these
properties are measured and their reliability is one factor in evaluating contaminant
transport and risk assessment models. Hydraulic properties and their definitions
include:
• Hydraulic conductivity: The rate of flow of water in gallons per day through a
cross-section of 1 ft2 under a unit hydraulic gradient at a prevailing temperature.

• Hydraulic gradient: The rate of change in total head per unit of distance of flow
in a given direction.
• Permeability: The property or capacity of a porous rock, sediment, or soil to
transmit a fluid.
• Porosity: The percentage of the bulk volume of a rock or soil occupied by inter-
stices, whether isolated or connected.
• Transmissivity: The rate at which liquid is transmitted through a unit width of an
aquifer under a unit hydraulic gradient.
The accuracy and representativeness of these values are in part dependent on whether
they are measured in the field or laboratory. Three methods used to measure the
saturated hydraulic conductivity of an aquifer (listed from least to most representa-
tive method) are laboratory permeater tests, slug tests (field), and pump tests (field).
Groundwater velocity is a key input parameter used for advective and for
contaminant transport models. Sources of error in acquiring this information include
the following:
1. Installing a well (to measure groundwater levels) near activities that disrupt the
aquifer, such as municipal or irrigation wells that are periodically pumped and/or
spreading basins used for groundwater recharge
2. Surface water bodies (e.g., streams, lakes, or reservoirs) with highly fluctuating
flows located near a monitoring well
3. Tidal cycles that affect groundwater levels
4. Leaking sewers, water mains, and/or ornamental irrigation that affect localized
hydraulic gradients
5. Inaccurate surveying of monitoring wells
In order to determine groundwater velocity, monitoring wells are surveyed on the

horizontal and vertical axis. Wells should be surveyed to a vertical accuracy of 0.01
ft. The water level depth in each well is adjusted to provide a standardized reference
point (usually mean sea level, MSL) which is used to create a groundwater contour
map. If the original vertical survey for a well is incorrect, subsequent measurements
can perpetuate this error, resulting in incorrect interpretations regarding groundwater
direction and velocity.
Incorrect water level measurements can occur as a function of the measuring
point or the equipment. The measuring point refers to the location at the ground
surface or well casing from which the depth is measured; the surface measuring point
must be consistent. In some cases, a well casing can settle over time, resulting in a
biased measurement; if this is suspected, re-survey the well.
Differences in water level measurements can also occur as a function of the
equipment (e.g., steel tape vs. a pressure transducer) (Rosenberry, 1990). There is
sufficient error in the two techniques to produce misleading information about the
direction of groundwater flow, especially for small groundwater gradients (@ 0.001).
Knowing what equipment was historically used for measuring the depth to ground-
water in a monitoring well and the consistency of the measurement technique may
explain apparent anomalies in groundwater flow patterns.

Another potential source of error in identifying the direction and velocity of
groundwater is combining groundwater level measurements from wells screened in
discrete aquifers, especially for unconfined and confined aquifers. Using regional
maps (e.g., 1 in. = 24,000 ft) to determine groundwater flow and direction rather than
installing on-site wells can also result in erroneous determinations of groundwater
direction and velocity.
Do not accept reported groundwater direction or velocity a priori without re-
viewing the actual measurements. This requires plotting groundwater level measure-
ments and creating a groundwater contour map. The groundwater direction obtained
from the graphing should be compared to the general direction of reported ground-
water flow in the environmental report.
3.5.1 MONITORING WELL LOCATION

Given a sufficient understanding of the hydrogeological environment and the origin
and physiochemical characteristics of the chemicals released into the subsurface,
monitoring wells can be designed to collect samples for the following purposes:
• Provide representative (i.e., the degree to which sample data are characteristic of
a population, variations at a point, or an environmental condition) samples.
• Avoid detecting contaminants.
• Underestimate contamination.
• Overestimate contamination.
• Generate anomalous data.
The location of a monitoring well and well screen interval has a profound impact on
the chemistry of groundwater samples collected from the well. Monitoring well
design features indicative of manipulation are summarized in Table 3.2. Other
sources of potential bias include well construction materials, grouting materials,
design of security covers, and drilling methods (Powell, 1997). If monitoring wells
are constructed from different materials, this might indicate an attempt to manipulate
the chemical data through well construction materials. It can also indicate several
generations of consultants working at the site with different preferences for well
construction material.
Elevating sample pH through improper grouting procedures or the use of grout-
ing materials containing potential contaminants can impact sample chemistry. Ce-
ment grout (CaCO3) can raise the pH of the surrounding soil several pH units.
Elevated pH values in the vicinity of the well screen may cause precipitation of
otherwise soluble metals as they enter a halo of higher pH groundwater. If this
phenomenon is suspected: (1) examine whether the pH values are high relative to
other wells in the area, and (2) excessively purge the well prior to sampling (e.g., 10
to 20 casing volumes) and measure the pH to observe if it suddenly drops several pH
units. If pH values decrease abruptly, this may suggest that the grout material has
impacted groundwater pH in the immediate vicinity of the well.

TABLE 3.2
Effect of Well Location on Sample Chemistry
Impact on Sample Chemistry Design/Location Characteristics
Contaminants non-detected Wells installed cross-gradient and/or upgradient of source areas;

wells with long screens (>20 ft) and contaminants present at low
concentrations
Contaminants underestimated Long screens (>20 ft); wells screened across geologic units with a
low probability of transporting contaminants
Contaminants overestimated Short screens located to intersect zones with a high probability of
contamination (i.e., LNAPLs at the water table); wells screened
across high- and low-contaminated zones that result in an averaged
concentration that is higher than the actual concentration in the
groundwater
Anomalous data Well located next to a surface water body whose chemistry is
dissimilar to the groundwater chemistry and whose presence im-
pacts the sample chemistry in a transient and unpredictable manner;
well located in an area of changing groundwater direction that
results in varied chemistry depending on the direction of groundwa-
ter flow.
Well construction can also impact sample chemistry. Poorly constructed security
covers or valve boxes that allow contaminated surface seepage into the well can
produce anomalous chemical results (see Plate 3.3*). It is the author’s experience that
street runoff containing soluble lead and high total petroleum hydrocarbon concen-
trations draining into a well via a cracked security cover can result in detection of
these contaminants in groundwater samples above regulatory action limits. When-
ever possible, arrange a site visit to identify the existence of these types of biases
prior to examining the groundwater chemical results.
Another area of inquiry for wells drilled through multiple aquifers is whether the
consultant drilled through a confining layer, thereby introducing contamination into
a deeper, previously uncontaminated aquifer. This situation is often identified on a
boring log that indicates that the borehole was over-drilled with the lower portion of
the hole backfilled with grout to seal off the penetration of the confining layer. A
variation to this scenario is if the well screen intersects multiple aquifers in which
only the upper horizon is contaminated. Contaminants from the upper, contaminated
zone enter the lower, previously uncontaminated zone. A reverse situation is shown
in Figure 3.11, where contamination from a lower aquifer is allowed to mix within
the well casing during pumping. Contaminants then flow into the shallower zones
when the pump is not operating. The result is the contamination of a previously
uncontaminated shallow water-bearing zone.

FIGURE 3.11 Cross-contamination of a shallow aquifer by a multiple-screened pumping
well.
3.5.2 INSTALLATION OF GROUNDWATER

MONITORING WELLS
Contaminant distribution in groundwater is defined by the horizontal placement of
the monitoring well as well as the screen length and interval. While federal and state
guidelines exist, the consultant or driller usually designs the well. As a result,
multiple well construction designs may be present which impact the chemical inter-
pretation of samples collected from the network.
If well construction is suspected of biasing sample chemistry in some manner, the
first step is to review the placement of the well screen. The location of the well screen
determines the vertical horizon from which a sample is collected, unless discrete
vertical depth sampling is performed. Questions to be answered during this analysis
include:

FIGURE 3.12 Hydrograph indicating the presence of two aquifers.
• Are the wells screened in similar water-bearing zones?

• Does the well screen length bias sample chemistry?
• Is the well screen providing a pathway for contaminant transport from areas of high
to low contamination or from contaminated to non-contaminated zones?
The first step in answering these questions is to construct a hydrograph. A

hydrograph plots time on the horizontal axis and the water level measurement for
each well on the vertical axis. If sufficient information is available, the water level
in each well for a point in time is plotted and the data connected. If the wells intersect
the same water-bearing zone (i.e., if they are hydraulically connected), the lines for
the various wells will follow a similar pattern over time. If the wells do not follow
the same general pattern, this may be evidence of multiple saturated zones that are
monitored by the well network. Separate water level contour maps should be created
for each aquifer indicated by the hydrograph. Figure 3.12 is an example of a hydro-
graph showing two distinct aquifers.
Another technique is to sketch all of the monitoring wells on a single sheet of
paper, adjusting for the surface elevation for each well, with the vertical axis
representing well depth. Mark the screen interval on each well along with the water
level. This sketch provides insight regarding the consistency of the well screens
between wells and patterns between well screen length and water levels.
Another area of inquiry is whether the screen interval biases sample chemistry.
If the predominant contaminant of interest is a light non-aqueous phase liquid
(LNAPL) and the well screen does not intersect the water table, the LNAPL will not
be detected. Other examples of high contaminant concentrations near the water table
that decrease sharply with depth include toluene, xylene, xylidine, dissolved oxygen,
and manganese concentration profiles (Kaplan et al., 1991) and BTEX concentra-
tions (Gibs et al., 1993; Martin-Hayden et al., 1991). An example of the latter is the
sampling for BTEX components at the water table with a short screen (<5 to 10 ft)
well vs. a longer screened (>20 ft) well. If this inquiry reveals potential patterns

between compound concentration depth profiles and screen length, examine the
screen length as a function of proximity to the contaminant source (if known). If
monitoring wells closest to the source area have long screens (possible sample
dilution) and those farthest from the source are short screened, a pattern of sample
chemistry manipulation and contaminant plume geometry via well screen length and
proximity to the source may become apparent (Martin-Hayden and Robbins, 1997).
The interpretation of the vertical distribution of a contaminant is especially
sensitive to well screen length, interval, and placement (Robbins and Martin-Hayden,
1991). Detailed studies of vertical spatial and temporal gradients indicate that trans-
port of contaminants is often limited; therefore, concentration profiles can be highly
variable with depth (Barcelona et al., 1989; Garabedian et al. 1987; Gibs et al., 1993;
Sudicky et al., 1983). The ability of the monitoring well to provide this resolution is,
then, spatially dependent, primarily on the monitoring well screen design.
An example of the impact of well screen length on source identification is shown
in Figure 3.13. The plan view in the upper panel of Figure 3.13 plots TCE concen-
trations from groundwater samples. During the first round of sampling, all of the
wells, except the demonstration well, were sampled (the demonstration well was
installed after the first round of sampling). The interpretation of the data indicated a
source in the vicinity of the 1650 ppb of TCE given the upgradient well value of 120
ppb. TCE concentrations relied upon for this conclusion were the 120 ppb from the
upgradient well, the 1650 ppb from the well near the source, and the downgradient
well with 1500 ppb. The source and downgradient wells were short screened (10 ft)
and completed in a silty sand. The upgradient well (120 ppb) was completed with a
20-foot screen that intersected the silty sand and a highly permeable sand and gravel
layer. Concern about the longer screened, upgradient well diluting the TCE concen-
tration via the uncontaminated sand and gravel layer resulted in installation of a
demonstration well screened in a manner identical to the source and downgradient
wells upgradient of these three wells. Sampling of the demonstration well shown in
the cross-section on the lower panel of Figure 3.13 resulted in a TCE value of 1600
ppb. This information is consistent with a revised interpretation that TCE migrated
onto the property from an upgradient source.
Ideally, monitoring wells are all short screened (approximately 5 to 10 ft) and
located at appropriate depths relative to the goal of the monitoring program. In most
cases, however, monitoring wells are constructed with different screen lengths and
may not be ideally located. While the potential bias associated with different moni-
toring well construction can be identified, quantification of this bias cannot be
assessed. The qualitative impact of different well construction designs in addition to
an evaluation of groundwater purging and sampling techniques should be examined
in total and a judgment made concerning the reliability of the chemical data.
3.5.3 SAMPLING PLAN

Environmental reports often include soil and groundwater sampling plans. Review
the sampling plan and compare it with the field notes describing the actual field

FIGURE 3.13 Impact of well screen length on source identification.
practice. This review can identify whether significant deviations from the sampling
plan occurred. A recommended step in performing this review is to compare the
following components of the sampling plan with what transpired during its imple-
mentation:
• Could purging, sampling, and handling procedures for compounds susceptible to

volatilization, precipitation, or other forms of known chemical transformation
result in chemical transformations?
• Was sample filtration and/or preservation properly implemented?
• Were sufficient field blanks, travel blanks, duplicate samples, and/or equipment
rinsate blanks incorporated into the sampling protocol to allow for the discrimina-
tion of potential sampling introduced bias?
• Were expedited storage and transportation of samples to the laboratory imple-
mented as specified in the sampling plan?

3.5.4 GROUNDWATER PURGING
A review of groundwater purging procedures is useful, as inconsistent purging
practices can result in different interpretations concerning the identification of zones
of low concentration, differences in the direction of contaminant flow, contaminant
plume geometry, and the identification of intermittent or multiple sources of ground-
water contamination (Martin-Hayden and Robbins, 1997). A lively discussion in the
environmental consulting industry during the past several years has occurred re-
garding the merits of purging two to five casing volumes of groundwater prior to
sampling or whether “micropurging” a smaller volume of water is adequate.
Micropurging and sampling can provide representative chemical results while mini-
mizing issues regarding disposal of purge waters and/or sample oxygenation. A
routine purging practice is to pump 5 to 10 times the volume of standing water in
the well to remove the stored water in the well casing (ASTM, 1992). For most
wells, three to five well volumes are purged, or until pH, conductivity, and water
temperature values stabilize. Stable sample chemistry is considered to occur if field
values of temperature, specific conductance, oxygen, pH, and turbidity are within
±10% in purge water pumped over at least two successive well volumes.
If a monitoring well slowly recharges, sufficient time should elapse so that at
least 95% of the purged water comes from the aquifer; wells should also be sampled
within 6 hr of purging (Csuros, 1994). At no times should a well be purged to dryness
if the recharge rate causes the formation water to cascade down the interior of the
well screen. For a well whose screen intersects a low-permeability formation,
desaturating the well during purging can also result in weighting the average con-
taminant concentrations near the bottom of the well and therefore underestimating
the concentration and size of the contaminant plume (Martin-Hayden et al., 1991).
Micropurging or low-flow sampling is generally considered to be between about
100 to 200 mL per minute (Puls et al., 1990). Higher rates are acceptable (i.e., 1 L
per minute) for more transmissive formations (Powell 1993). Research indicates
that a representative groundwater sample for volatile organic sampling is achievable
via micropurging without pumping 2 to 5 well casing volumes (Kearl et al., 1994;
Powell et al., 1997; Puls et al., 1995). The U.S. Environmental Protection Agency
advocates micropurging coupled with turbidity, pH, redox potential, and dissolved
oxygen measurements using downhole meters or flow-through cells until stability
is achieved. These measurements are considered stabilized when the values are
within approximately 10% over at least two measurement events. Stabilization can
also occur prior to the removal of one well casing volume or may require excessive
purging (Barcelona et al., 1994; Robin et al., 1987). Research indicates that for fully
hydrogeologically characterized sites with long-term monitoring data, micropurging
and the measurement of water quality parameters such as pH, turbidity, and total
conductance may not be necessary. Groundwater sampling for uranium at the
Fernald facility in southwestern Ohio, for example, indicated that representative
samples were collected with micropurging sampling without water quality param-
eter measurements (Shanklin et al., 1995).

In a California study involving trace metal contamination, low-flow purging and
sampling in addition to rigorous adherence to sampling and handling procedures
were examined. When low-flow and trace metal clean techniques were employed,
resultant trace element concentrations were notably lower than for values obtained
with conventional methods. The trace element concentrations from groundwater
wells were 2 to 1000 times lower than those previously reported by consultants using
conventional sampling techniques at the same wells. While the consultant reported
that cadmium and chromium concentrations exceeded the California maximum
contaminant levels (MCLs), these levels appeared to be artifacts of inappropriate,
albeit standard, sampling techniques (Creasey, 1996).
The use of micropurging can bias sample chemistry due to the small capture zone
associated with low purging rates. Consider a monitoring well with phase-separate
TCE in the groundwater that is 25 feet down-gradient from the well. Historical TCE
concentrations in groundwater from this well are consistently in the parts-per-million
range. Purging rates of 5 gallons per minute and greater were used. Subsequent
sample results collected via micropurging (100 mL/min) are non-detect because the
purging and sampling capture zone does not extend to the vicinity of the phase-
separate and dissolved TCE.
3.5.5 GROUNDWATER SAMPLING

When reviewing groundwater sampling procedures, identify the type of sampling
equipment (e.g., bailer, submersible pump, peristaltic pump) and sampling proce-
dures used. Groundwater samplers vary in their impact on sample chemistry. The
greatest opportunity for negative bias occurs when sampling groundwater to be
testing for volatile organic compounds. Because the true value of a volatile organic
compound is unknown, the bias introduced by equipment selection and operation is
relative. Sampling equipment and procedures that result in higher levels of volatile
compounds are therefore considered most accurate (i.e., unless evidence of a false
positive bias is identified).
Numerous studies have evaluated the attributes of groundwater sampling equip-
ment and procedures on sample quality (Stolzenberg et al., 1986). Many of these
investigations examined the precision (i.e., a measure of the reproducibility of a set
of replicate results among themselves or the agreement among repeated observations
made under the same conditions) and recovery of volatile organic compound deter-
minations on replicate samples collected in the field or laboratory. Volatile com-
pounds are particularly sensitive to losses by degassing at reduced pressures from
suction devices such as peristaltic or centrifugal pumps or turbulence created by
mechanical sampling devices such as gas lift samplers and bailers. Volatile organic
compound losses from improper sampling equipment selection and use are cumula-
tive in nature. Sampling procedures that represent potential sources of volatile
organic compound loss include:

FIGURE 3.14 State-of-the-art sampling equipment used to strip volatile organic compounds
from a groundwater sample by over-pressurizing the pump. (Courtesy of QED; Ann Arbor, MI.)
• Sampling with a bailer and aerating the sample during transfer from the bailer into
the sample container
• Over-pressurizing (see Figure 3.14) or depressurization (Barcelona, 1990)
• Insufficient decontamination between sampling or lack of equipment blank samples
between sampling, if non-dedicated sampling equipment is used
• Not placing the cap on the sampling container or immediately chilling the sample
This level of information is usually not included in the environmental report but
may be available in field notes acquired via deposition testimony of the sampler. In
general, positive displacement pumps (e.g., bladder pumps) provide accurate, repro-
ducible sampling performance over a range of lifts, hydraulic heads, and depths.
Dedicated sampling systems suitable for both purging and sampling are also pre-
ferred based on sample integrity as well as convenience and cost.
3.5.6 SAMPLING EQUIPMENT AND SEQUENCE

In general, the compatibility of the sampler material(s) with the analysis to be
performed is obvious (e.g., iron bailer when testing for trace metals). Subtle chemical
biases can be introduced, however, from a polyethylene bailer manufactured from
plastic regrinds or plastics that contain additives vs. a sampler manufactured from
virgin material. A bailer manufactured from solid rod or block stock may similarly
contain potential cross-contaminants from the machining process, as opposed to a
bailer that is injection molded without release agents such as waxes or petroleum-
based lubricants. Depending on the level of scrutiny required and the potential bias
relative to the allegations in the case, this level of inquiry may or may not be
necessary.

TABLE 3.3
Effect of Sampling Equipment on Benzene
and Chlorobenzene Concentrations
Sampling Benzene Chlorobenzene
Equipment (ppb) (ppb)
West Bay sampler 114 651

Bailer 179 1034
Pump with packer 205 1447
Dedicated bladder pump 279 1463
Compounds susceptible to chemical changes due to redox shifts from the sam-
pling equipment and field procedures are most vulnerable to bias, as are compounds
with low detection limits. With volatile organic compounds, losses are more likely
to increase due to operator procedures (Imbrigiotta et al., 1986). Table 3.3 summa-
rizes the impacts of sampling equipment (and procedures) on benzene and chloroben-
zene concentrations (Blegen et al., 1988). If the opportunity exists to re-sample the
well from which suspect data were collected, the well can be re-sampled with
identical equipment but with different procedures or different equipment so that the
potential source of the bias can be identified.
If a monitoring well is no longer available or if the monitoring well construction
is in question, groundwater sampling using direct push technology (e.g., Hydropunch,
Geoprobe, Strataprobe, etc.) can be used at the same location. Standardized sampling
guides are available for using direct push technologies for collecting groundwater
samples (ASTM, 1997c). Comparisons between groundwater sample chemistry ob-
tained from direct push samples and standard monitoring wells are reported to be
statistically similar (Bergren et al., 1990; Church et al., 1996; Kaback et al., 1990).
Sampling recommendations that minimize sampling bias, especially redox-sen-
sitive and volatile compounds, include the following (Puls et al., 1989a,b; 1992):
• Isolate the sampling zone with packers to minimize the amount of purge water.
• Use low-flow pumping to minimize sample aeration and turbidity.
• Monitor water quality parameters while purging to establish baseline or steady-
state conditions to initiate sampling.
• Perform filtration to estimate the total dissolved species present and collect unfil-
tered samples for estimations of contaminant mobility.
In addition to potential chemical biases introduced via the selection of sampling

equipment and materials of construction, the sampling sequence can also impact
sample chemistry. Figure 3.15 depicts a site with monitoring wells located on and off
site with the property boundary depicted by a dotted line. Groundwater flows to the
north. PCE concentrations in groundwater for the previous quarter and the sampling
sequence were obtained from the chain of custody (see Table 3.4). In addition, the
sampling equipment and procedures were described in the work plan. For on- and

FIGURE 3.15 Map illustrating the impact of sampling equipment and sequence on ground-
water chemistry results.
TABLE 3.4
Summary of Sampling Results, Sampling Sequence,
and Sampling Equipment for Site Shown in Figure 3.15
Sampling Sampling
Sequence Equipment
Well PCE (mg/L) On-Site Off-Site Purging Sampling
B3 ND 1 — Peristaltic Teflon® bailera

B6 ND 2 — Peristaltic Teflon® bailera
B14 160 3 — Peristaltic Teflon® bailera
MW1 ND — 1 Submersible Submersibleb
MW9 ND — 2 Submersible Submersibleb
MW5 30 — 3 Submersible Submersibleb
a Disposal Teflon® bailer.

b Submersible pump operated at maximum pumping rate for purging and sampling.

off-site sampling, groundwater sampling proceeded from wells with no detectable
PCE to wells with higher PCE concentrations, an observation which may indicate an
intent to minimize the potential for cross-contamination via the sampling sequence.
The purging and sampling equipment used also suggests a knowledge of the impact
of sampling equipment on sample chemistry. Equipment that introduces the least
potential of sample chemistry bias (e.g., peristaltic pumps and Teflon® bailers) was
selected for on-site wells, while off-site groundwater samples were collected with
equipment that introduced a significant potential for sample loss via volatilization
(submersible pumps). A conscious attempt by the consultant to minimize the off-site
detection of PCE may therefore be suspected.
The sampling sequence may also be designed to maximize particular temporal
impacts on sample chemistry. Figure 3.16 illustrates the impacts of some of these
factors on groundwater chemistry. If such relationships exist, identify whether the
sampling schedule results in a systematic impact on sample chemistry, and, if so,
incorporate this information into your analysis.
3.5.7 EQUIPMENT DECONTAMINATION

The chemical results from equipment decontamination samples allows an assessment
of the presence and nature of cross-contamination originating from the sampling
equipment. Federal, state, and American Society for Testing Materials (ASTM)
standards are available which describe decontamination procedures for contact and
non-contact equipment used for soil and groundwater sampling (ASTM, 1990). In
general, sampling equipment is washed with a detergent solution followed by a series
of water, desorbing agents, and deionized water rinses. A decontamination procedure
for sample contact equipment includes the following tasks (Wilson 1998):
1. Wash with a detergent solution (Alconox® or Liquinox® or similar nonphosphate/

ammonia detergent) with a brush made or an inert material.
2. Rinse with water of a known chemical composition.
3. Rinse with an inorganic desorbing agent (10% nitric or hydrochloric acid made
from reagent-grade nitric or hydrochloric acid and deionized water); this step may
be deleted if the samples will not be tested for organics.
4. Rinse with deionized water.
5. Air dry prior to next use (ascertain whether fugitive or vapors can contaminate the
equipment; if this is a possibility, then air dry in an environment where airborne
contamination is not a consideration).
6. Wrap the equipment for transport with an inert material such as aluminum foil.
The U.S. Environmental Protection Agency recommends a similar procedure for

equipment used to collect samples tested for organic and inorganic constituents
according to the sequence in Table 3.5 (U.S. EPA, 1991). Non-sample contact
equipment can be rinsed with a portable power washer or steam cleaner. In addition,
handwashing with a brush and detergent solution may be required, followed by
rinsing with water of a known chemical composition (ASTM, 1990). Examples of

FIGURE 3.16 Examples of temporal variations on groundwater chemistry and LNAPL
thickness.

TABLE 3.5
Decontamination Procedures for Sampling
Equipment Used To Collect Samples for
Organic and Inorganic Analysis
Organic Compounds Inorganic Compounds
Tap water Dilute (0.1-N) hydrochloric

Organic-free reagent water or nitric acid
Reagent grade acetone Tap water
Pesticide-quality hexane, Reagent-grade water
methyl alcohol, or
isopropanol alcohol,
depending on the analysis.
noncontact equipment include drilling augers and cone penetrometer rods (see Figure
3.17).
For rigorous quality assurance and quality control situations, the rinse water used
for equipment decontamination is sampled and tested for the same compounds to be
analyzed as the sample obtained with the decontaminated sampling equipment.
Referred to as an equipment rinsate blank, it is a sample of the last decontaminated
water poured over the equipment. Equipment rinsate blanks are collected from non-
dedicated equipment such as pumps used for sampling, interface probes, mixing
bowls, sampling scoops, split-spoon samplers, Hydropunches, bailers, and cone
penetrometer testing tips. Equipment rinsate blanks should be collected at a rate of
FIGURE 3.17 Decontamination of groundwater sampling equipment and rinsate troughs for
cone penetrometer rods.

TABLE 3.6
Appropriate Sample Containers and Analysis
Container Description Analysis
80-oz amber glass bottle with Teflon®-lined black phenolic cap Extractable organics
40-mL glass vial with Teflon®-backed silicon septum cap Volatile organics
1-L high-density polyethylene bottle with polyethylene-lined, Metals, cyanide, and sulfide
white polyethylene cap
120-ml glass vial with Teflon®-lined, white polyethylene cap Volatile organic (soil)
16-oz wide-mouthed glass jar with Teflon®-lined, Extractable organics/metals
polylyethylene cap (water analysis)
8-oz wide-mouthed glass jar with Teflon®-lined, black Extractable organics and
polyethylene cap (water) metals in soil
4-oz wide-mouthed glass jar with Teflon®-lined, black Extractable organics and
polyethylene cap (water) metals in soil
1-L amber glass bottle with Teflon®-lined, black polyethylene cap Extractable organics
4-L amber glass bottle with Teflon®-lined, black phenolic cap Extractable organics
500-mL high-density polyethylene bottle with polyethylene- Metals, cyanide, and sulfide
lined, baked-polyethylene cap
one blank per every 10 samples or one per day (U.S. EPA, 1995). Care must be taken
to label the rinsate sample and the corresponding sample collected with this equip-
ment correctly, so that any cross-contamination from the decontamination procedure
can be identified and quantified.
3.5.8 SAMPLE CONTAINERS

Recognized protocols are available that define the proper size and appropriate
container material for soil and water samples for a given analysis. When reviewing
the chain of custody, identify whether proper containers were used and, if not,
whether this represents a potential false or negative bias. Generally, these types of
issues are only significant when trace concentrations are of interest. Table 3.6
summarizes containers relative to the analyses to be performed (U.S. EPA, 1995).
For liquid samples, the appropriate container for volatile compounds is a 40-mL vial
sealed with a Teflon®-lined cap. The vial is filled with the meniscus above the top of the
vial so that when the sealed vial is inverted, there are no air bubbles. Most laboratories
will note on the sample receipt checklist log if vials are received with bubbles and
may not analyze the sample without client authorization. Many laboratories will not
accept samples for analysis if the bottles were uncertified clean by a supplier or
cleaned by another laboratory. Table 3.7 summarizes recommended cleaning proce-
dures for reused sampling containers (Wilson, 1998). If a concern exists about the
chemical integrity of reused sample containers, fill several containers with distilled
water and analyze them for the compounds for which the samples will be tested.

TABLE 3.7
Recommended Decontamination Procedures for Sample Containers
Bottles
Separate the cap and Teflon® septum, rinse in tap water, and soak in warm, soapy water using
laboratory-grade, nonphosphate detergent. Scrub the vials with a brush. Rinse the vials with
tap water until the soap residue is gone, followed by a triple rinse of deionized water. Place
the vials in a metal basket, right side up, and place in a ventilated oven at 105∞C for at least
3 hr. Remove the vials from the oven and allow to cool for at least 20 min. Cap each vial with
a heated septum and store within a sealable (Zip-Lok®) bag.
Caps
Wash the caps in soapy water to remove dirt. Rinse with tap water to remove the soapy water.
Allow to air dry, and store until needed.
Septum
Wash the septum in soapy water. Rinse with tap water to remove soap residue, then triple rinse
with deionized water. Spread the septum in a single layer on a cleaned, stainless steel tray lined
with laboratory-grade tissue paper. Dry in an oven at 105∞C for no more than 1 hr. Remove,
cool, and immediately cap. Containers used for semivolatile organic compounds should be
washed in soapy water, water washed, and rinsed with a methanol or isopropanol alcohol.
Sample cross-contamination can result if samples with significant differences in

concentration are shipped together. For example, samples of free-phase gasoline and
groundwater samples to be analyzed for BTEX compounds should be shipped
separately. The shipping container can also cause cross-contamination. Cross-con-
tamination originating from an ice chest can be identified via the travel blanks results.
When designing a sampling plan, buy new ice chests rather than using ones provided
by the laboratory (which may have compounds sorbed into their plastic). Consider
segregating highly contaminated samples (e.g., oily soil, samples with high photoion-
ization detector readings) from samples without gross indications of contamination
in separate shipping containers.
3.5.9 SAMPLE FILTRATION, PRESERVATION,

AND HOLDING TIMES
Water samples analyzed for metals may require filtration in the field. Generally,
samples analyzed for trace metals, inorganic anions, and cations are filtered, while
water to be tested for total organic carbon and volatile organic compounds is
unfiltered (Barcelona and Morrison, 1988). The U.S. Environmental Protection
Agency recommends collecting one unfiltered sample for total metals and one
filtered sample for dissolved metals (U.S. EPA, 1986). If the contaminant concentra-
tion in an unfiltered sample is higher than for a filtered sample, a portion of the
contaminant may be sorbed onto the solid particulate matter in the water. Colloids
as large as 0.45 to 3 mm can be mobile and capable of transporting contaminants large

FIGURE 3.18 Impact of 0.10-, 0.40-, and 10.0-mm filters on elemental analysis of a ground-
water sample. (Adapted from Puls, R. and Barcelona, M., Hazardous Waste and Hazardous
Materials, 6(4), 385–393, 1989.)
distances. If a chemical is transported via colloidal transport, field filtering can

remove this colloid and the associated contaminant. If the purpose of the sampling
is to estimate the extent of metal contamination, substantial underestimation of
contaminant mobility can result due to metal/colloidal associations with filtered
samples. At a Superfund site in California, groundwater samples tested for lead were
filtered with a 0.45-mm filter; the lead concentrations in the unfiltered samples were
20 to 600 times greater than the filtered samples. For chromium, concentrations were
6 to 24 times greater in the unfiltered samples than in the filtered samples (Puls and
Barcelona, 1989).
The standard 0.45-mm filter is the standard opening size, although this is an
artificial convention. A 0.45-mm filter used to determine the extent of metal contami-
nation in a dissolved state can overestimate the actual concentration due to the
association of metals with colloidal material less than 0.45 mm. If the accuracy of the
dissolved metal concentrations is of concern, samples can be field filtered through a
1-mm pore size filter using an in-line filter, and acidified immediately to <2 pH with
concentrated HNO3 (Puls et al., 1992). Another option is to filter the sample with
multiple filter sizes (the opening of a filter can also clog during filtering, resulting in
a diminished filter pore size) and analyze the filtrate and dissolved component.
Figure 3.18 illustrates the impact of filtration with three pore sizes on elements from
a groundwater sample.
Another recommendation is no filtration or a 4-mm filter for the determination
of mobile metals and in-line filtration with a large non-metallic (e.g., 142-mm),
polycarbonate type, 0.1-mm pore size filter, for geochemical speciation modeling
(i.e., the dissolved fraction) (Puls and Barcelona, 1989). Metal analysis is especially
sensitive to aeration introduced by filtering. A small volume of oxygen introduced
in a reduced groundwater sample can result in decreases of up to 100% of lead,
cadmium, zinc, arsenic, vanadium, and phosphate. The amount of adsorption of a
trace metal onto ferric hydroxide also depends on the extent of iron oxidation that can
be introduced via filtering. It is not unusual to observe differences greater than 10%
between filtered and unfiltered samples for many elements.
Field filtration devices include in-line filters, positive pressure filtration, and
vacuum filtration (Figure 3.19). If sample containers contain a preservative such as

FIGURE 3.19 In-line field filtering with a disposable cartridge. (Courtesy of QED; Ann
Arbor, MI.)
nitric acid, the samples must be field filtered prior to placement in the container.
Conversely, if a container does not contain a preservative, the laboratory can filter
the sample.
Filtering can result in as much disturbance as the process of sample collection
(Stolzenburg, 1986). For example, if a sample is anaerobic with a pH greater than 7.4,
dissolved ferrous iron oxygenation can result in the precipitation of amorphous ferric
iron hydroxide occurring seconds after the initial aeration. The iron precipitation can
impact sample pH, total conductance, alkalinity, ionic strength, turbidity, and color.
Filtering can also exclude contaminants present in karst terrains, where contaminant
transport is more likely to occur in conduit flow via colloidal transport. Contamina-
tion from the filter is another possibility; filter blank results should be collected prior
to filtering so that this potential bias can be evaluated. A filter blank is an analyte-
free solution that is passed through the filter and tested.
Issues regarding sample filtration may be significant in an environmental
case. For example, in May of 1992, a federal appeals court overturned a decision by
the U.S. Environmental Protection Agency to place a landfill in Delaware on the
National Priorities List (NPL). The reason for this ruling was because EPA acted
in an arbitrary and capricious manner in collecting only unfiltered groundwater
samples (Wilson, 1998). While the issue is still outstanding, it highlights the need
to examine filtered data carefully to determine their impact on the contaminants of
interest.

TABLE 3.8
Preservation and Holding Times
Description and
Measurement Preservative Holding Time
Physical property
Color Cool, 4∞C 48 hr
Conductance Cool, 4∞C 28 d
Hardness HNO2 to pH <2 6 mth
Odor Cool, 4∞C 24 hr
pH None required Immediately
Residue filterable Cool, 4∞C 7d
Residue non-filterable Cool, 4∞C 7d
Total residue Cool, 4∞C 7d
Volatile residue Cool, 4∞C 7d
Settleable matter Cool, 4∞C 48 hr
Temperature None required Immediately
Turbidity Cool, 4∞C 48 hr
Samples with low concentrations may require preservation by refrigeration or the

addition of chemical reagents to slow physical chemical or biological changes.
Chemical preservatives usually have a relatively short shelf-life and should be
supplied fresh by the laboratory. Chemical and biological activities altering the
sample chemistry include the formation of metal and organic complexes, adsorption/
desorption reactions, acid-base reactions, redox reactions, precipitation/dissolution
reactions, and microbiological activities affecting the disposition of metals, anions,
and organic molecules. Groundwater samples tested for general chemical parameters
are not chemically preserved. Samples analyzed for volatile organic compounds,
however, are acidified because hydrochloric acid (HCl) effectively prevents biodeg-
radation of many volatile organic compounds (Maskarinec et al., 1990). The U.S.
Environmental Protection Agency requires that samples analyzed for volatile organic
compounds by EPA Standard Method 524.2 be preserved with hydrochloric acid to
a pH of less than 2. Research has demonstrated that the addition of HCl does not
result in the formation of trihalomethanes (Squillace et al., 1999).
Water samples analyzed for metals are stabilized by the addition of nitric acid
(HNO3) to a pH of 2. Samples tested for nitrogen and phosphorus are stabilized with
sulfuric acid (H2SO4). pH adjustments in the field can be performed by using a plastic
dropper bottle containing a 1:1 hydrochloric acid (Draper et al., 1998). If residual
chlorine in the water is a concern, a reducing agent such as thiosulfate or ascorbate
is used. The chain of custody should describe whether preservatives were added to
the sample containers.
Examine the sample collection times on the chain of custody and compare it with
the analysis date to determine if the proper holding time was exceeded. Care is
required that the “reporting date” of the laboratory is not confused with the date of
analysis. Table 3.8 lists appropriate preservation and holding times for selected
analyses (U.S. EPA, 1995).

TABLE 3.8 (cont.)
Preservation and Holding Times
Description and
Measurement Preservative Holding Time
Metals
Dissolved Filter on-site, HNO2 to pH <2 6 mth
Suspended Filter on-site, HNO2 to pH <2 6 mth
Total Cool, 4∞C 6 mth
Hexavalent chromium (Cr+6) Filter, HNO2 to pH <2 24 hr
Dissolved mercury (Hg) HNO2 to pH <2 28 d
Total mercury (Hg) — 28 d
Inorganics, non-metals
Acidity Cool, 4∞C 14 d
Alkalinity Cool, 4∞C 14 d
Bromide None required 28 d
Chloride None required 28 d
Chlorine None required Immediately
Cyanides Cool, 4∞C, NaOH to pH >12 14 da
0.6 g ascorbic acidb
Fluoride None required 28 d
Iodide Cool, 4∞C 24 hr
Nitrogen
Ammonia Cool, 4∞C, H2SO4 to pH <2 28 d
Total Kjeldahl Cool, 4∞C, H2SO4 to pH <2 28 d
Nitrate/nitrite Cool, 4∞C, H2SO4 to pH <2 28 d
Nitrate Cool, 4∞C 48 hr
Nitrite Cool, 4∞C 48 hr
Dissolved oxygen
Probe None required Immediately
Winkler method On-site fixation, store in the dark 8 hr
Phosphorous
Ortho-phosphate (dissolved) On-site filtration, cool, 4∞C 28 d
Hydrolyzable:
Total Cool, 4∞C —
Total dissolved Cool, 4∞C, H2SO4 to pH <2 28 d
Silica Cool, 4∞C 7d
Sulfate Cool, 4∞C, add 2 mL zinc Immediately
acetate plus NaOH to pH >9
Organics
Volatile organics Cool, 4∞C, HCL to pH 2 Immediately
Biological oxygen demand (BOD) Cool, 4∞C 48 hr
Chemical oxygen demand (COD) Cool, 4∞C, H2SO4 to pH <2 28 d
Oil and grease Cool, 4∞C, H2SO4 to pH <2 28 d
Organic carbon Cool, 4∞C, H2SO4 or HCL to pH <2 28 d
Phenolics Cool, 4∞C, H2SO4 to pH <2 28 d
a The maximum holding time is 24 hr if sulfide is present. Samples may be tested with lead acetate paper
to determine if sulfide is present. If sulfide is present, the sulfide is removed by adding cadmium nitrate
powder until a negative acetate paper test is obtained. The sample is filtered and NaOH is added until a
pH of 12 is attained.
b Used only in the presence of residual chloride.

FIGURE 3.20 Loss of gasoline with time from soil samples. (Adapted from King, A., in
Proc. of the National Symposium on Measuring and Interpreting VOCs in Soils: State of the
Art and Research Needs, January 12–14, 1993, Las Vegas, NV, sponsored by the U.S.
Environmental Protection Agency, American Petroleum Institute, and University of Wiscon-
sin Engineering Extension Program, p. 7.)
The regulatory pre-analytical holding temperature for volatile organic compounds

in soil is 4∞C (39.2∞F). A significant body of evidence indicates that this practice results
in unacceptably high losses of volatile organic compounds (Jenkins et al., 1993;
Maskarinec et al., 1990). Current research suggests that refrigeration at –20∞C (–4∞F) is
a more appropriate temperature for soils impacted by volatile organic compounds.
Figure 3.20 graphs different concentrations of gasoline from soil spiked with a
known concentration of gasoline. Samples were stored according to U.S. Environ-
mental Protection Agency procedures and analyzed for total petroleum hydrocarbons
as gasoline (TPHg) from 1 to 14 days after the soil was spiked. As shown in Figure
3.20, the TPH concentration is reduced by one half of the original concentration when
analyzed 3 days after storage at 4∞C (King, 1993).
Another example is the effect on holding time on toluene in water. Researchers
at the U.S. Environmental Protection Agency in Region I found that when a non-
acidified water sample was spiked with 300 ppm of toluene, 95% of the sample was
lost due to biological degradation after 10 days of storage (see Table 3.9) (Bruya,
1996). For higher toluene concentrations, the loss was less, due to the partially toxic
effect of higher levels of toluene on microbes.
3.5.10 FIELD MEASUREMENTS

Environmental reports describing field investigations often contain values obtained
with X-ray fluorescence or organic vapor meters. Regardless of the equipment, a

TABLE 3.9
Aerobic Biodegradation of
Toluene after 10 Days at Varying
Concentrations as Determined
Using Gas Chromatography/Mass
Spectrometry
Initial Concentration Toluene Loss
(ppm) (%)
300 95
500 60
1000 45
2000 40
determination is required concerning the weight given to field measurements and

how to use them in concert with other lines of evidence. Descriptions of X-ray
fluorescence and organic vapor meters are summarized in Table 3.10. Organic vapor
analyzers are used in lieu of laboratory analysis to guide soil excavations on a real-
time basis or to select samples for stationary laboratory analysis. The importance of
properly calibrating and maintaining this field equipment is critical when relying on
these readings for any purpose. Figure 3.21 is an example of a blank multiple-
component calibration form used for equipment calibration.
The qualitative nature of field measurement devices cannot be overemphasized.
Figure 3.22 is a plot of 15 organic vapor meter values of soil samples collected and
analyzed for total petroleum hydrocarbons as gasoline. The purpose of the OVA
measurements was to determine the extent of the soil excavation. The clean-up level
was 250 ppm; 11 samples exceeded this value. Fifteen soil samples from the same
location were collected during the excavation and tested by a stationary laboratory
using EPA Standard Method 8015. Results from the stationary laboratory were
provided after the excavation was completed, indicating that, except for five samples,
all the samples were less than 250 ppm. The possibility exists, therefore, that some
volume of soil was needlessly excavated. In order to confirm this possibility,
analysis of the calibration sheets was required to determine if the equipment was
properly calibrated.
Another example is the relationship between laboratory and headspace analysis
for 9 soil samples collected from a manufactured gas plant that were analyzed for
BTEX. Values for benzene in parts per million are shown in Figure 3.23. The
headspace analysis was performed by piercing the Teflon® septum of the volatile
organic analysis vial with a gas-tight syringe, withdrawing between 10 and 400 mL
of headspace vapor and injecting this into a portable gas chromatograph equipped
with a photoionization detector (Robert and Cutlet, 1989). The generally higher
values (5 out of 9) obtained from the laboratory vs. headspace analyses for benzene
are believed to be due to differences in the soil/contaminant matrix (i.e., tar and
petroleum/soil mixture) and the ability of benzene to volatilize from the matrix.

TABLE 3.10
Descriptions of Field Equipment
Field Equipment Description and Comments
X-ray fluorescence X-ray fluorescence (XRF) spectroscopy is a non-destructive qualita-

tive and quantitative analytical technique used to determine the el-
emental composition of metals (usually in soils, although it is also
used for solid, powder, liquid, and thin films or coatings) (Foley,
1998c). The detection limit is usually in the lower parts per million.
XRF is based on the bombardment of a sample with photons to
produce fluorescence (U.S. EPA, 1997). When interpreting XRF re-
sults, examine the equipment calibration charts to confirm that the
equipment was properly calibrated. Calibration is properly performed
with a full range of target element samples analyzed by atomic absorp-
tion or inductively coupled plasma emission spectroscopy (ICAP). A
full concentration range of the target element or elements of interest
is therefore needed to generate a representative calibration curve. It is
recommended that at least five samples per element be used to develop
the calibration range.
Photoionization detector The HNu ™ photoionization detector is a portable, nonspecific, va-

(HNu™) por/gas detector that uses photoionization to detect a variety of
organic and inorganic volatile compounds. The HNu ™ utilizes two
different source lamps for photoionization: a 10.2- or 11.7-eV
lamp. An HNu ™ is incapable of detecting compounds with photo-
ionization potentials below 10.2 and 11.7 eV, such as methane. If
the lamp window of an HNu ™ meter is not periodically cleaned,
complete ionization of the air contaminants may not occur, result-
ing in biased values. Measurement errors can occur if the probe is
held close to an AC power line or transformers. The device should
be calibrated daily with a commercially prepared standard (usually
100 ppm of isobutylene). When relying upon HNu™ measurements,
obtain the calibration charts to confirm that calibration occurred. If
the battery charge is low, the instrument should be recharged be-
fore making any measurements, as a low battery can impact the
measurement results.
Organic vapor analyzer The OVA has an application similar to the HNu™ for detecting organic
(OVA) vapor meters, but uses a flame ionization detector (FID) rather than a
photoionization detector (PID). An organic vapor analyzer provides a
measurement of the combined concentration of organic vapors. An
organic vapor analyzer has an ionization potential of 11.9 cV and can
detect more compounds than an HNu™. Some organic vapor analyzers
are equipped with an optional gas chromatograph that allows identifi-
cation and measurement of specific compounds. An organic vapor
analyzer responds differently to different compounds. Because the
instrument is factory calibrated to methane, all responses to various
compounds are given in percent relative to methane at 100%.

FIGURE 3.21 Example of an organic vapor analyzer calibration sheet.
3.5.11 FIELD QUALITY CONTROL SAMPLES

Quality control samples are used to assess sampling problems such as field contami-
nation from incomplete decontamination or cross-contamination, container cross-
contamination, and atmospheric contamination. Common field quality assurance/
quality control samples and their functions are summarized in Table 3.11 (Mabey,
1996; Simes and Harrington, 1993).
3.6 SOIL VAPOR SURVEYS

Soil gas surveys were used as early as 1929 as a surface geochemical technique in
oil and gas exploration. This technology evolved in environmental investigations as

FIGURE 3.22 Graph of organic vapor analysis vs. laboratory values for total petroleum
hydrocarbons as gasoline.
a means to measure the soil atmosphere as an indicator of the presence, composition,

and origin of contaminants in the unsaturated and saturated (groundwater) zones. Soil
gas measurements do not permit quantifying soil or groundwater contamination
(Robbins et al., 1990). The primary use of soil gas surveys is as a screening method
for detecting volatile organic contaminants. Soil gas surveys are traditionally used to
provide the following information:
FIGURE 3.23 Comparison of headspace and laboratory results for benzene for nine soil
samples.

TABLE 3.11
Quality Assurance and Quality Control Field Samples
QA/QC
Samples Description and Comments
Background A sample taken from characteristics of the media which is sampled at a site but which
sample is outside the zone of contamination. A minimum of two per sampling event is recom-
mended by the U.S. Environmental Protection Agency (U.S. EPA, 1987). Literature or
monitoring data should be consulted to determine appropriate background locations.
Historical aerial photographs are useful in verifying undisturbed conditions in an area
selected for collecting background samples. Ideally, a soil background sample is col-
lected in similar textured materials and at a depth comparable to the on-site samples.
Field blank A container, usually filled with distilled water from the analytical laboratory, that is
opened at the site when sampling occurs. In some cases, it remains opens throughout the
time that the sampling team is at the site. The inclusion of a field blank is crucial in
deciphering if the contamination is from in situ materials or from the ambient environment.
Field Homogenized samples from a single location used to assess the quality of sampling
duplicates methods and handling. Field duplicates are used to check laboratory procedures. The U.S.
Environmental Protection Agency recommends one field duplicate sample for every ten
samples collected; if the samples are used as evidence in litigation, a higher number of
duplicates may be selected (U.S. EPA, 1987). Split samples are submitted to multiple
laboratories and evaluated to determine agreement in accuracy and precision among the
labs.
Field reagent Solutions used in the field and submitted to a laboratory for analysis. A field reagent
blank blank evaluates chemicals introduced from the use of field chemicals.
Equipment Sample of the last decontamination liquid poured over equipment prior to contact with
rinsate blank a sample. The U.S. Environmental Protection Agency recommends that equipment
rinsate blanks be collected at a rate of one blank for every ten samples collected or one
per day (U.S. EPA, 1987).
Matrix spike A sample that is three times the normal volume required for a specific chemical analysis.
duplicate One MSD sample per matrix is collected for every 20 samples. A matrix spike duplicate
(MSD) is a second aliquot of sample (matrix) that is spiked and subjected to the same procedure
as a matrix spike. The results are used to measure precision.
Matrix spike Samples to which a known quantity of a chemical constituent is added. They are sent to
samples the laboratory without informing the laboratory that the samples were spiked. Sample
spiking is undertaken to measure the laboratory’s ability to measure accurately a constitu-
ent of concern. In general, one spiked sample per 20 water samples is appropriate.
Trip blank Used to evaluate the possible introduction of cross-contamination during transit and
storage, a trip blank is a sample of laboratory-grade distilled water that is poured into a
sample container at the laboratory. The trip blank follows the sample containers, coolers,
and samples throughout the field event. The trip blank measures the amount of volatile
contaminants absorbed through the container in the field. The trip blank sample is sent
to the laboratory at the end of the sampling event. The U.S. Environmental Protection
Agency recommends one trip blank per sampling event. If multiple sampling activities
occur over a large area, one trip blank per sampling location or one per shipping container
is appropriate. The detection of a compound in a sample is considered valid if the
concentration is greater than the amount detected in a trip blank.

FIGURE 3.24 Example of an active soil gas sampler probe.
• Identify and assess the distribution of a contaminant present in the soil vapor phase.
• Approximate the location of soil contamination.
• Assess the distribution of groundwater contamination.
• Evaluate the potential risk of upward transport of vapors.
• Monitor the progress of in situ remediation.
The three types of equipment used to collect soil gas samples are active (Figure
3.24), passive, and flux chambers. An active soil gas survey consists of the with-
drawal of an aliquot of soil vapor from the subsurface, typically with a perforated
sampling probe, followed by analysis in a mobile laboratory. Vapor analysis is
performed with a gas chromatograph and the results reported in units of parts per
million in vapor (ppmv). Soil samples can also be collected within a glass or metal
container (summa canister) and transferred off-site to a stationary laboratory. This
is the most popular soil vapor method due to the availability of companies providing
this service and relatively low cost. Active surveys are conducive to locations with
highly permeable soils (i.e., high gas permeability) and high concentrations of a
volatile compound(s).
Passive soil gas surveys are designed for shallow deployment to identify a broad
range of volatile and semivolatile organic compounds (Foley, 1998a,b). The adsor-
bent (usually composed of polymeric and/or carbonaceous resins) is buried 2 to 3 ft
below the subsurface. The adsorbent is typically removed in 1 to 2 weeks for
extraction and analysis by a stationary laboratory (Tetra Tech, 1998). Reported
advantages include smoothing of daily fluctuations in soil gas concentrations due to
climatic factors and the collection of a time-integrated sample. Passive technique
results are reported only as the total adsorbed mass because the amount of vapor that
comes into contact with the absorbent is unknown. Soil gas results, therefore, cannot

TABLE 3.12
Mean Chemical Concentrations for TCE and PCE Collected
with Passive and Active Soil Gas Sampling Methods
TCE PCE
Passive Active Passive Active
mg/Sample)
(m (ng/L) mg/Sample)
(m (ng/L)
1.97 <50 0.06 <50

108 1250 1.02 <50
195 9.390 0.42 <50
34.8 2010 0.08 <50
<0.02 NAa <0.03 NAa
255 41,800 411 330,000
318 89,500 341 223,000
252 22,200 351 192,000
217 11,500 327 98,500
a NA = not analyzed.
be correlated to soil contamination, the presence of a vapor cloud, or groundwater

and/or free product contamination. Trip blanks used for passive soil gas modules are
manufactured and packaged the same as soil gas modules placed in the subsurface.
The trip blanks, however, remain unopened during all phases of the soil gas survey.
In the 1980s, passive soil gas data were obtained primarily from Petrex tubes.
Petrex samplers contained a thin ferromagnetic (Curie-point) wire coated with
activated charcoal. The wire accumulator is housed within a glass tube (Petrex tube)
and buried 6.5 inches below the ground surface for several weeks. When the sample
is retrieved, the wire is placed into a vacuum chamber and heated, and the volatile
compounds are analyzed by Curie-point mass spectrometry and reported in ion
counts.
Mean chemical concentrations of data collected with passive and active soil gas
sampling methods and tested for PCE and TCE are summarized in Table 3.12.
Samples were collected from sites located in Albert City, IA, and Denver, CO (Tetra
Tech, 1998). Given that the passive sampler yields results in micrograms per sample
and the active soil gas survey produces results in nanograms per liter, a statistical and
interpretative comparison of the data is limited to qualitative observations. The
higher concentrations obtained with the active soil gas survey may be due to extrac-
tion from the polymeric or carbon resins which occurs via placement of the absorbent
into a jar from which a headspace analysis is performed.
Flux chambers consist of an enclosed chamber that is placed on the ground
surface for a specific time period and in which vapor concentrations are measured
through time (Figure 3.25). The chamber is equipped with ports for sweep air inlet
and outlet, thermocouples for measuring the inside air and surface temperature, and
pressure outlets. Flux chamber measurements are common in research applications,

FIGURE 3.25 Flux chamber used for soil gas measurements. (From ASTM, ASTM Standards
on Environmental Sampling, 2nd ed., American Society for Testing Materials, West
Conshohocken, PA, 1997, p. 211. With permission.)
risk assessments, and toxicological studies when direct vapor fluxes out of the
subsurface are required (ASTM 1997b; Hartman, 1998c). For the latter, the emission
rate (ER, expressed in mg/min/m2) for a species is equal to (Q)(CI)/A, where Q is the
sweep air flow rate (m3/min), CI is the concentration of the contaminant (mg/m3), and
A is the sampling area (m2). The term “sweep air” refers to air that is fed into the
chamber at a metered flow rate (e.g., 5 L/min or a chamber retention time of about
6 min) and is then withdrawn until steady-state conditions are attained within the
chamber.
Volatile compounds amenable to detection in a soil gas survey are identified by
examining their partition ratio values. Soil/air partitioning is the process by which
volatile compounds move between the sorbed phase and a vapor phase. A general
rule is that compounds with a Henry’s Law constant of at least 0.05 kPa/m3/mol and
a vapor pressure of 1.0 mmHg at 20∞C or greater are amenable to a soil vapor survey
(Marrin, 1988). Compounds with low Henry’s Law values do not readily partition out
of the aqueous phase into vapor. Another means to identify candidates conducive to
soil gas sampling is to identify compounds with partition ratios above 0.1 (Erickson
and Morrison, 1995). Table 3.13 lists the partition ratios for commonly encountered
volatile compounds.
3.6.1 INTERPRETATION OF SOIL VAPOR DATA

A common error associated with soil gas data is confusion about the reported units.
Soil gas data are usually reported on a volume-per-volume basis (volume of contami-
nant per volume of soil air) and mass per volume (mass of contaminant per volume
of soil air). Examples of volume-to-volume and mass-per-volume relationships are
provided in Table 3.14 (Hartman, 1998b).

TABLE 3.13
Partition Ratios of Volatile Compounds
Compound Partition Ratio
Methane 7982.99
Ethane 874.02
Freon-12 108.87
Vinyl chloride 105.11
Cyclohexane 8.55
Freon-11 4.86
1,1,1-TCA 1.35
Tetrachloroethylene 1.29
Carbon tetrachloride 0.88
Trichloroethylene 0.52
Ethylbenzene 0.39
Toluene 0.30
Benzene 0.25
Xylene 0.24
Chloroform 0.17
1,2-Dichloroethane 0.05
Bromoform 0.03
In most cases, soil vapor data reported in mg/L is assumed to be equivalent to

parts per billion. While correct for water due to the density of water being equal to
1 gram per milliliter (g/mL), it is not correct for soil gas data. The conversion of vapor
data from units of mg/L to ppbv is (Hartman, 1998b):
Csoil gas (ppbv) = (Csoil gas [mg/L] ¥ 24,000)/molecular weight of the compound
where the 24,000 is the milliliters per mole at 20∞C. For example, the molecular
weight of PCE is 165, so 1 mg/L is equal to about 145 ppbv. Soil samples collected
TABLE 3.14
Units Used in Soil Gas Surveys
Volume-by-volume basis
Microliters of compound per liter of soil air (mL/L)
Nanoliters of compound per liter of soil air (nL/L)
Parts per billion by volume (ppbv)
Parts per million by volume (ppmv)
Percent by volume (%)
Mass-per-volume basis
Micrograms of compound per liter of soil air (mg/L)
Milligrams of compound per cubic meter of soil air (mg/m3)
Millimoles of compound per cubic meter of soil air (mmol/m3)

Surface Deep Surface and Deep Co-mingled
FIGURE 3.26 Plot of soil vapor data with depth. (Adapted from Hartman, B., MTBE:
Beware the False Positive, LUSTline Bull. No. 26, New England Interstate Water Pollution
Control Commission, Wilmington, MA, 1998, p. 18. With permission.)
at multiple depths can be plotted as a function of concentration vs. depth. Figure 3.26
depicts four common scenarios and corresponding interpretations regarding the
origin of the contamination.
Numerous factors affect the observed distribution of the volatile organic com-
pounds in soil gas. Considerations in the interpretation of soil gas data include the
following variables:
• Presence of contamination at the capillary fringe

• Liquid/gas partitioning coefficient of the compound(s) detected
• Velocity or vapor diffusivity of the compound
• Preferential migration of vapor through soil with different gas permeabilities such
as high gas-permeable bedding in utility line trenches or road beds — examples of
the gas permeability (in cm/sec) of various soils include gravel, 103 to 10; clean sand,
(10 to 10–2; silty sand, 1 to 10–3; loess, 10–1 to 10–5; and glacial till, 10–2 to 10–9
(Peargin, 1994)
• Vapor retardation and/or biodegradation
• Presence of low gas permeability (also called pneumatic permeability) layers such
as moist silt or clay layers, caliche horizons, a perched water table, or barriers such
as building foundations and high moisture content soils caused by uneven surface
irrigation
• Presence of contaminants from discrete surface releases and soil gas displacement
via wetting fronts from recharge events or as a result of barometric pressure
changes (storm fronts)
• Comparison of shallow soil gas data collected on different days with significant
ambient air temperature differences

In addition to these issues, differences in the type of data obtained with the specific
types of soil gas survey equipment must be considered. Issues specific to passive and
active surveys are summarized in Table 3.15 (Hartman, 1999).
While it is important to collect sufficient vapor to purge the system, collecting
excessive volumes is discouraged. The larger the soil vapor volume withdrawn, the
greater the uncertainty regarding the origin of the sample. This subsequently in-
creases the potential that atmospheric air is drawn down the outside of the probe
body. Sampling equipment with small internal volumes offers advantages over
systems with larger empty volumes, because the former systems require significantly
less vapor to be withdrawn.
3.7 ANALYTICAL METHODS
The selected analytical method determines what can be identified relative to the goal
of the sampling and analysis (e.g., remediation, forensic analysis, cost allocation).
The axiom — “What you find is what you look for” — is true for the selection of
an appropriate analytical method given the chemical usage history at the site. The
first level of analysis is to examine the analytical methods used and compare it with
the known chemicals used at a site.
The second level of analysis includes examination of the following six sources
of potential bias from the analytical measurement process (Mishalanie, 1995):
• Misidentification of compounds (false and negative bias)

• Chemical interference (false and negative bias)
• Incomplete recovery of analytes from the sample matrix (negative bias)
• Matrix effects (false and positive bias)
• Instrumentation calibration (false and positive bias)
• Cross-contamination (positive bias).
An example of the impact of analytical methods on sample results is the analysis

of methyl-tertiary-butyl-ether (MTBE). There currently is no official U.S. Environ-
mental Protection Agency standard method for MTBE analysis (Draper et al., 1998).
For MTBE analysis using EPA Standard Method 8020, shortened run times (i.e., 20
to 10 minutes) can result in the co-elution of alkane compounds that elute similarly
to MTBE being reported as MTBE (false positive). EPA Standard Methods 8240 and
8260 are gas chromatography methods using a mass-selective detector that can
quantify MTBE and other compounds that co-elute with it; as a result, these methods
tend to be more reliable. A solution is to use a combination of these methods; EPA
Standard Method 8020, for example, is appropriate if the results are non-detect.
MTBE values from samples with total petroleum hydrocarbon (TPH) as gasoline less
than 5 ppm (water) and 100 mg/kg (soil) are more likely to be reliable because low
values of the co-eluting alkanes are likely (Hartman and Hitzig, 1998). As gasoline
values increase, the potential for over-reporting MTBE values also increases. Con-
firmation testing using EPA Standard Method 8020 with a sufficiently long run time

TABLE 3.15
Effects of Soil Gas Sampling Equipment
on Sample Results and Interpretation
Passive Soil
Vapor Surveys Considerations
Sample spacing The selection of sampling locations for passive soil vapor surveys is predicated
on considerations identical to those used in active soil vapor methods. These
include the program objectives, the need for adequate spatial coverage, and the
budget. Predetermined and widely spaced grid patterns are commonly em-
ployed for reconnaissance work, while higher density, irregularly situated loca-
tions are used to bracket specific source areas.
Collection depth Passive collectors are buried near the ground surface (6 inches to 3 feet). This
procedure originates from the convenience in deploying and retrieving the
collector. Ideally, similar to active surveys, collectors are located close to the
suspected contamination source to minimize the effects of vapor movement.
Collectors buried within several feet of the ground surface are susceptible to air
infiltration due to changes in barometric pressure and surface temperature. If the
ambient air is contaminated (e.g., at an operating gasoline station or inside of
a drycleaning operation), the collector can conceivably adsorb more contami-
nation from infiltration of the surface air than from subsurface contamination.
In this situation, it is advisable to bury the collector deeper than 3 feet below
the ground surface.
Exposure period The exposure period for passive collectors is generally selected more for
convenience than for technical reasons. An assumption inherent with the inter-
pretation of passive soil gas data is that the each collector is exposed to the same
quantity of soil vapor. Passive collectors are typically deployed for the same
period (several days to three weeks) so that the data are normalized based on the
exposure time. The exposure period for a passive collector can depend on the
concentration of the contaminant of interest and the desired detection levels. In
areas of suspected high concentration, collectors remain in the ground for
shorter periods (1 to 5 days) relative to areas of suspected low concentrations
(2 to 3 weeks).
Method blanks Because the passive soil vapor method does not enable real-time data to be
collected, analysis of method blanks is important to verify that detected con-
tamination is not from another source; therefore, a method blank or trip blank
should be included as part of the sample batch. If data from method and/or trip
blanks are unavailable, it is possible that values from the collectors can be
argued as being due to contamination from other sources.
Active Soil
Vapor Survey Considerations
Sample spacing The selection of sampling location is dependent on the objectives of the program,
the need for adequate coverage, and the budget. Predetermined and widely spaced
grid patterns are commonly used for reconnaissance work, while closely spaced,
irregularly situated locations are used for identifying specific source areas.

TABLE 3.15 (cont.)
Active Soil
Collection depth Collection depths should maximize the probability of detecting contamination,
yet minimize the effects of vapor movement, changes in barometric pressure,
surface temperature, or breakthrough of atmospheric air from the surface. To
optimize the probability of contaminate detection and minimize biases associ-
ated with vapor movement, soil vapor samples are collected as close to the
suspected contamination source as possible.
Probe seals For collection systems with large purge volumes or designed to collect large
sample volumes, it is often necessary to seal the probe at the ground surface.
Surface seals are necessary for small volume systems if the soil is highly porous
and the sampling depth is close to the ground surface (approximately 3 ft).
Common sealing techniques include packing the upper contact of the probe and
the soil with grout or the use of an inflatable seal. Seal integrity is tested with
a tracer gas (e.g., propane or butane) that flows around the probe at the contact
point with the ground surface. A soil vapor sample is then collected and
analyzed for the presence of the tracer compound.
Probe decontamination All external parts should be wiped clean and washed as necessary to remove any
soil or contaminant films. The internal vapor pathway should be purged with a
minimum of five volumes of air or an inert gas, or replaced or washed if
contamination or water is present in the probe. Probes fitted with internal tubing
offer advantages because the internal tubing can be replaced.
Excessive vacuums Soil vapor samples collected under high vacuum conditions may reflect con-
applied during taminants that are desorbed off the soil grains created by the collection process,
during sample rather than contaminants present in the undisturbed soil vapor. For collection
collection systems employing vacuum pumps, the vacuum applied to the probe should be
measured and recorded.
Systems with vacuum Soil vapor samples from collection systems employing vacuum pumps should
pumps be collected on the intake side of the pump to prevent potential contamination
from the pump. Because the pressure on the intake side of the pump is below
atmospheric, soil vapor samples must be collected with appropriate collection
devices, such as gas-tight syringes and valves, to ensure that the samples are not
diluted by outside air.
Sample containers/ On-site analysis is recommended to ensure sample integrity. Soil vapor samples,
sample storage however, are often collected and analyzed off-site. To minimize potential
effects on sample integrity, the maximum storage time should be no more than
48 hr after sample collection. For fuel-related compounds (e.g., BTEX) and
biogenic gases (methane, carbon dioxide, and oxygen), only the following
containers are allowable: Tedlar bags, gas-tight vials (glass or stainless steel),
and summa canisters.

TABLE 3.15 (cont.)
Active Soil
Purge volume Sample collection equipment used for active soil vapor surveys has an internal
volume filled with air or some inert gas prior to insertion into the ground. This
internal volume must be completely purged and filled with soil vapor to ensure
that a representative soil vapor sample is collected. While different procedures
are available for obtaining the optimum purged volume, sufficient vapor should
be extracted prior to sample collection to purge the probe and collection system
of all ambient air or purge gas (one purge volume). Another procedure specifies
the removal of four system volumes. Most samplers purge a minimum of one
to five system volumes prior to sample collection. Because soil vapor data are
interpreted qualitatively, the purge volume should be consistent for all samples
collected from the site.
or by GC/MS is one option. Another reported technique is a modified ASTM Method

D4815 that was specifically designed to test for MTBE, ETBE, and TAME, as well
as methanol, ethanol, and tertiary-butyl alcohol in soil and groundwater (Global
Geochemistry, 1998).
3.7.1 MISIDENTIFICATION OF ANALYTES

The misidentification and laboratory misrepresentation of compounds is common. A
report performed by the Advancement of Sound Science Coalition for the U.S.
Environmental Protection Agency found that 11% of 2000 reports showed “serious
deficiencies” with pesticide testing (Meyer, 1999). In some cases, fraud is the culprit,
such as in the case of the United States v. Hess Environmental Laboratories and
United States v. Klusaritz, where the director of a testing laboratory accepted pay-
ment for fabricated data from testing that was not performed. Numerous reasons for
misidentification are possible, including the co-elution of compounds (e.g.,
dibromochloromethane, dichloropropene, and 1,1,2-trichloroethane). Laboratories
may automatically assign the name of a product type of material that elutes within
a given carbon range or retention range — results reported as in the “gasoline range”
are not the same as “gasoline”.
Another example is shown in Table 3.16 for TPH analysis for gasoline and diesel
using a gas chromatograph equipped with a flame ionization detector (Bruya, 1994;
1998).
These test results were performed according to standard state- and U.S. Environ-
mental Protection Agency-mandated total petroleum hydrocarbon testing protocols.
If the purpose of these data is to demonstrate that common plants contain organic

TABLE 3.16
Total Petroleum Hydrocarbon Values
in Various Materials
TPH as Gasoline TPH as Diesel
Matrix (ppm) (ppm)
Spinach <10 60
Carrots <10 10
Orange juice 300 <10
Cedar tree 1400 2200
Pine tree 450 400
Dandelion <10 140
Daisy 40 40
Moss <10 <10
compounds that boil in the same boiling ranges associated with gasoline and diesel,
then the data are usable. If the goal is to identify the type of blended fuel for
remediation purposes, the value of the data is questionable.
The selected extraction method can bias sample results. For example, for TPH
analysis, an acetone/methylene chloride extractant is more rigorous than methanol;
the former extractant extracts more hydrocarbons from the sample, resulting in a
higher sample concentration. The extractant used is often selected from among
several recommended compounds.
The use of multiple laboratories in a project can produce dramatically different
analytical and interpretative results. A 10 to 20% variation in reported concentrations
for the same sample (spiked concentration) tested by several laboratories is not
uncommon. The presence of laboratory contaminants should also be examined.
Common laboratory contaminants and sources are listed on Table 3.17 (Erickson and
Morrison, 1995; Mabey, 1995). Benzene, toluene, ethylbenzene, and xylene (BTEX)
are common laboratory artifacts due to the large volume of BTEX analyses processed
through many laboratories.
3.7.2 LABORATORY DOCUMENTATION

The underlying laboratory documentation is required for forensic review of chemical
data, including judging the validity of reported analytical results (Maney and Wait,
1991; Zurer, 1991). Depending on the level of review required, the following informa-
tion can be requested or subpoenaed from the laboratory (Rosecrance et al., 1988).
3.7.2.1 Chain of Custody

A copy of the chain of custody is available from the laboratory that performed the
analysis as well as the firm that performed the sampling if it was not the laboratory.
A chain of custody form provides evidence concerning sampling procedures and

TABLE 3.17
Common Laboratory Contaminants and Sources
Compound Potential Source
Methylene chloride, MEK, Laboratory solvents
Freon-113 (1,1,2-trichlor-1,2,2-trifluoroethane),
chloroform, carbon tetrachloride
bis(2-Ethylhexyl)phthalate, di-butylphthalate, adipates Tubing plasticizers
Trihalomethanes Domestic water
N-Nitrosodiphenyl amine Rubber additive (diphenyl amine).
Toluene Electrical tape
2-butanone (MEK) Duct tape
Acetone, isopropyl alcohol Field decontamination solvent, drilling aid
Carbon disulfide, methyl chloride Natural products
Fluorobenzene, chlorobenzene-d5, Laboratory internal standardsa
1,4-dichlorobenzene-d4
Bromofluorobenzene; 1,4-difluorobenzene, Laboratory matrix spikes used
chlorobenzene-d5 for volatile organic tests (Bruya, 1994).
Dibromofluoromethane; 1,2-dichloroethane-d4, Laboratory system monitoring compoundsb
toluene d8, 4-bromofluorobenzene
a Internal standards are typically analytes of interest that are spiked into a blank prior to analysis for the
purpose of measuring the accuracy of the measurement.
b System-monitoring compounds used by laboratories in volatile compound analyses; detection of these
chemicals is usually only considered positive when their concentrations are greater than ten times the
amount detected in any blank samples.
sample integrity. A sample chain of custody is a form that documents the collection
and possession during each stage of sample collection, shipment, storage, and the
process of analysis. The review of the chain of custody is important because it
provides information concerning the temporal sequence of sampling, the personnel
responsible for sampling, and a means to evaluate if holding times were exceeded.
A standard guide for chain of custody procedures has been established by the
American Society for Testing Materials (ASTM, 1995).
While the chain of custody form differs depending upon the organization, the
basic format and information required are similar. This information includes:
• Sample identification
• Sampling location, sampling point, date, and sampling date interval
• Signatures of sampling personnel and signatures of all personnel handling and
receiving the samples
• Project identification
• Sample preservation (type and concentration)
• Number of containers and their volume
• Air bill or carrier identification
• Analyses desired along with specific instructions (e.g., accelerated analyses)
• Sample type (e.g., grab, composite)

When the analytical laboratory takes possession of the samples, they should ac-
knowledge receipt on the primary laboratory chain of custody form. At that point, the
recipient should inspect the condition of the samples and reconcile the sample labels
with the chain of custody information. While in the custody of the laboratory, the
analyst should be able to testify that no one tampered with the samples without their
knowledge. The samples should be stored in a secure (preferably locked) environ-
ment prior to analysis.
If the primary laboratory is subcontracting to another laboratory for specialized
testing, the chain of custody should remain with the primary laboratory. The prime
laboratory should prepare a receipt providing information about which samples are
being split, where they were delivered, the time and date of the transfer, and the
persons involved with the transfer.
When reviewing a chain of custody form, examine whether more than one person
has handled the samples; ideally, the assigned field sampler should be personally
responsible for the care and custody of the samples until they are surrendered to the
laboratory. The sample is considered to be in the sampler’s custody if the following
criteria are met (U.S. EPA, 1995):
• The sample is in the possession of the sampler or is in view after collection.

• The sample was in the sampler’s possession and then locked up or sealed in a
manner to prevent tampering.
• The sample is in the sampler’s possession and then placed in a secure area.
When transferring sample possession, the individuals relinquishing and the individu-
als receiving the samples should sign, date, and note the time on the custody record.
If the ice chest or other shipping container was opened, it should be noted on the
chain of custody. The field personnel whose signatures are on the chain of custody
should be able to testify that no one was able to tamper with the samples without their
knowledge.
Review the chain of custody to determine the condition of the ice chest upon
receipt by the laboratory. The sequence of the sampling is also worth noting (see
Section 3.5.6). For example, if cross-contamination is suspected, knowing whether
suspected cross-contaminated samples were collected after a sample with a signifi-
cant contaminant concentration was sampled may assist in this examination.
The use of custody seals is recommended when the results are used in litigation.
A custody seal has the sample number, date of collection, and the signed and printed
name of the sampler. The seal is placed over the sampling cap so that anyone opening
the sample container breaks the seal. Custody tape is wrapped around the shipping
container and similarly dated and signed by the person in whose custody the samples
have remained. If the sample containers or shipping container are tampered or
violated in some manner, the analytical laboratory can record this violation. The
chain of custody is placed within a Zip-Lok™ bag within the shipping container to
prevent melting ice from obscuring the ink on the form.
A chain of custody form also originates with the laboratory that prepared the
sample containers. Each time samples are exchanged, the chain of custody form is

signed. Security seals can be placed over the caps of empty, clean sample containers
or blanks and signed by the laboratory that prepared the containers. The person who
broke the laboratory security seals should be able to testify as to when this occurred.
The field logbook should also contain this information.
3.7.2.2 Document Control/Control Log

A document control log contains a list of all laboratory documents such as logbooks,
forms, quality assurance manuals, standard operation procedures for the laboratory,
and software. A document control log includes the title of the document, the assigned
document control number, assigned field or laboratory section, location or personnel,
the date issued, and the date archived.
3.7.2.3 Signature List

A signature list contains the record of the signatures and initials of all personnel that
completed log records or approved data. The signature list includes each employee’s
typed or printed name and initials, a handwritten signature and initial, the employ-
ment start date, and termination date (if applicable). Temporary employees are
included on the signature list.
3.7.2.4 Logbook Cover Sheet

The logbook cover sheet documents the purpose of the logbook and contains the
document control number. The logbook cover sheet includes the document control
number, analytical methods and parameters, instrument identification (if applicable),
and date issued.
3.7.2.5 Sample Kit Preparation Log

Sample kit preparation logs document the preparation of sample bottles and sampling
kits. Kit preparation logs include the following information:
• Project identification and sample kit identification

• Type of bottles and lot number, if certified bottles are used
• Intended analysis to be performed for samples placed into each bottle or vial
• Preservatives and reagent in the sample containers
• Preparation of field and trip blanks
3.7.2.6 Field Logs

Field logs document events associated with sample collection. If personnel from the
laboratory performed the sampling, the laboratory maintains the field log. Field logs
contain a detailed chronology on numbered log pages that contain information such
as sample location, time of sample location, atmospheric conditions, sampling de-
scriptions such as odors and colors, field measurements, and any difficulties in

TABLE 3.18
Examples of Information in a Field Logbook
Well identification
Well depth
Static water level depth and measurement techniques
Presence of immiscible layers and instrument/detection method used
Well yield (high or low)
Purge volume and pumping rate
Time well purged
Collection method for immiscible layers and sample identification number(s)
Well evacuation procedure/equipment
Sample withdrawal procedure/equipment
Date and time of collection
Well sampling sequence
Types of sample containers used and sample identification numbers
Preservative(s) used
Parameters requested for analysis
Field analysis data and method(s)
Sample distribution and transporter
Field observations during sampling
Name of collector
Climatic condition
Internal temperature of field and shipping (refrigerated) containers
Shipper and shipping number
Photograph identification, photographer and orientation
obtaining samples or unusual circumstances. An example of information included in

a field logbook used to record a groundwater sampling event is shown in Table 3.18.
3.7.2.7 Sample Receipt Checklist and/or Log

Sample receipt logs are used to evaluate and document the condition of a sample
received by the laboratory. Information contained on the sample receipt checklist
includes:
• Client sample identification

• Laboratory sample identification
• Presence or absence of custody seals
• Acceptability of sample container for the analysis requested
• Volume and preservation (if any)
• Sample condition at receipt
• Temperature of the ice chest
• Presence or absence of headspace in samples submitted for volatile organic analysis
• Assigned number used by the laboratory in their computer tracking system
• Any discrepancies between the chain of custody record and sample labels

A laboratory phone log may be available if the laboratory contacted the client
regarding unacceptable samples and/or on a sample condition notification form. The
sample condition notification form documents and communicates to the client any
noncompliance with the sample condition at the time of receipt by the laboratory,
such as:
• Broken bottles
• Headspace in volatile organic vials
• Sample labels not matching the chain of custody
• Incorrect sample containers for the analysis requested
Directions from the client in response to any noncompliance issues are recorded on
the sample condition notification form.
3.7.2.8 Sample Preparation Logbook

This log documents sample preparation activities such as sample extractions and/or
metal digestions. Information includes the sample number, sample type or matrix,
parameter and method number, date and time of preparation, the analyst’s signature,
initial and final sample volume or weight, the volume and identification of spikes,
and surrogate and quality control samples included in the sample batch.
3.7.2.9 Sample Analysis Log

This logbook contains information pertaining to the analysis and calculation of the
final sample result. Data recorded in this log include the following:
• Sample identification number

• Parameter/analyte to be tested
• Analytical method number
• Sample matrix
• Instrument identification
• Reagent and calibration standard identification
• Date and time of analysis
• The analyst’s signature
• Sample aliquot
• Dilution factors and final dilution volumes (if any)
• Calibration data
• Calibration correlation coefficient
• Percent recovery for laboratory control standards and matrix spikes
• Comments on reruns
• Unusual observations noted during analysis
3.7.2.10 Instrument Run Log

This log maintains an accurate record of the analysis of the calibration standards,
field samples, and quality control samples processed during an analytical run. This

information is included in a contracts laboratory program (CLP) documentation
package.
3.7.2.11 Instrument Maintenance Log

This log documents the maintenance and repair activities performed on major instru-
ments. This log usually contains the instrument name, manufacturer, model and serial
number, date received and placed into service, service contract information, and the
date, time, and description of each maintenance activity. The initials of the person
who performed maintenance or repair activity on the equipment are usually included
on the log. The routine and periodic equipment maintenance record for 30 days prior
to sample analysis should be provided to determine whether the analytical equipment
was properly maintained.
3.7.2.12 Certificates of Analysis

Certificates of analysis for standards and reagents are provided by the manufacturer
to document the lot number, composition, purity, and grade of the material. The
laboratory should produce this information if issues regarding the integrity of the
calibration standards arise. If a CLP data format is produced, the lot numbers
associated with the various reagents are identified and further review of the supplier
and purity of the standard can be examined. It is not uncommon that reagents used
in instrument and sample calibrations are purchased from 40 to 50 different suppliers.
If a non-CLP laboratory package is not available, the production of this information
is usually burdensome and time intensive.
3.7.2.13 Laboratory Certification

Laboratory certification (state and federal) and a laboratory’s internal quality assur-
ance/quality control package should be requested to ensure that the laboratory is
certified to perform the requested tests.
3.7.3 LABORATORY QUALITY CONTROL SAMPLES

The U.S. Environmental Protection Agency has created a structured process that
identifies data quality objectives for accuracy, precision, sensitivity, representa-
tiveness, comparability, and completeness. Environmental reports routinely contain
the sample quality assurance/quality control (QA/QC) procedures associated with
the analytical laboratory. Laboratory QA/QC samples allow evaluation of in-
strument and laboratory performance in addition to providing a means to deter-
mine the quality of the analyses. Terminology and definitions used in QA/QC
reports are summarized in Appendix F. Table 3.19 summarizes laboratory QA/QC
samples.
A reporting item for internal analytical control and included in laboratory pack-
ages is the percent recovery of the matrix spike. For example, if bromofluorobenzene

TABLE 3.19
Description of Laboratory Quality Assurance/Quality Control (QA/QC)
Samples
QA/QC Sample Description and Comment
Duplicate sample Subsamples or aliquots obtained from a sample. A duplicate

sample is a measure of the precision of analysis in terms of
relative percent difference (RPD).
Instrument blank An analyte-free sample introduced at the point of detection or
measurements for the purpose of evaluating potential artifacts
from the instrument or detection system.
Laboratory reagent blank Reagents used in the laboratory to analyze for the analytes of
interest for the purpose of evaluating the introduction of chemi-
cals via the use of laboratory reagents.
Matrix spike (MS) sample A measure of the method used relative to the sample matrix.
Matrix spike/duplicate (MSD) sample An MSD sample is collected from a matrix spike sample and
measures the precision of analysis in terms of the RPD.
Method blank, reagent blank Laboratory-grade water or clean soil that is analyzed with the
soil or water samples. It provides a measure of interferences
introduced by laboratory practices; one method blank per ten
samples is required. Some laboratories may perform multiple
analyses of a method blank until contaminants are non-detected.
If this is suspected, obtain the results of these multiple analyses.
Method spike Laboratory-grade water that is spiked with the analyte of interest
to monitor the accuracy of the laboratory performance.
Performance sample A quarterly or biannual performance evaluation performed by
the Environmental Protection Agency or the National Bureau of
Standards.
is added to the sample and less than 70% of it is recovered, then the analysis may be
interpreted as inadequate. In order to determine if a surrogate standard falls within
an acceptable accuracy and precision limit, perform the following procedure:
1. Calculate the percent recovery of each surrogate in each sample. A surrogate is a

compound not normally found in an environmental sample which is spiked into
matrix or blank samples and then subjected to the entire preparation/analysis
procedure to measure recovery. Surrogate results are used to measure accuracy.
2. Once 30 samples of the same matrix are analyzed, calculate the average percent
recovery and standard deviation of the percent recovery for each surrogate.
3. For a given matrix, calculate the upper and lower control limit for method perfor-
mance for each surrogate standard as follows: upper control limit (UCL) = average
percent recovery plus 3 standard deviations, and the lower control limit (LCL) =
average percent recovery minus 3 standard deviations.
4. Compare to the control limits in Table 3.20.

TABLE 3.20
Analytical Control Limits for Selected Surrogate Chemicals
Surrogate Low/Medium Low/Medium
Compound for Water for Soil/Sediment
4-Bromofluorobenzene 86–115 74–121

1,2-Dichloroethane-d4 76–114 70–121
Toluene-d8 88–110 81–117
TABLE 3.21
Acceptance Limits for Duplicate or Matrix
Spikes in Groundwater Samples
Recovery of Matrix Spike
Compound (%)
Metals 80–120
Volatile organic compounds 70–130
Anions 80–120
Nutrients 70–130
Herbicides 40–160
While the acceptance limits for the recovery of a matrix spike varies between state
and federal programs, typical acceptance limits for duplicate or matrix spike samples
for groundwater are shown in Table 3.21. If a significant number of the samples are
outside of these deviation standards for various compounds, the reasons for these
errors, deficiencies, or analytical reasons should be investigated and documented and
a judgment made as to the reliability of these data.
REFERENCES
ASTM, 1997a. Specific waste Sampling procedures, in ASTM Standards on Environmental

Sampling, 2nd ed., American Society for Testing Materials, West Conshohocken, PA, pp.
558–658.
ASTM, 1997b. Standard guide for soil gas monitoring in the vadose zone (D 5314-92), in
ASTM Standards on Environmental Sampling, 2nd ed., American Society for Testing
Materials, West Conshohocken, PA, pp. 185–215.
ASTM, 1997c. Standard guide for direct-push water sampling for geoenvironmental investi-
gations (D 6001-96), in ASTM Standards on Environmental Sampling, 2nd ed., American
Society for Testing Materials, West Conshohocken, PA, pp. 444–457.
ASTM, 1997d. Composite sampling and field subsampling for environmental waste manage-
ment activities (D 6051-96), in ASTM Standards on Environmental Sampling, 2nd ed.,
American Society for Testing Materials, West Conshohocken, PA, pp. 514–520.

ASTM, 1996. Standard practices for preparation of sample containers and for preservation
of organic constituents (D 3694-96), in ASTM Standards on Environmental Sampling,
2nd ed., American Society for Testing Materials, West Conshohocken, PA. pp. 584–
589.
ASTM, 1995. Standard guide for sampling chain of custody procedures (D 4840-95), in
ASTM, 1993. Standard practice for description and identification of soils: visual manual
procedure (D 2488-93), in ASTM Standards on Environmental Sampling, 2nd ed.,
ASTM, 1992. Standard guide for sampling groundwater monitoring wells (D 4448-85a), in
ASTM, 1990. Standard practice for decontamination of field equipment use at nonradioac-
tive waste sites (D 5088-90), in ASTM Standards on Environmental Sampling, 2nd ed.,
Barcelona, M., 1988. Uncertainties in ground water chemistry and sampling procedures, in
Melchior, E. and R. Bassett (Eds.), Chemical Modeling of Aqueous Systems II, Ameri-
can Chemical Society Symposium Series 416, American Chemical Society, Los Ange-
les, CA, pp. 310–320.
Barcelona, M. and R. Morrison, 1988. Sample collection, handling and storage: water, soils,
and aquifer solids, in Proc. of Groundwater Quality Methodology Workshop, November
1–3, Arlington, VA, Cooperative States Research Service, Omaha, NE, p. 13.
Barcelona, M., Wehrmann, H., and M. Varljen, 1994. Reproducible well-purging procedures
and VOC stabilization criteria for ground-water sampling, Ground Water, 32(1):12–22.
Barcelona, M., Holm, T., Schock, M., and G. George, 1989. Spatial and temporal gradients
in aquifer oxidation-reduction conditions, Water Resources Research, 25(5):991–1003.
Bergren, C., Tuckfield, R., and N. Park, 1990. Suitability of the Hydropunch for assessing
groundwater contaminated by volatile organics, in Fourth National Outdoor Action
Conference on Aquifer Restoration, Ground Water Monitoring, and Geophysical Meth-
ods, National Ground Water Association, Dublin, OH, pp. 387–399.
Blegen R., Hess, J., and J. Denne, 1988. Field Comparison of Ground-Water Sampling
Devices, National Water Well Association Second Annual Outdoor Action Conference,
May, Las Vegas, NV, p. 24.
Bruya, J., 1998. Review of analytical data, in Proc. of the 1998 National Environmental
Forensic Conference: Chlorinated Solvents and Petroleum Hydrocarbons, College of
Engineering and Engineering Professional Development, University of Wisconsin,
Madison.
Bruya, A., 1996. Overview of hydrocarbon fingerprinting techniques: sources of analytical
error, in Proving the Technical Case: Chlorinated Solvents and Petroleum Hydrocar-
bons, College of Engineering and Engineering Professional Development, University of
Bruya, A., 1994. Interpretation of laboratory analysis of chlorinated solvents, in Proving the
Technical Case: Soil and Groundwater Contamination Litigation with Emphasis on
Chlorinated Solvent Contamination, Department of Engineering and Engineering Pro-
fessional Development, University of Wisconsin, Madison, p. 140.
Church, P., and E. Gvanato, 1996. Bias in ground-water data caused by well bore flow in
long screen wells, in Ground Water, National Ground Water Association, Dublin, OH,
pp. 313–327.

Creasey, C., 1996. Low flow sampling and trace metal clean techniques: demonstrated
applicability for trace metal analyses of groundwater, No. H22D-51440h, EOS Trans-
actions, 77(46):1.
Csuros, M., 1994. Environmental Sampling and Analysis for Technicians, Lewis Publishers,
Boca Raton, FL, p. 320.
Draper, W., Remoy, J., and S. Perera, 1998. Getting reliable data from water labs testing for
MTBE (or any other volatile contaminant), in The Southwest Focused Ground Water
Conference: Discussing the Issue of MTBE and Perchlorate in Ground Water (Suppl.),
National Ground Water Association, Dublin, OH, pp. 19–51.
Erickson, R. and R. Morrison, 1995. Environmental Reports and Remediation Plans: Forensic
and Legal Review, John Wiley & Sons, New York, p. 570.
Foley, G., 1998a. Passive Soil Gas Sampler: Gore-Sorber Screening Survey Passive Soil Gas
Sampling System, EPA/VS/SCM/19, Environmental Technology Verification Program
Verification Statement, U.S. Environmental Protection Agency, Washington, D.C., p. 3.
Foley, G., 1998b. Passive Soil Gas Sampler: Emflux Soil Gas Investigation System, EPA-VS-
SCM-22, Environmental Technology Verification Program Verification Statement, U.S.
Environmental Protection Agency, Washington, D.C., p. 3.
Foley, G., 1998c. Field Portable X-Ray Fluorescence Analyzer: Sefa-P Analyzer, EPA-VS-
SCM-05, Environmental Technology Verification Program Verification Statement, U.S.
Environmental Protection Agency, Washington, D.C., p. 3.
Garabedian, S., LeBlank, D., Hess, K., and R. Quadri, 1987. Natural-gradient tracer test in
sand and gravels: results of spatial moments analysis, in U.S. Geological Survey Program
on Toxic Waste Ground-Water Contamination: Proc. of the Third Technical Meeting,
March 23–27, Pensacola, FL, pp. B13–B16.
Gee, G. and J. Bauder, 1986. Particle-size analysis, in Methods of Soil Analysis. Part I.
Physical and Mineralogical Methods, 2nd ed., American Society of Agronomy, Madison,
WI, pp. 383–411.
Gibs, J., Brown, G., Turner, K., MacLeod, C., Jelinski, J., and S. Koehnlein, 1993. Effects of
small-scale vertical variations in well-screen inflow rates and concentrations of organic
compounds on the collection of representative ground water-quality samples, Ground
Water, 31(2):201–208.
Global Geochemistry Corporation, 1998. Announcing a New Environmental Test for Oxygen-
ate Additives (promotional material), Canoga Park, CA, p. 2.
Hartman, B., 1999. Soil vapor analysis and interpretation, in Chlorinated Solvent Contamination:
Legal and Technical Issues, Argent Communications Group, Forresthill, CA, pp. 84–123.
Hartman, B., 1998a. To Methanol Preserve or Not To Methanol Preserve?, LUSTline Bull.
No. 28, New England Interstate Water Pollution Control Commission, Wilmington, MA,
pp. 17–18.
Hartman, B., 1998b. MTBE: Beware the False Positive, LUSTline Bull. No. 26, New England
Interstate Water Pollution Control Commission, Wilmington, MA, p. 18.
Hartman, B., 1998c. Applications and interpretation of soil vapor data, in Petroleum Hydro-
carbon Contamination: Legal and Technical Issues, Argent Communications Group,
Forresthill, CA, pp. 81–110.
Hartman, B. and R. Hitzig, 1998. A Layman’s Guide to the New EPA Methods for VOC
Analysis, LUSTline Bull. No. 30, New England Interstate Water Pollution Control
Commission, Wilmington, MA, pp. 21–23.
Hewitt, A., Miyares, P., Leggett, D., and T. Jenkins, 1992. Comparison of analytical methods
for determination of volatile organic compounds in soils, Environmental Science and
Technology, 28(10):1932–1938.

Hillel, D., 1982. Introduction to Soil Physics, Academic Press, Orlando, FL, p. 364.
Imbrigiotta, T., Gib, T., Fusillo, J., Kish, G., and J. Hochreiter, 1986. Field evaluation of seven
sampling devices for purgeable organic compounds in ground water, prepared for ASTM
Symposium on Field Methods for Ground Water Contamination Studies and Their
Standardization, February 2–7, Coca Beach, FL, p. 23.
Jenkins, R., Bayne, C., Maskarinec, M., Johnson, L., Holladay, S., and B. Tomkins, 1993.
Experimental determination of pre-analytical holding times for volatile organics in se-
lected soils, in National Symposium on Measuring and Interpreting VOCs in Soils: State
of the Art and Research Needs, January 12–14, sponsored by U.S. Environmental
Protection Agency, American Petroleum Institute, and University of Wisconsin Engi-
neering Extension Program, Madison.
Kaback, D., Bergren, C., Carlson, C., and C. Carlson, 1990. Testing a ground water sampling
tool: are the samples representative?, in Fourth National Outdoor Action Conference on
Aquifer Restoration, Ground Water Monitoring and Geophysical Methods, National
Ground Water Association, Dublin, OH, pp. 403–417.
Kaplan, E., Banerjee, S., Ronen, D., Machlin, A., Sosnow, M., and E. Koglin, 1991. Multilayer
sampling in the water-table region of a sandy aquifer, Ground Water, 29(2):191–198.
Kearl, P., Korte, N., Stites, M., and J. Baker, 1994. Field comparison of micropurging vs.
traditional ground water sampling, Groundwater Monitoring Review, Fall:183–190.
King, A. 1993. Evaluation of sample holding times and preservation methods for gasoline in
fine grained soils, in National Symposium on Measuring and Interpreting VOCs in Soils:
State of the Art and Research Needs, January 12–14, sponsored by U.S. Environmental
Protection Agency, American Petroleum Institute, and University of Wisconsin Engi-
neering Extension Program, Madison, p. 7.
Kollmorgen Corp., 1975. Munsell Soil Color Charts, Macbeth Division of Kollmorgen Corp.,
Baltimore, MD, p. 18.
Lancaster, V. and S. Keller-McNulty, 1998. Composite sampling II, Environmental Testing
and Analysis, 7(5):14–15.
Lancaster, V. and S. Keller-McNulty, 1988. Composite sampling I, Environmental Testing and
Analysis, 7(4):15–18, 32.
Maney, J., and A. Wait, 1991. The importance of measurement integrity, Environmental
Laboratory, 3(5):20–25.
Marrin, D., 1988. Soil-gas sampling and misinterpretation, Ground Water Monitoring Review,
8(2):54–57.
Martin-Hayden, J. and G. Robbins, 1997. Plume distortion and apparent attenuation due to
concentration averaging in monitoring wells, Ground Water, 35(2):339–347.
Martin-Hayden, J., Robbins, G., and R. Bristol, 1991. Mass balance evaluation of monitoring
well purging. Part II. Field tests at a gasoline contamination site, Journal of Contaminant
Hydrology, 8:225–241.
Maskarinec, M., Johnson, L., Holladay, S., Moody, R., Bayne, C., and R. Jenkins, 1990.
Stability of volatile organic compounds in environmental water samples during transport
and storage, Environmental Science and Technology, 24(11):1664–1670.
Maybey, W., 1995. Verifying data quality-quality assurance, in Environmental Chemistry for
Investigating and Remediating Soil and Groundwater Contamination, Department of
Engineering and Engineering Professional Development, University of Wisconsin, Madi-
son, p. 15.
Meyer, C., 1999. Distinguishing good science, bad science and junk science, in Meyer, C.
(Ed.), Expert Witnessing: Explaining and Understanding Science, CRC Press, Boca
Raton, FL, pp. 99–120.

Mishalanie, E., 1998. Measurement bias in analytical methods for determination of chlorinated
solvents and petroleum hydrocarbons in environmental samples, in National Environ-
mental Forensic Conference: Chlorinated Solvents and Petroleum Hydrocarbons, De-
partment of Engineering and Engineering Professional Development, University of Wis-
consin, Madison, p. 27.
Mishalanie, E., 1995. Testing biases associated with chlorinated solvents and hydrocarbon
analyses, in Environmental Litigation: Hydrocarbon, Chlorinated Solvents and Visual
Display of Evidence, Department of Engineering and Engineering Professional Develop-
ment, University of Wisconsin, Madison, p. 41.
Peargin, T., 1994. Unsaturated zone air flow and soil vapor extraction theory, in Designing
Air-Based In Situ Soil and Groundwater Remediation Systems, Department of Engineer-
ing and Engineering Professional Development, University of Wisconsin, Madison.
Powell, R., 1997. Hitting the bull’s eye in groundwater sampling, Pollution Engineering,
June:51–54.
Powell, R. and R. Puls, 1993. Passive sampling of groundwater monitoring wells without
purging: multilevel well chemistry and tracer disappearance, Journal of Contaminant
Hydrology, 12:51–77.
Puls, R. and C. Paul, 1995. Low-flow purging and sampling of ground water monitoring wells
with dedicated systems, Groundwater Monitoring Review, Winter:116–123.
Puls, R. and M. Barcelona, 1989. Filtration of ground water samples for metals analysis,
Hazardous Waste and Hazardous Materials, 6(4):385–393.
Puls, R., Clark, D., Bledsoe, B., Powell, R., and C. Paul, 1992. Metals in ground water:
sampling artifacts and reproducibility, Hazardous Waste and Hazardous Materials,
9(2):149–162.
Puls, R., Eychaner, J., and R. Powell, 1990. Colloidal-Facilitated Transport of Inorganic
Contaminants in Ground Water. Part I. Sampling Considerations, EPA/600/M-90/023,
Robert S. Kerr Environmental Research Laboratory, U.S. Environmental Protection
Agency, Ada, OK, p. 12.
Ramsey, C., 1996. Chlorinated solvent and hydrocarbon sampling techniques: what are the
biases?, in Proving the Technical Case: Chlorinated Solvents and Petroleum Hydrocar-
bons, College of Engineering and Engineering Professional Development, University of
Rhodes, I., 1999. Pitfalls using conventional TPH methods for source identification, in Proc. of
Environmental Forensics: Integrating Advanced Scientific Techniques for Unraveling Site
Liability, International Business Communications, June 24–25, Washington, D.C., p. 11.
Robbins, G. and J. Martin-Hayden, 1991. Mass balance evaluation of monitoring well purging.
Part I. Theoretical models and implications for representative sampling, Journal of
Contaminant Hydrology, 8:203–224.
Robbins, G., Deyo, B., Temple, M., Stuart, J., and M. Lacy, 1990. Soil-gas surveying for
subsurface gasoline contamination using total organic vapor detection instruments. Part
II. Field experimentation, Ground Water Monitoring Review, Fall:110-117.
Robertson, C. and J. Cutler, 1989. Soil Gas Investigations at MGP Sites: An Evaluation of
Alternate Compounds, Rep. No. GRI-89/0166, Gas Research Institute, Chicago, IL, p. 58.
Robin, M. and R. Gillham, 1987. Field evaluation of well purging procedures, Groundwater
Monitoring Review, Fall:85–93.
Rosecrance, A. and L. Kibler, 1988. A guide to improved documentation and record keeping,
Environmental Testing and Analysis, 7(4):26–30.
Rosenberry, D., 1990. Effect of sensor error on interpretation of long-term water-level data,
Ground Water, 28(6):927–936.

Shanklin, D., Sidle, W., and M. Ferguson, 1995. Micro-purge, low-flow sampling or uranium-
contaminated ground water at the Fernald environmental management project, Ground-
water Monitoring Review, Summer:168–176.
Siegrist, R., 1993. VOC measurement in soils: the nature and validity of the process (abstract),
in National Symposium on Measuring and Interpreting VOCs in Soils: State of the Art
and Research Needs, January 12–14, sponsored by U.S. Environmental Protection Agency,
American Petroleum Institute, and University of Wisconsin Engineering Extension Pro-
gram, Madison, p. 10.
Siegrist, S. and P. Jenssen, 1990. Evaluation of sampling method effects on volatile organic
compound: measurements in contaminated soils, Environmental Science and Technol-
ogy, 24(9):1387–1392.
Simes, G. and J. Harrington, 1993. The measurement of contamination in environmental
samples, Air and Waste, 43:1155–1160.
Squillance, P., Pankow, J., Barbash, J., Price, C., and J. Zogorski, 1999. Preserving ground
water samples with hydrochloric acid does not result in the formation of chloroform,
Ground Water Monitoring and Review, 19(1):67–74.
Stolzenburg, T. and D. Nichols, 1986. Effects of filtration method and sampling devices on
inorganic chemistry and sampled well water, in Proc. of the Sixth National Symposium
and Exposition on Aquifer Restoration and Ground Water Monitoring, National Water
Well Association, Dublin, OH.
Sudicky, E., Cherry, J., and E. Frind, 1983. Mitigation of contaminants in groundwater at a
landfill: a case study. 4. A natural-gradient tracer test, Journal of Hydrology,63:81–108.
Tetra Tech, 1998. Environmental Technology Verification Report: Passive Soil Gas Sampler,
EPA/600/R-98/095, Office of Research and Development, U.S. Environmental Protec-
tion Agency, Washington, D.C., p. 44.
U.S. Corps of Engineers, 1960. Unified Soil Classification System, Vol. 1, rev. ed., Technical
Memorandum No. 3-357, Omaha, NE.
U.S. EPA, 1997. Field Portable X-Ray Fluorescence Analyzer: Measurement of Metals in
Soils, EPA/VS/SCM/03, Environmental Technology Verification Program, Office of
Research and Development, U.S. Environmental Protection Agency, Washington, D.C.,
p. 3.
U.S. EPA, 1995. RCRA Sampling Procedures Handbook, U.S. Environmental Protection
Agency, Washington, D.C. (revised by A.T. Kearney).
U.S. EPA, 1991. Chapter 11 (final draft), in Ground Water-Monitoring, SW-846, U.S. Envi-
ronmental Protection Agency, Washington, D.C.
U.S. EPA, 1987. Data Quality Objectives for Remedial Response Activities, Development
Process, EPA/540/G-87/003, Office of Emergency Response and Office of Waste Pro-
grams Enforcement, U.S. Environmental Protection Agency, Washington, D.C.
U.S. EPA, 1986. RCRA Ground-Water Monitoring Technical Enforcement Guidance Docu-
ment (TEGD), U.S. Environmental Protection Agency, Washington, D.C., p. 215.
Wilson, G., Gwo, J., Jardine, P., and R. Luxmoore, 1998. Hydraulic and physical nonequilibrium
effects on multiregion flow, in Selim, H. and L. Ma (Eds.), Physical Nonequilibrium in
Soils: Modeling and Application, Ann Arbor Press, Chelsea, MI, p. 492.
Wilson, N., 1998. Soil Water and Ground Water Sampling, CRC Press, Boca Raton, FL, p.
188.
Zurer, P., 1991. Contract labs charged with fraud in analyses of Superfund samples, Chemical
and Engineering News, 69:14–16.

Plate 3.1 Soil stains of a dyed fluid infiltrating around a coarse-grained sedi-
ment via unsaturated flow.
Plate 3.2 Collection of a gasoline-impacted soil sample from the crust of a

soil stockpile with a brass tube.

Plate 3.3 Monitoring well valve-box designs.

4 Forensic Techniques
Used in Environmental
Litigation
Scientific method vs. junk science
4.1 INTRODUCTION
When evaluating the merits of performing non-intrusive forensic analysis (e.g.,

contaminant transport modeling or aerial photo-interpretation) and/or intrusive sam-
pling and testing, three questions should be considered:
1. Does the analysis or testing advance the understanding of the technical aspects of
the case?
2. Can the test results be damaging to your client?
3. Is the testing cost effective relative to the allegations in the case?
When answering the third question, be aware that many forensic techniques, espe-
cially specialty analytical testing, are marketed and monopolized by a small number
of companies. These firms, therefore, have a proprietary interest in their use.
The following recommendations are offered for consideration when examining
the applicability of forensic techniques:
• Use multiple forensic methods whenever possible.

• To the extent possible, isolate your forensic evidence from other groups of evidence
so that each group of forensic evidence is a “stand-alone” line of evidence. This
practice avoids the domino effect of multiple lines of evidence being successfully
challenged if one domino is successfully challenged.
• Corroborate your forensic results with other types of evidence (direct testimony,
blueprints, aerial photography, etc.) for consistency.

A common issue in environmental litigation is the determination of the origin of a
contaminant release, timing of the release, and distribution of the contamination.
Forensic procedures that provide this information include (Morrison, 1998a):
• Aerial photography interpretation

• Underground storage tank corrosion models
• Identification of the date when a chemical became commercially available
• Association of a particular chemical with a manufacturing process
• Chemical profiling (fingerprinting) and chemical degradation models
4.2 AERIAL PHOTOGRAPHY

Aerial photography offers an established application for identifying historical infor-
mation concerning a site’s waste-handling practices, as well as its potential to provide
information regarding the timing of a contaminant release (Erb et al., 1981; Lyon
1987; Pope et al., 1996; Weil et al., 1994). Successful use of this technique is
dependent on acquiring a complete list of coverage dates and retaining an expert in
this discipline.
Two fields of discipline within aerial photography are photo-interpretation and
photogrammetry. Photo-interpretation is the identification of objects seen on aerial
photography. Photogrammetry is the measurement of features on aerial photo-
graphs. Both disciplines are important, as aerial photo-interpretation is dependent
on the sophistication of the diagnostic equipment as well as the experience of the
interpreter.
Several sources of aerial photography are available, including the U.S. Geologi-
cal Survey, the U.S. Department of Agriculture, the U.S. Forest Service, the National
Oceanic and Atmospheric Administration (NOAA), the Army Corps of Engineers,
the U.S. Soil Conservation Service, the U.S. National Archives, local and state
highway departments, and private collections. The U.S. National Archives located in
Betheseda, MD, for example, has aerial photography of all of the airfields in the
United States in the 1940s. Another source is the Earth Resources Observation
Satellites (EROS) collection in Sioux Falls, SD (800-252-4547). A historical search
of federal aerial photography can be performed by EROS at no charge within 24 to
48 hours.
Acquisition of a complete list of aerial photographs requires the use of a firm
specializing in this service. These firms have access to private collections and aerial
photography brokers (for example, Chinese and Russian satellite imagery) who can
provide crucial evidence for identifying a key surface feature or activity. Acquire
stereoscopic (stereo pairs) rather than monoscopic photographs whenever possible so
that a three-dimensional analysis of relevant features can be performed. Anaglyphs
can also be used for stereo viewing. Analglyphs are red-blue images that allow stereo
viewing of the aerial photo with red and blue glasses or on some computer screens.
Stereoscopic aerial photography consists of two or more overlapping frames of
vertical photography that combine to create three-dimensional coverage of a site. In

most cases, aerial camera stations are spaced to provide for about 60% forward
overlap of aerial photographs along each flight line and a 20 to 30% percent overlap
for adjacent flight lines. The U.S. government and private industry have been
photographing large portions of the United States in stereoscopic coverage, and most
aerial photographs are available as 9 ¥ 9-inch contact prints or negatives. It is better
to order the negatives/transparencies, as one can lose up to four times the resolution
with a contact print. The emulsion in a contact print provides a less precise resolution
than a negative or transparency. Request the provider to document the film scale,
focal length of the camera, and the correct date when the photograph was taken. If
the photograph is cropped or enhanced, the impacted area should be identified and
documented (see Figure 6.7 in Chapter 6).
When multiple aerial photographs are obtained from different elevations and
angles, registration (also known as geo-referencing) is required. Commercial soft-
ware is available for translating and registering aerial photographs to a base image.
Commercial firms usually scan photographs at a resolution of 12.5 microns (2032
dots per inch) with a photographic scanner, thereby producing high-resolution digital
images suitable for trial exhibits (Grip, 1998). Mounted, scaled, and cropped 30 ¥ 40-
inch prints of selected photos or features are commonly used for trial exhibits. Once
the photo is digitally scanned, it is possible to enlarge the photograph up to 50 times
without losing resolution. In some cases, an enhancement equal to 1 ft2 for each
scanned pixel is possible.
Distortion effects in vertical and oblique aerials are removed so that an overhead-
like view is obtained from an oblique photograph. Aerial photographs can also be
enhanced in a consistent manner between the registered aerial photographs. The
benefits of digitally scanning and registering historical aerial photographs include
(Soby et al., 1992):
• An overhead-like view of the site can be viewed during a period when no vertical
aerial photos are available.
• Scanning allows a rapid historical and forensic examination of key areas which can
then be used as trial exhibits (stills, bar-coded images, or animation).
• The photograph can be combined with a geographic information system (GIS) for
detailed forensic review of chemical/spatial relationships.
While an aerial photograph can identify a dark “stain” or other evidence of

surface contamination, it is two dimensional and does not provide information
regarding the depth of contamination. One means to discriminate between a creosote
stain and ponded water, for example, is to obtain precipitation records for at least 10
days prior to the date of the aerial photograph to determine whether rainfall was
recorded in the vicinity of the site. Another exercise is to ask the photograph
interpreter to examine similar-appearing features around the site for several miles to
compare with the stain of interest. Aerial photographs must be combined with other
causal information (historical, chemical, deposition testimony) to develop a direct
link between the aerial photograph and subsurface contamination. In many instances,
detailed features such as the number of barrels, their position, and the presence of

FIGURE 4.1 Aerial photograph with details of 55 gallon barrels.
stains or drainage patterns associated with the barrels can be identified. Figure 4.1 is
an example of an aerial photograph with this level of resolution.
Aerial photography interpretations are useful for identifying potential source
areas indicative of a contaminant release such as drum storage areas, open drainage
ditches, standing liquid, landfills, stains, access and egress routes from buildings,
and/or storage areas. Aerial photographs can be combined with soil chemistry results
to associate the release of specific contaminants with a particular time frame. The
technique combines identifying a unique chemical associated with a discrete soil
horizon with aerial photo-interpretation to bracket when the contaminant was re-
leased. The concept is similar to dating discrete levels in an archaeological excava-
tion. A hypothetical case illustrates this approach. Assume that an asphalt emulsion
plant and its associated contaminants are identified by aerial photographs as having
been operational between 1960 and 1969. Excavations in the area reveal discrete soil
horizons contaminated with asphalt and related compounds indicative of an asphalt
emulsion plant overlain by several feet of uncontaminated soil and asphalt/concrete
road bases. The various road bases and filling activities are identified in aerial

photographs, thereby bracketing a time when the release occurred. Given this infor-
mation, the hydrocarbon release into a discrete soil horizon can be linked to a
particular activity and time period. In some cases, the placement of subsequent
contaminant layers can be identified, resulting in forming multiple bracketed time
periods.
Plate 4.1* shows the sidewall of a trench with two layers of concrete and a clean
layer between the two concrete pavement layers. The material in the clean fill layers
is associated with a nearby quarry which allowed dating of the fill excavation and
placement to complement the aerial photography information. Additional layers A
through D are similarly associated with discrete activities and time periods. By
combining aerial photography depicting the surface features with the chemical
profiling information shown on Plate 4.1, the various layers can be associated with
various tenants. Historical aerial photographs and tenant information can then be
used to establish the causal relationships and provide a basis for allocating remediation
costs.
4.3 UNDERGROUND STORAGE

TANK CORROSION MODELS
The use of tank corrosion to identify the timing of a release from an underground
storage tank (UST) has been proposed as a means to age-date a release. Ideally, tank
inventory records are available, and variables due to delivery discrepancies, tempera-
ture effects, pump meter errors, non-standard UST geometry, and gauging errors can
be identified to determine when the leak occurred. In the absence of this direct
information, indirect predictive techniques based on tank corrosion are available. In
order for tank corrosion to occur, the following components must be present:
• Anode (a negative electrode that is consumed)

• Cathode (a positive electrode that is protected)
• Electrolyte (soil seawater, etc.)
• Metallic connection between the anode and cathode
A corroding steel tank acts as both an anode and a cathode simultaneously but
at different locations on the tank. Anodic sites on the tank surface exist where the
metal is deformed, the oxygen concentration is low, the rust layer is disrupted,
impurities or precipitates exist, higher temperatures exist, and backfill material
boundaries (i.e., different soil textures) are present. The corrosion rate is controlled
by the following variables:
• Voltage between the anode and cathode

• Resistance between the anode and cathode
• Resistance of the soil backfill

• Resistance of any anodic or cathodic films
• Type of fluid and material of tank and/or piping construction
The primary variable is the anodic current density. A steel tank may suffer
negligible corrosion even if a substantial anodic current is present but is distributed
uniformly over the surface of the tank; however, if the same anodic current is
confined to a discrete location, perforations in a tank may occur within a matter of
days.
Soil characteristics influencing the corrosion rate include soil electrical resistiv-
ity, pH, moisture content, sulfide content, and chloride content (U.S. EPA, 1988a).
Corrosion rates are increased due to flowing water, the presence of fluctuating saline
water in contact with the tank, the presence of certain bacteria, high temperatures,
and increasing oxygen concentration. In general, factors indicative of a high corro-
sion risk include high soil moisture, saline soils, high groundwater levels that
fluctuate above and below the tank, low soil pH, and improper backfill placement.
Factors considered indicative of a low corrosion risk include high soil resistivity, low
soil moisture, high soil pH, low age, non-corrosive tank materials and piping mate-
rials, and the presence of cathodic protection devices and coatings. As soil resistivity
decreases, soil corrosivity increases. Given that soil corrosivity is closely related to
the electrical resistivity of the soil, a general classification of soil resistivity values
vs. corrosivity is as follows:
• <1000 ohm-cm is extremely corrosive

• 1000 ohm-cm to 10,000 ohm-cm is corrosive
• 10,000 ohm-cm is progressively less corrosive
The type of liquid and tank and/or piping construction has a significant impact on the
corrosion rate. Chlorinated solvents, for example, are transported through pipes and
tanks composed of nickel-based alloys. In the presence of water, however, the
chlorinated solvents can hydrolyze to form hydrochloric acid which results in accel-
erated corrosion.
External corrosion accounts for approximately 85% of the perforations associ-
ated with unprotected steel underground storage tanks. Tank corrosion occurs when
underground storage tanks are installed without cathodic protection. The soil sur-
rounding the tank acts as an electrolyte and galvanic current flow from the tank
surface to other structures in the vicinity or from various parts of the tank surface to
other areas where the metal composition differs.
Types of external corrosion affecting steel underground storage tanks include
uniform corrosion, pitting, and crevice corrosion (Figure 4.2), dissimilar metal
(galvanic) corrosion, concentration cell corrosion, and stray current corrosion (Liebert,
1990). Uniform corrosion results when the galvanic current voltage is uniform over
the entire surface of the underground storage tank. This occurs when the backfill
surrounding the tank is homogenous and uniform and the tank surface is not scratched
or gouged. The corrosion rate is then uniform over the entire tank surface and
proceeds until a thin layer of iron oxide coats the tank surface, at which point

FIGURE 4.2 Mechanism of formation and photograph of pit corrosion. (From Pickering, H.
and R. Frankenthal, in Localized Corrosion, International Corrosion Conference Series, Na-
tional Association of Corrosion Engineers, Houston TX, 1974, pp. 261–269. With permission.)
corrosion ceases, as this iron oxide layer protects it against further deterioration.
Corrosion under these conditions occurs uniformly and slowly over the tank surface
(Pourbaix, 1971).
Pitting (also called crevice, point, or localized corrosion) occurs whenever, in the
course of tank installation, a condition arises which concentrates the galvanic current
at one or several points on the tank surface. This can occur due to mill scale abrasion,
lack of impurity or uniformity in the backfill material, and tank abrasion that may
occur during installation (Pickering and Frankenthal, 1974). Given that pit corrosion
is not uniform, high corrosion rates are possible because the pit formed at the point
of galvanic concentration creates iron oxide, which can fall away from the steel
surface, which then becomes susceptible to further corrosion. The corrosion, there-
fore, continues as long as the corrosion-inducing influences are present. Approxi-
mately 77% of the corrosion observed in underground storage tank installations is pit
corrosion; uniform corrosion accounts for the remaining 23%.

A statistical technique based on a survey of underground storage tanks in the U.S.
and Canada is often proposed as a means to estimate when an underground tank
began leaking. The method, known as the Mean Time to Corrosion Failure (MTCF®)
model, assumes that uniform and pitting corrosion are the primary corrosion mecha-
nisms. This method originated from an American Petroleum Institute (API) study
that concluded that tank failures due to external corrosion occurred from as little as
5 and up to 35 years. Absent other information, the age of an underground storage
tank did not provide a basis to determine the probability of failure due to corrosion.
The MTCF® model evolved from the results of a survey from a 1979 survey by the
American Petroleum Institute and the Petroleum Association for the Protection of the
Canadian Environment in which over 2000 UST sites in the U.S. and Canada were
excavated and their condition documented. Based on this research, a field procedure
was developed to obtain the necessary information from the tank backfill material to
allow a statistical estimation using MTCF®. The MTCF® relies upon characteristics
of the tank backfill material (e.g., soil moisture content, pH, soil resistivity, and
sulfide content) along with the tank age; the probability of failure at any point in time
is then calculated. The mean time to failure for an unprotected carbon steel under-
ground storage tank is described in Equation 4.1 (Warren Rogers & Assoc., 1981):
Age = 5.75(R0.05)(S–0.018)exp(0.13 pHsoil – 0.41 M – 0.26 Su) (Eq. 4.1)
where
R = calculated soil resistivity in ohm-cm that is obtained from conductivity measure-
ments (inverse of resistivity, or R = 1/conductivity), because conductivity values
are reproducible whereas resistivity measurements are operator sensitive.
S = capacity (gallons) of the underground storage tank.
M = 1, if soil is saturated; 0 if soil is not saturated.
Su = 1, if sulfides are present; 0 if sulfides are not present.
A 90% confidence level is defined if the following values are substituted into
Equation 4.1: R(0.049, 0.051), S(–0.019, –0.0170), –0.119, 0.141 pHsoil, 0.31–0.51 and 0.25–0.27
Su. This technique has been implemented at over 30,000 sites in the United States.
Actual tank removals and physical examinations have reportedly established its
accuracy as being between 95 and 98% (Warren Rogers and Assoc., undated).
Another study of 800 tanks at retail service stations in Ohio indicated that at least one
tank failure could be expected in 55% of the stations in 15 years and that failure could
be expected at 70% of the stations in 20 years (Garrity, 1996).
Challenges to the MTCF® approach are that, in many cases, the tank has been
removed and measurements of the soil properties of interest are not available. In
addition, information concerning where a leak occurred (i.e., a leak in the fill pipe
vs. corrosion) may not be resolvable. The MTCF® does not account for mechanical
failure, only failure due to corrosion. Studies performed by the U.S. Environmental
Protection Agency show that delivery piping releases and spills or overfills are the
most common sources of releases and that equipment at the top of tanks leaks during
overfills more frequently than do tanks and delivery piping (U.S. EPA, 1987). For

underground storage tanks, about 65% of all releases are from product lines, 25%
are from the tanks, and the remainder from overfilling or spillage. MTCF® data are
also skewed to some degree in that primarily tanks that had failed were excavated
and examined.
In the absence of physical evidence, patterns in contaminant distribution may be
inconclusive in terms of the ability to determine whether the contamination occurred
via corrosion or from overfilling of the spill boxes (usually ranging from 5 to 25
gallons, with 5-gallon models being the most common) (McCan, 1996). In addition,
if stray DC currents are present, parameters other than the nature of the tank backfill
material are required to estimate corrosion rates.
The National Fire Protection Association (NFPA) is a source for historical
standards for underground storage tank installation and maintenance. This associa-
tion maintains documents that date from the 1920s.
4.4 INVENTORY RECONCILIATION
Inventory reconciliation includes (1) review of inventory (sticking records), if avail-

able, and (2) precision tank testing as a means to date the release of a fluid from a
tank (U.S. EPA, 1988b,c,d 1989; 1990). Inventory control requires recording daily
accurate measurements of the fluid level in the tank and performing monthly calcu-
lations to determine if the tank is leaking.
The examination of inventory records is a straightforward means to assess
whether a significant volume of fuel has been lost, as inventory records contain the
volume of product dispensed from a tank and deliveries. It is the author’s experience
that sources of error in inventory reconciliation include product delivery discrepan-
cies, errors in addition and subtraction, pump meter reading errors, non-standard tank
geometry, gauging errors, and theft. Temperature differences between the delivered
product and the product in the storage tank can also account for discrepancies found
in the inventory reconciliation calculations.
Statistical inventory analysis can be performed to detect whether a leak has
occurred; the following requirements must be satisfied when using this approach
(Kroon and Baach, 1996):
• 0.2 gal/hr minimum detectable leak

• 150 gal/mth minimum detectable leak
• 95% minimum probability of detection
• 5% maximum probability of a false positive
Precision tank testing to ascertain tank integrity is used to determine an estimated

tank interval during which a tank began leaking. A tank integrity test consists of
precisely monitoring the fluid level and the tank temperature for a period of several
hours. The fluid level is adjusted for temperature drifts to determine if there is a leak.
A 10∞F temperature change in gasoline in a 10,000-gallon storage tank, for example,
produces a 70-gallon change in volume.

Tank testing technology became available in about 1945. Tank tightness tests
should be in accordance with ASTM Standards or a method that is certified in
accordance with U.S. Environmental Protection Agency and/or state requirements.
Tank tightness results should be examined in conjunction with inventory control
sheets to identify when a leak may have commenced. A leaking tank is one from
which the loss of liquid is greater than 0.05 gal/hr based on National Fire Protection
Authority Bulletin #329. Variables in tank tightness tests that can introduce measure-
ment uncertainty include the temperature of the liquid within the tank, vapor pockets,
deflection at the ends of the tank, a high water table, nearby road vibrations, operator
error, and electronic noise in the measurement equipment (U.S. EPA, 1988b, 1989).
4.5 COMMERCIAL AVAILABILITY

OF A CHEMICAL
The date that a compound became commercially available can often bracket the
earliest time period of its release. Chlorinated hydrocarbons, chemicals associated
with fuel additives, pesticides, herbicides, fungicides, and insecticides are espe-
cially amenable to this dating analysis. Chlorofluorocarbons released into the atmo-
sphere since the 1940s have been used for this purpose (Plummer et al., 1993).
Knowledge of the synonyms and trade names of the chemical is often necessary to
perform this analysis, as a chemical has commercial names often dissimilar to its
chemical name. Trade names for commonly encountered contaminants are summa-
rized in Appendix E. Table 4.1 lists dates when commonly encountered compounds
became commercially available (IARC, 1979; Morrison, 1999c).
A similar issue is the evolution of chlorinated solvent use at a facility as a means
to date when a release occurred. General events such as the Montreal Protocol (see
Chapter 1, Section 1.2) and state regulations can provide a means to identify when
various solvents were used. In California, Rule 66 promulgated by the Los Angeles
Air Pollution Control District in July 1966 limited trichloroethylene (TCE) emission
from any type of equipment to 40 pounds over 24 hours. The installation of control
equipment was required if this limit was exceeded. Tetrachloroethylene (PCE) and
fluorinated hydrocarbons were exempt. Given that TCE boils at 184∞F and a steam
supply of 15 pounds per square inch at gauge (psig) is required for heating, PCE
with a 50- to 60-psig and boiling point at 250∞F was not a viable replacement for
a majority of the existing equipment, such as degreasers. 1,1,1-Trichloroethane
(1,1,1-TCA), however, with a boiling point of 158∞F, was a viable replacement
solvent for many degreasers. A knowledge of these regulations and the operating
characteristics of the equipment can provide a basis for bracketing the time period
that a solvent was used at a facility.
While the gross chronological transitions in solvent usage for an industry can be
identified, they cannot be used as evidence of solvent use at a site. Figure 4.3 is an
example of solvent usage at Hill Air Force Base (Stewart et al., 1991), an aircraft
engine degreasing facility, and a semiconductor manufacturing company. As de-
picted in Figure 4.3, solvent transitions between these three sites do not correlate.

TABLE 4.1
Commercial Availability of Selected Compounds
Chemical Date
Aldrin 1948
Bromacil 1963
Carbon tetrachloride 1907
Chlordane 1947
Chloroform 1922
DDT 1942
Dieldrin 1948
Dinoseb 1945
Dibromochloropropane (DBCP) 1955
1,2-Dichloroethane 1922
Parathion 1947
Perchloroethylene (PCE) 1925
Phorate 1954
Trichloroethylene (TCE) 1908
1,1,1-Trichloroethane (1,1,1-TCA) 1946
1,1,2-Trichloroethane 1941–43
Trifluralin 1960
Toxaphene 1947
FIGURE 4.3 Solvent transitions at three facilities between 1940 and 1990.

TABLE 4.2
Boiling Point of Selected Chlorinated Solvents
Compound Boiling Point (∞C)
Carbon tetrachloride 76.7

1,1,2,2-Trichloroethane 146.4
Trichlorofloromethane (Freon-11) 23.8
1,1,2-Trichlorotrifluoroethane (Freon-113) 47.7
4.6 CHEMICALS AND FORMULATIONS

UNIQUE TO A MANUFACTURING
PROCESS OR ACTIVITY
An understanding of a site’s manufacturing processes and material handling systems

can provide insight regarding probable locations of a contaminant release. An ex-
ample of the former approach is identification of potential source areas at a semicon-
ductor facility. Potential source locations where chlorinated solvents can enter the
subsurface include neutralization sumps, corroded sewer and transfer piping, and
chemical storage areas. The chemical distribution of chlorinated solvents in the
subsurface in relation to these features is used to develop a causal relationship
between these features and the observed soil contamination.
Chemicals, such as chlorinated solvents, that are unique to particular equipment
can provide insight into probable source locations. An example is the use of chlori-
nated solvents in degreasing operations. A vapor degreaser may be specifically
manufactured to use solvents with boiling points within a discrete range. Obtaining
the manufacturer’s operating manual or degreaser specifications can provide infor-
mation concerning the inclusion or exclusion of chemicals used by a particular
degreaser model as well as capacity. Degreasing manufacturers such as Phillips,
Baron Blakeslee, Deltasonics, Detrex, Sonicor, Talley, and Ultraclean can often
provide operating instructions for a particular degreaser model or maintain this
information on Web pages on the Internet. The boiling points of selected solvents are
provided in Table 4.2 (Montgomery, 1992; Pankow and Cherry, 1996).
Opportunities may exist to associate a solvent with a particular activity in order
to bracket the location and/or timing of a release. For chlorinated solvents, unique
applications or impurities in the solvent may assist in dating or identifying the origin
of the release. 1,1,2,2-trichloroethane, for example, is used almost exclusively in
military applications. Examples of uses of various chlorinated solvents are summa-
rized in Table 4.3 (Mabey, 1995; Montgomery, 1991; Pankow et al., 1996).

TABLE 4.3
Uses of Selected Chlorinated Solvents
Chlorinated Solvent Applications
Tetrachloromethane Solvent used as a chemical intermediate, agricultural fumigant, de-worming

(carbon tetrachloride) agent, grain fumigant, and anaesthetic; also used in semiconductor manu-
facturing, drycleaning operations, fire extinguisher manufacturing, refriger-
ant manufacturing, veterinary medicine, manufacture of dichlorodifluo-
romethane, metal degreasing, extraction of seed oils, removal of soot from
industrial boilers, and manufacture of paint removers and printing inks.
Chloroform Solvent used for cleaning electronic circuit boards; preparation of fluorocar-
(trichloromethane) bon refrigerants, plastics, and refrigerants; and rubber manufacturing. Used
as an anesthetic, soil fumigant, insecticide solvent, and solvent for fats, oils,
rubber, waxes, and resins. Also used in toothpaste and liniments. Product of
chlorination from water treatment.
Chloromethane Natural product in seawater. Used as a coolant and refrigerant, as an
(methyl chloride) herbicide and fumigant, and in the manufacture of silicone polymer pharma-
ceuticals, tetraethyl lead, synthetic rubber, methyl cellulose, agricultural
chemicals, methylene chloride, carbon tetrachloride, methylcellulose, and
chloroform. Also used as fluid for thermometric and thermostatic equip-
ment.
Freon-11 Used as refrigerant, blowing agent for polyurethane foam, fire extinguish-
(trichlorofluoromethane) ing agent, aerosol propellant, solvent.
Freon-12 Used as blowing agent, refrigerant, propellant.
(dichlorodifluoromethane)
Freon-113 Used in fire extinguishers, solvent drying, stripping of flux from printed
(trichlorotrifluoroethane; circuit boards (often combined with alcohol), vapor degreasing, aerosols,
CFC-113) cold cleaning, and manufacture of chlorotrifluoroethylene. Also used as
drycleaning solvent and feedstock in the production of other CFCs and
fluoropolymers.
1,1-DCA Reduction product of 1,1,1-TCA. Used in paint, varnish, and finish remov-
(1,1-dichloroethane) ers; manufacture of vinyl chloride and 1,1,1-TCA; in rubber cement; as a
solvent for plastics; and as an insecticide and fumigant.
1,2-DCA Used as gasoline additive, chemical intermediary, solvent, insecticide, seed
(1,2-dichloroethane) fumigant, and solvent for rubber, resin, gums, waxes, fats, and oils. Also
used in the manufacture of acetyl cellulose and vinyl chloride.
1,2-Dibromomethane Used in anti-knock gasoline, insecticides, medicines, and waterproofing
(ethylene dibromide) preparations; also used as a grain and fruit fumigant.
1,1-DCE Hydrolysis product of 1,1,1-TCA and daughter product of TCE. Used as a
(1,1-dichloroethene) chemical intermediate in vinylidene fluoride synthesis, coating resins, and
synthetic fibers and adhesives. Used in the manufacturing of dyes, plastics,
perfumes, paints, and adhesives.
1,2-DCE Reduction product of TCE. Used as an industrial solvent in the manufacture
(1,2-dichloroethene) of dyes, plastics, perfumes, and lacquers.

TABLE 4.3 (cont.)
1,4-Dioxane Used in paint and varnish strippers, dye baths, stain and printing composi-
tions, cosmetics, fumigants, automotive coolant liquids, scintillation counters,
and preparation of historical slides. Also used as a stabilizer in 1,1,1-TCA,
as a wetting agent and dispersing agent in textile processing, and as a
solvent for cellulose acetate.
Methylene chloride Secondary blowing agent in the production of low-density flexible poly-
(dichloromethane) urethane foam used to produce upholstered furniture, bedding, and carpet
underlay. Also used as an extractant for decaffeinated coffee; as an extrac-
tion solvent for hops; as a pill coating in pharmaceuticals (in Western
Europe, in 1994, this application accounted for 41% of total usage; ECSA,
1997); as a carrier solvent and reaction medium in the pharmaceutical
industry; as an inactive ingredient in pesticide formulations; in various
chemical processing applications; in adhesive formulations used to bond
contact cements for wood, metal, and upholstered furniture; as a process
solvent for production of cellulose esters, polycarbonate, triacetate, and
triacetate ester; in solvent welding of plastic parts; dewaxing solvent; in
paint stripping for the aerospace industry; as a solvent for cleaning paint
booths, paint lines, and spray guns; in food processing; in vapor degreasing;
in vapor pressure depressant aerosol; in adhesives for mining applications;
as a photoresist stripper in the manufacture of printed circuit boards; as a
stripper for aircraft coatings.
PCE (tetrachloroethylene) Used in drycleaning fluid; as a metal degreaser; as a solvent for waxes,
greases, fats, oil, gums; in the manufacture of printing ink; as a paint
remover; in the preparation of fluorocarbons and trichlroacetic acid; as
feedstock for the production of CFC-113, hydrofluorocarbon refrigerant
134a, and hydrochlorofluorocarbon-123, -142b, and -141b; as a maskant
coating used to protect surfaces from chemical etchants in the aerospace and
electronics industries; in paper coatings and silicones (in small quantities);
as aerosol brake cleaners; in cold cleaning; and as an insulating fluid in
some electrical transformers as a substitute for PCBs (Halogenated Solvents
Industry Alliance, 1994).
TCE (tetrachloroethylene) Used as a metal degreasing solvent; in cold cleaning; as a paint remover; as
a heating transfer medium in organic synthesis; as a solvent for waxes,
greases, fats, oils, and gums; as a solvent base for metal phosphatizing
systems; in the preparation of fluorocarbons and trichloroacetic acid; as a
chain terminator in the production of vinyl chloride polymerization; as a
molecular weight control agent; as a carrier solvent in the textile industry for
spotting fluids; in synthesis of hydrofluorocarbons; for degreasing alumi-
num and cleaning sheet and strip steel prior to galvanizing; and to clean
liquid oxygen and hydrogen tanks.
1,1,1-TCA (trichloroethane) Used in the production of vinylidene chloride; as a primary solvent for cold
cleaning; in the photoresist process for developing and stripping electronic
circuit boards; as ingredients in aerosol pesticides; in adhesive formulation;

TABLE 4.3 (cont.)
1,1,1-TCA (cont.) in coatings for wood furniture, metal substrates, and traffic paints for signs
and road lines; as inactive ingredients in pesticide formulations; in Califor-
nia, after 1988, as a blowing agent in the production of flexible foam used
to make upholstered furniture, bedding, and carpet underlay; as a solvent for
fats, resins, and waxes; as an aerosol; in textiles; in formulations for inks,
adhesives, and correction fluid. Also used in the manufacture of plastics and
metals.
Vinyl chloride Reduction product of 1,1- and 1,2-DCE. Gas is used in the manufacture of
(chloroethene) polychloride vinyl (PVC) pipes and wire coatings. Also used in the automo-
bile upholstery; in copolymers; in adhesives for plastics; as a refrigerant; as
an extraction solvent; and in plastic housewares.
The presence of stabilizers in chlorinated solvents presents another opportunity

to date the timing and/or origin of a solvent release. In 1985, for example, 90% of
all of the dioxane produced in the U.S. (primarily by Ferro Corp.; Dow Chemical,
which also imported dioxane; and Stephan Company) was used as a stabilizer in
1,1,1-TCA. While this application continues, it is being quickly phased out. The
author has observed using the detection of 1,4-dioxane to distinguish among multiple
sources of 1,1,1-TCA in groundwater where it was associated with TCA at one
facility while absent at others.
The low concentrations of most stabilizers must be considered when using this
approach. The absence of a solvent stabilizer in a sample may not be evidence that
it was present in the solvent. Examples of additives and/or chemical impurities in
selected chlorinated solvents are listed in Table 4.4 (IARC, 1979; Morrison et al.,
1999).
Although reliance on signature chemicals unique to a manufacturing process or
equipment usually significantly narrows the potential source areas, further site spe-
cific identification is required. For example, perchlorate (ClO–4) is used in over 150
facilities in the U.S. While the presence of perchlorate is primarily associated with
its use as an oxidizer in solid rocket fuel propellants (approximately 90%), it is also
used in the production of fireworks, matches, and pyrotechnics and in analytical
chemistry (10%), in addition to its previous use in fertilizers (Brothers and Zikmund,
1998). Similarly, mundane equipment such as cooling towers can be a source of
arsenic or cyanide used to control biological growth. Water treatment chemicals such
as sodium bisulfide, sulfamic acid, polyacrylate, organophosphonate, orthophos-
phate, quaternary amines, and chlorine are also used in cooling water. An association
of these water treatment chemicals in conjunction with cyanide or arsenic may
provide a means to identify the source of these metals.

TABLE 4.4
Additives in Selected Chlorinated Solvents
Chemical Additive/Impurity
Dichloromethane Stabilizers (0.0001–1%) may include phenol, hydroquinone, para-cresol,

resorcinol, thymol, 1-naphthol, or amines.
Trichloroethylene (TCE) For technical-grade TCE, the purity is around 99.97% with no free chloride
and stabilizers, such as tymiol or hydrochloromonomethylether, present at
concentrations greater than about 0 to 2 and 80 to 120 ppm, respectively.
Antioxidants such as amines (0.001–0.01%) or combinations of epoxides
such as epichlorohydrin and esters (0.2–2% total) are added to TCE.
1,1,1-Trichloroethane Stabilizers (3–8%) include nitromethane, n-methylpyrrole, 1,4-dioxane,
butylene oxide, 1,3-dioxolane, and secondary butyl alcohols. 1,4-Dioxane
may constitute 0–4% by weight. An MSDS sheet for Solvent 111® listed
1,4-dioxane at 25 ppm (Unocal, 1989).
Tetrachloroethylene (PCE) Stabilizers are believed to include amines or mixtures of epoxides and
esters.
1,2-Dichloroethane 1,2-DCA produced in Japan is reported to contain polychlorinated ethanes.
Chloroform Ingredients may include bromochloromethane; carbon tetrachloride;
dibromodichloroethane; dibromodichloromethane; 1,1-dichloroethane; 1,2-
dichloroethane; cis-1,2-dichloroethene; trans-1,2-dichloroethene; dichloro-
methane; diethyl carbonate; ethylbenzene; 2-methoxyethanol; nitromethane;
pyridine; 1,1,2,2-tetrachloroethane; trichloroethylene; and meta-, ortho-,
and para-xylene. In Japan, chloroform has a minimum purity of 99.95% and
may contain chlorinated hydrocarbons as impurities.
4.6.1 POLYCHLORINATED BIPHENYLS

Detailed investigations concerning the commercial availability and formulations can
frequently provide valuable information for bracketing the age of a chemical and
timing of a release. Polychlorinated biphenyls (PCBs) provide an example of this
technique. Monsanto discovered PCBs in 1889 and produced them commercially,
primarily from 1930 until 1977, when Monsanto voluntarily halted production. PCBs
were manufactured by the catalytic chlorination of biphenyls to produce complex
mixtures, with each mixture containing up to 209 possible congener structures (Wait
1999). In the U.S., the manufacture of PCBs was halted on July 2, 1979. While
Monsanto was producing PCBs in the U.S., PCBs were also being produced in Italy,
Germany, and Japan. Manufacturers of PCBs worldwide and the respective trade
names of their products are summarized in Table 4.5 (Fisher 1988).
Polychlorinated biphenyls are listed on laboratory reports with a numbered
designation, such as PCB-1254; the 12 refers to the number of carbon atoms, while
the 54 refers to the number of chlorines. Different carbon and chlorine combinations
were manufactured for specific uses during discrete time periods. For example,
PCB-1016 was manufactured between 1971 and 1976 and used primarily as an

TABLE 4.5
Trade Names and Manufacturers of
Polychlorinated Biphenyls (PCBs)
Trade Name Manufacturer/Country
Aroclor Monsanto Chemical Corporation/U.S.

Phenoclor Prodelec/France
Kaneclor Kanegafuchi Chemical Company, Japan
Clophen Bayer/West Germany
Aroclor, Santotherm Mistubishi-Monsanto/Japan
Fenclor, Apirolio Caffaro/Italy
Soval Soval/USSR
insulator fluid for electric condensers and as an additive in high-pressure lubricants.

PCB-1254 was used as a secondary plasticizer in the manufacture of polyvinyl
chloride (PVC) and in capacitors; it was produced from 1957 to 1977 by Monsanto.
Since 1970 in the U.S., over 98% of the PCBs manufactured by Monsanto were
Aroclor-1260, -1254, -1248, -1242, -1232, -1221, and -1016; less than 2% were
Aroclor-1268 and -1262 (Ramamoorthy et al., 1997). Prior to 1970, analytical
limitations precluded the detection of PCBs in environmental samples (Shifrin and
Toole, 1998). Subsequent refinements in analytical instrumentation allowed the
detection of PCBs that were usually reported as total Aroclors by laboratories. With
the advent of high-resolution capillary gas chromatography columns in the early
1990s, all 209 PCB congeners were able to be calibrated (Frame et al., 1996; Frame
1997). Congeners are PCBs with the same structural backbone but differing in the
number and or position on the chlorines. PCB congener analysis, in addition to
isolation of the formulation period for a particular congener, offers an opportunity to
fingerprint PCBs for source identification. Examples of these approaches include
PCB pattern recognition in fish tissue collected in the St. Lawrence River, in
sediments in the Milwaukee Harbor Estuary in Wisconsin, and in water samples from
San Francisco Bay (Hwang et al., 1993; Johnson, 1999; Kannan et al., 1997;
Rachdawong and Christense, 1997). The date of formulation can, therefore, be
combined with its particular use to bracket the date at which it was available and to
identify probable locations at the facility that would use a particular PCB formula-
tion. Table 4.6 lists various applications of polychlorinated biphenyls (Montgomery,
1991; Pankow and Cherry, 1996).
In cases where PCBs from multiple manufacturers are present, radioactive
isotope analysis can be used to distinguish the manufacturer based on manufacture-
specific 13C ratios (Jarman et al., 1998). Significant differences in d13 ratios have
been reported for PCBs manufactured in Germany, Italy, Japan, and the U.S. This
method assumes that a product sample from each suspected manufacturer is avail-
able and that it is chemically identical to the fluid released.
Knowledge of the transition from PCBs to other dielectric fluids may provide a
basis for dating releases in a relative sense from one another. An example of

TABLE 4.6
Uses of Polychlorinated Biphenyls (PCBs)
PCB Applications
Aroclor-1016 Used as an insulator fluid for electric condensers and as an additive in

very high-pressure lubricants.
Aroclor-1221 Used as a plasticizer for polystyrene; in epoxy resins; as an insulator
fluid in electric condensers; as an additive in very high-pressure lubri-
cants; as dielectric fluid in capacitors and gas-transmission turbines; in
adhesives.
Aroclor-1232 Used as dielectric fluid in hydraulic oils; as adhesives; as an additive
in high-pressure lubricants; as a plasticizer in rubber. Also used as an
ingredient in polyvinyl acetate that improves fiber-tear properties.
Aroclor-1242 Used as a plasticizer in vinyl and chlorinated rubbers; as a wax ex-
tender; in carbonless reproducing paper; as a plasticizer in cellulosics;
in polyvinyl acetate to improve fiber-tear properties; as dielectric liq-
uids; as swelling agents for transmission seals; as an ingredient in
lubricants, oils, and greases; as a heat transfer liquid in transformers; as
a wax extender.
Aroclor-1248 Used as an additive in high-pressure lubricants; in epoxy resins; as an
insulator fluid in electric condensers; as a plasticizer in rubber; in
vacuum pumps; as dielectric fluid in gas-transmission turbines.
Aroclor-1254 Copolymer of styrene-butadiene and chlorinated rubber. Used as a
secondary plasticizer for polyvinyl chloride (PVC); as an insulator fluid
used in capacitors; in hydraulic oils; in vacuum pumps; in adhesives; in
wax extenders; in dedusting agents; as an extender in cutting oils,
lubricants, inks, and pesticides; as a resin plasticizer.
Aroclor-1260 Used as a secondary plasticizer for PVC; in varnish formulations; as
insulator fluid for electric condensers; as an additive in high-pressure
lubricants; as an ingredient in polyester resins used in fiberglassing.
Included in fire retardants and varnish to improve water and alkali
resistance.
segregating the chemical composition of a dense non-aqueous phase liquid (DNAPL)

to identify different reservoirs of DNAPLs can be found at the General Electric
Hudson Falls Plant located about 200 miles north of New York (Rawson et al., 1998).
The plant manufactured capacitors containing primarily Aroclor-1242 which were
discontinued in 1977. After 1997, dielectric fluids used were mixtures of bis-(2-
ethylhexyl)-phthalate (BEHP), phenyl-xylyl-ethane (PXE), and trichlorobenzene
(TCB). DNAPLs were characterized by the percent of the relative chromatographic
area of PCBs, BEHP, PXE, and TCB in the analysis by:
(Area of the individual components)/

(Eq. 4.2)
(PCB + BEHP + PXE + TCB Area) ¥ 100%

Given the sequential use of PCB, BEHP, PXE, and TCB, DNAPLs that contain
>90% PCBs were termed “old” while DNAPLs containing less than 10% area PCBs
and primarily BEHP, PXE, and/or TCB were referred to as “new”. DNAPLs contain-
ing more than 10% area PCBs but less than 90% PCBs were referred to as “mixed”.
This ranking has allowed identification of these DNAPL pools with various locations
and activities at the Hudson Falls plant site.
When forensically reviewing PCB data for source identification, recognize that
sources of uncertainty beyond the analytical discrimination of isolating distinct PCB
congeners exist. These include the small variances in PCB formulations, difficulties in
accurately quantifying a mixture of PCBs, co-extraction and co-elution of other interfer-
ing organic compounds, and co-mingling of multiple PCB mixtures (Wait, 1999). For
Askarels (i.e., a generic term used for nonflammable liquids used in transformers and
capacitors that are usually mixed with organic solvents such as chlorobenzenes),
numerous PCB congeners are present, thereby making individual PCB congener
identification difficult. Weathering may also preferentially degrade certain PCB
congeners, making it difficult to discern individual PCB fingerprint patterns.
4.7 PETROLEUM REFINERY

THROUGHPUT ANALYSIS
A variation to the technique of associating a chemical to a particular manufacturing

process is used in the case of a petroleum refinery with different historical tenants but
similar unit processes. This technique is referred to as a refinery throughput analysis
(Morrison, 1998b). This method also assumes that detailed information regarding
changes in refinery processes (i.e., detergent alkylate units, polymerization plants,
aromatic-isomerization, etc.) and the subsurface characterization of contaminants
from these operations are insufficient to “fingerprint” precisely the date of their
release and/or origin. This method assumes that solid waste residuals (spent catalysts
and catalyst cracker fines, spent caustic, treating clays, API separator bottoms, tank
bottoms, cooling tower sludges, trash, etc.) are produced as a function of the crude
oil throughput at the refinery and unit process configuration factors. The volume of
the crude oil throughput is required for the refinery, along with general information
regarding chronological development of the refinery.
Unit processes and waste streams associated with a particular distillation process
can be associated with a particular time frame; wastes unique to this process that
require remediation can be dated for the interval of time that the unit process
operated. This technique is used as a basis for cost allocation by acquiring the crude
oil throughput for the refinery on at least a yearly or, preferably, monthly basis.
Sources for providing the total volume of crude throughput and unit processes for
each owner/operator include site documentation and blueprints, historical aerial
photographs, Oil & Gas Journal, and state agencies, such as the Texas Railroad
Commission (TRC). The Oil & Gas Journal, for example, has summarized the
refining capacities of refineries in the U.S. since the early part of the century, while
the TRC has crude oil throughput for Texas refineries dating back 50 years.

TABLE 4.7
Example of Throughput Analysis Information
Crude Vacuum Thermal Catalytic
Year Capacitya Distillation Operations Alkylation Reforming
1950 18,000 0 6470 1890 6320

1951 38,000 0 5790 1200 2063
1952 45,000 0 6587 2400 5400
1953 65,000 1710 1200 1910 6500
1954 70,000 2700 500 2700 7000
a Barrels of crude oil per calendar day (b/cd).
Once this information is compiled, unit processes and chemicals unique to these
processes that are detected in the subsurface and require remediation are identified
for the years during which the release may have occurred. Complications in the
analysis arise if waste from a nonoperating unit process is stored at the facility for
some subsequent time period (i.e., co-mingled waste from multiple sources stored in
a surface impoundment). Table 4.7 shows an example of this method and the crude
oil throughput for specific unit processes. In instances where multiple parties oper-
ated the same unit, a weighing factor based on the crude oil throughput for that unit
process is developed for allocation between multiple tenants. Table 4.8 illustrates a
simple example of an allocation scheme for a time period for which the unit processes
are assumed to be identical for three refinery owners (absent detailed process
information).
In this example, the three parties would allocate the remediation costs according
to the percentage basis shown on Table 4.8. When unit process and specific waste
streams are available, further refinement to these the allocation percentages is
possible.
4.8 CHEMICAL IDENTIFICATION OF

PETROLEUM HYDROCARBONS
Chemical identification or “fingerprinting” describes the ability to distinguish the age

and often the origin of a chemical. Chemical fingerprinting is most commonly used
in hydrocarbon contamination cases. In its simplest form, it identifies the type of
hydrocarbon (diesel, gasoline, jet fuels, kerosene, and Stoddard solvent, etc.) as a
means of identifying the source and often the timing of a release. This identification
is performed through analysis of soil or groundwater samples or more qualitatively
with in situ techniques such as a cone penetrometer (CPT) equipped with a laser-
induced fluorescence sensor (Kram, 1988; U.S. EPA, 1997). This process of chemi-
cal fingerprinting is most commonly performed through “pattern recognition” or

TABLE 4.8
Example of Throughput Analysis Allocation
Year Crude Oil Throughput (Barrels of Oil per Year)
Operator A Operator B Operator C
1945 22,545,732
1946 29,673,382
1947 43,456,978
1948 53,567,567
1949 49,876,374
Total Operator A ª29%)
199,120,033 (ª
1950 45,567,879
1951 55,556,987
1952 43,456,879
1953 42,345,451
1954 39,354,567
1955 42,345,596
1956 41,956,936
Total Operator B ª45%)
310,584,295 (ª
1957 45,987,264
1958 43,659,286
1959 47,978,374
1960 45,867,375
Total Operator C ª26%)
183,492,299 (ª
“pattern matching” of gas chromatogram traces of different samples. For example,

comparison of chromatograms of two products designed as hydraulic fluids can
provide a means for distinguishing whether the fluid is petroleum or synthetically
derived which may assist in identifying a source or performing an allocation analysis.
Figure 4.4 shows chromatograms for a petroleum and synthetic hydraulic fluid
(Bruya, 1999).
Key compounds used in pattern recognition analysis includes the following
(Harvey, 1997; Stout, 1999; Stout et al., 1999c):
• Light petroleum products (BTEX and heavier aromatics; alkylate paraffins)

• Diesel fuels and distillates (normal alkanes and isoprenoid paraffins)
• Biomarkers such as sesquiterpanes (C15), diterpanes (C20), triterpanes (C30), steranes
(C30), and hopanoid compounds (i.e., present in some petroleum products but not
creosote; Butler, 1999)
• Crude oils and heavy fuels (substituted polyaromatic hydrocarbons and thiophenes)
Chromatograms for various fuels are shown in Figure 4.5 (Zemo et al., 1993; Bruya,
1999). The use of chromatographic pattern recognition is used to distinguish between
products as well as to develop qualitative estimate regarding the age of the product

FIGURE 4.4 Chromatograms of a synthetic and petroleum-based hydraulic fluid. (Courtesy
of Jim Bruya, Friedmand & Bruya, Inc., Seattle, WA.)
by comparing the chromatograms of fresh vs. weathered fuels. More sophisticated

analytical methods include examination of the composition of fuels as a function of
a unique formulation or additive packages associated with a discrete time interval.
These advanced forensic approaches can often reveal whether a chemical release was
a single event, a series of events, or a continuous release.

FIGURE 4.5 Examples of fuel chromatograms. (Courtesy of Jim Bruya, Friedmand & Bruya,
Inc., Seattle, WA.)
4.8.1 ANALYTICAL STRATEGY

An analytical strategy for performing a first cut to distinguish cumulative differences
in a product is a PIANO analysis, organic lead testing, and oxygenate characteriza-
tion analysis (Uhler et al., 1998). PIANO is an acronym for the primary hydrocarbon
constituents in a gasoline (paraffins, isoparaffins, aromatics, naphthenes, and ole-
fins). Depending on the results and interpretation of this analysis, additional testing

TABLE 4.9
Example of Analytical Strategies and Test Methods
Description of Analysis Method and Analytical Equipment
PIANO analysis of 50+ paraffins, isoparaffins, Modified EPA Method 8260, HRGC/MS
aromatics, naphthenes, and olefins
Organic lead analysis for five organic lead HRGC/MS or GC with ECD detector similar
species (TML, TMEL, DMDEL, MTEL, TEL) to EPA Method 608/8080 for PCB analysis
and associated lead scavengers (EDB, EDC)
Testing for oxygenates additives (MTBE, TAME, Modified EPA Method 8020 or 8260,
DIPE, ETBE, and alcohols); GC/MS
Note: TML = trimethyl lead; TMEL = trimethylethyl lead; DMDEL = dimethyldiethyl lead; MTEL =
methyltriethyl lead; TEL = triethyl lead; EDB = ethylene dibromide; EDC = ethylene dichloride; MTBE
= methyl-tertiary-butyl-ether; TAME = tertiary-amyl-methyl-ether; DIPE = diisopropyl ether; ETBE =
ethyl-tertiary-butyl-ether; HRGC/MS = high-resolution gas chromatography/mass spectrometry; GC/MS
= gas chromatography/mass spectrometry.
can provide confirmatory evidence. The PIANO analysis and analytical equipment
required are summarized in Table 4.9.
The bulk PIANO composition, showing relative contents of major hydrocarbon
groups in the fuel, is a useful cumulative parameter for fuel type differentiation,
especially the octane grade. The higher the relative content of iso-octanes (especially
2,2,4-trimethylpentane, or TCM) and aromatic hydrocarbons, such as toluene, the
higher the octane rating (Kaplan et al., 1997). This type of first cut using the octane
rating obtained via PIANO analysis thus provides a potential basis to distinguish
between gasoline and light petroleum products. Average values of bulk PIANO
composition for dispensed gasoline as a relative percentage are shown in Table 4.10
(Kaplan et al., 1995; 1997).
These results are often presented in a five-point star diagram, with each arm of
the star representing a distinct PIANO percentage. Distinguishing among different
TABLE 4.10
PIANO Composition of Dispensed Gasoline
Grade Paraffins Isoparaffins Aromatics Naphthenes Olefins
of Gasoline (%) (%) (%) (%) (%)
Regular leaded 10.7 32.0 45.0 7.8 4.6

Regular unleaded 10.2 37.6 38.7 6.0 7.1
Unleaded plus 10.8 37.0 41.5 5.6 5.1
Premium unleaded 9.4 34.9 48.4 2.9 3.9
JP-4 29.3 31.02 23.9 13.2 2.6
Aviation gasoline 3.3 74.2 22.0 0.5 0.01

TABLE 4.11
PIANO Composition of Selected Fuels
Paraffins Isoparaffins Aromatics Naphthenes Olefins
Hydrocarbon (%) (%) (%) (%) (%)
Gasoline, 87 octane 9.6 38.3 38.6 6.1 7.4

Gasoline, 89 octane 9.1 38.1 43.4 3.8 5.6
Gasoline, 92 octane 7.5 39.7 43.4 3.3 6.2
JP-4 29.3 31.0 43.4 3.3 6.2
Aviation gasoline 3.3 74.2 22.0 0.5 0.01
Diesel No. 2a 55 12b 24.0 — 5.0
Bunker Cc 21 21b 34.0 — —
a Residuals account for 4%.

b Cycloparaffins.
c Polar and associated residuals account for 45%.
products is often pronounced with this type of presentation, especially if the samples
are “fresh” fuels. PIANO ratios are also used for distinguishing among the relative
weathering rates of different fuels, whether in soil or groundwater.
PIANO results can be correlated with the octane rating of a fuel. The PIANO
compositions for different fuels are listed in Table 4.11 (Galerpin, 1997; Kaplan et
al., 1996). Due to the alkylation of fuels, the content of the major isoalkane generated
(2,2,4-trimethylpentane, or TMP) increases in the finished gasoline relative to the
methylcyclohexane (MCH) content. MCH is a common constituent of crude oil and
refined volatile fuels. Low-octane fuels (87) have a TMP/MCH ratio less than 2.5,
while high-octane gasolines (92 to 93) have TMP/MCH ratios greater than 5. Inter-
mediate-grade gasolines have TMP/MCH ratios in the 2.5 to 5.0 range.
Additional analyses to complement the available information may be performed.
Table 4.12 summarizes various analyses, target compounds, and the advantages and
disadvantages of various tests from a forensic perspective (Uhler et al., 1998). When
examining, interpreting, or challenging the results from these tests, the limitations of
the tests should be considered. Table 4.13 lists some of these concerns (Uhler et al.,
1998). In addition to these standard analytical techniques used to identify the age of
a hydrocarbon release, other approaches include analysis of proprietary additives, the
composition of anti-knock formulations, trace metals analysis, hydrocarbon profil-
ing, physical characteristics, and degradation models.
4.8.2 PROPRIETARY ADDITIVES:

Proprietary additives are compounds blended with refined products such as fuels. A
blended additive is a refinery product manufactured for bulk mixing with the fuel

TABLE 4.12
Opportunities and Challenges of Analytical Tests for Petroleum
Hydrocarbons
Analytical Method Target Compounds Utility
Modified EPA Method 8015; Extractable hydrocarbons; Basic-level product identification

TPH and product identification total petroleum hydrocarbons by GC/FID; all petroleum
contamination identified —
light distillates to asphalts;
quantification of these
compounds
Modified EPA Method 8015; C8 to C40 normal and branched Determination of petrogenic vs.
saturated hydrocarbons by alkanes (acyclic isoprenoids) biogenic input ratios and degree
GC/FID of weathering; biodegradation
of crude oil and middle distillates
Modified EPA Method 8260; C5 to C12 PIANO analysis Light distillate product
volatile organic compounds (paraffins, isoparaffins, identification and differentiation;
by GC/MS; purge and trap aromatics, naphthenes, and determining the refining history
olefins); gasoline additives of the gasoline and the degree of
(MTBE, EDB, EDC) weathering
Modified EPA Method 8270; 50+ diagnostic PAH; Long-term product/source identi-
PAH and heteroatomic aromatic 2 to 6 ring polyaromatic fication, particularly middle
hydrocarbons by GC/MS hydrocarbons; C1 to C4 distillates and crude oil; long-
alkyl homologues; nitrogen-, term weathering patterns; bio-
sulfur-, and oxygen-containing degradation indices; crude oil
PAHs vs. other feedstocks (coal, etc.)
and/or product. Additives often have discrete time intervals during which they were
introduced into a product formulation. The use of additives for hydrocarbon finger-
printing requires a prior knowledge of the additive package and the ability to detect
a unique additive not masked by other chemicals or obscured by environmental
degradation. An example of the former is the polybutene additive present in the
Chevron detergent F-310 in gasoline in 1982. In practice, identification of an
additive is not always straightforward. Many additives contain oxygen in their
molecular structure and therefore are soluble and biodegradable. Furthermore, the
polymers tend to depolymerize rapidly in the environment and convert into their
respective monomers, which can be rapidly metabolized, thereby making it difficult
to identify the parent additive compound (Galperin, 1997). Additives are sold to
refineries by specialty companies with little or no chemical alteration by the refin-
ery; as a result, the same additive may be present in the parent compounds of a co-
mingled gasoline or fuel plume (Kaplan et al., 1997). Categories of fuel additives
for different refined products and examples are shown in Table 4.14 (Ethyl Corpo-
ration, 1998; Gibbs, 1990, 1993; Harvey, 1997; Kram, 1988; Morrison, 1999b). The
composition of additive packages for refined products varies with time. For ex-

TABLE 4.12 (cont.)
Opportunities and Challenges of Analytical Tests for Petroleum
Hydrocarbons
Analytical Method Target Compounds Utility
Modified EPA Method 8270; >50 steranes, diterpanes, and Target compounds used to
biomarkers by GC/MS triterpanes: cyclic alkanes distinguish between petroleum
sources; refractory marker(s) for
improved biodegradation
monitoring; identification of
terminal petroleum degradation
products
Modified EPA Method 8270; Polyaromatic hydrocarbons, Distinguishes sources (manufac
semi-volatiles by GC/MS alkyl polyaromatic hydrocarbons tured gas plants vs. gasoline,
etc.)
Trace metal analysis, Trace metals, total lead, Possible delineation between
especially vanadium and nickel organic lead, nickel and sources of crude oil and
(EPA Method 6010 by ICP) vanadium presence of waste/crankcase oil
Ancillary analysis; simulated Carbon, hydrogen, sulfur, Source identification and
distillation testing (ASTM nitrogen isotope analysis; differentiation; age-dating of
Method D3328); density dyes, lead speciation, gasoline and crude oils
physical testing
Adapted from Uhler, A. et al., in Proc. of the Environmental National Environmental Forensics Confer-
ence: Chlorinated Solvents and Petroleum Hydrocarbons, Department of Engineering and Engineering
Professional Development, University of Wisconsin, Madison, 1998, p. 24. With permission.
ample, a typical additive package for gasoline formulated in the 1980s was 62%
tetraethyl lead, 18% ethylene dibromide, and 2% inactive ingredients such as
stability improvers, dyes, and antioxidants (Younglass et al., 1985).
Diesel and jet fuels contain additive packages. Additive packages for diesel include
quality-enhancing packages such as diesel ignition and stability improvers, antistatics,
corrosion inhibitors, and surfactants which are associated with discrete periods of
time (Barker et al., 1991). Different sources of diesel can often be distinguished by
analyzing the sulfur content of the diesel, which is usually different, depending upon
the original source of the crude oil. Another method for distinguishing among
different sources of diesel is to perform an analysis of the polynuclear aromatic
(PNA) compounds in a sample and then perform a “peak-to-peak” comparison of
these PNAs results between samples. PNA analysis in addition to the sulfur analysis
can usually distinguish between two different diesel sources, prior to co-mingling.
The identification of biomarkers such as isoprenoids that are unique to a particular
diesel can also be used to distinguish differences between fuels. PNA analysis can
assist in defining the relative age or use of motor oil. Used motor oil, for example,
will contain more PNAs than a sample of the same oil that has not been used.

TABLE 4.13
Potential Limitations of Analytical Test Methods
EPA Method Potential Limitations
413.1 Gravimetric Provides results for total petroleum extractables; subject to
interference and detection limit limitations
418.1 Infrared Provides results for total petroleum extractables; subject to
multiple interferences; false positive/negatives common,
especially in organic matter; detection limit limitations
8015 GC/FID Product identification subject to interpretation; similar product
types cannot be differentiated (e.g., aviation gasoline vs.
gasoline); false positives are common, especially biogenic
sources.
8270 GC/MS Reports only 16 priority pollutant polycyclic aromatic
hydrocarbons; ignores important petroleum-related polycyclic
aromatic hydrocarbons and provides little or no diagnostic
qualitative information; detection limit limitations
8020/8260 GC/PIC and GC/MS BTEX only (8020); 8260 misses 100+ important volatile
hydrocarbons; detection limit limitations
Adapted from Uhler, A. et al., in Proc. of the Environmental National Environmental Forensics
Conference: Chlorinated Solvents and Petroleum Hydrocarbons, Department of Engineering and
Engineering Professional Development, University of Wisconsin, Madison, 1998, p. 24. With
permission.
TABLE 4.14
Examples of Additives for Selected Fuels
Blended Product Additive Category, Purpose, (Examples)
Gasoline Anti-knock compounds to increase the octane rating, prevent engine knock, and
reduce automobile emissions (alkyl leads, organo-manganese compounds)
Antioxidants/stabilizers to prevent gum formation and degradation during storage
and transport (p-phenylenediamine; alkyl-substituted phenols)
Corrosion inhibitors to prevent storage/pumping failures (carboxylic acids and
diimides)
Detergents to prevent carbon deposits on carburetors and fuel injectors (amines,
amine carboxylates)
Dyes to provide color differentiation (azo- and other oil-soluble compounds such
as azo-benzene-azo-naphthols, phenyl-azo-naphthols [red, orange, bronze],
and alkylamino-anthraquinones [blue])
Anti-icers to prevent icing in carburetor and fuel systems (short-chained n-
alcohols (freeze-point depressants; amines and ethoxylated alcohols with long
hydrocarbon chains)

TABLE 4.14 (cont.)
Examples of Additives for Selected Fuels
Blended Product Additive Category, Purpose, (Examples)
Oxygenates to increase the octane number and respond to environmental require-

ments (methanol, methyl-tertiary butyl-ether [MTBE], methyl ether)
Lead scavengers to prevent precipitation of lead in the engine and exhaust system
(ethylene dibromide [EDB], ethylene dichloride [EDC])
Metal deactivators to inhibit oxidation and gum formation catalyzed by certain
metals, particularly copper (chelating agents)
Demulsifiers to improve water separation (polyglycol derivatives)
Deposit control agents to prevent and remove deposits throughout the fuel intake
system (polybutene amines, polyether amines)
Diesel Antioxidants, stabilizers, and anti-rust inhibitors such as ethoxylated alkyl phenols,
alkenyl succinic acids, and amine phosphates used to prevent degradation and
rusting during storage and transport
Cetane improvers for consistent combustion characteristics and emission reduction
(alkyl nitrates, hydroperoxides)
Cold-flow improvers to enhance fuel pumping
Conductivity modifiers to neutralize static charge build-up in fuel
Detergents/dispersants to prevent carbon deposits on engine parts (synthetic
sulfonates, phenates, salicylates, phosphonates, Mannich bases, succinate esters,
succinimides)
Dyes for fuel identification and leak detection (see dyes for gasoline)
Biocides used to inhibit the proliferation of bacteria and fungi (organo-boron
compounds)
Lubrication agents
Pour-point depressants used to reduce the yield stress of the fuel and improve the
flow of the diesel at low temperatures (polymethacrylates, alkylated naphthenes,
ethylene vinyl acetate copolymers, fumarate-binylacetate copolymers, alkylated
polystrene, acylated polystrene, polyolefins, aliphatic amine oxides, and oxidized
wax)
Crankcase oils Antioxidants to resist high-temperature degradation
Anti-wear agents to protect metal surfaces from abrasion
Corrosion inhibitors to protect metal parts
Detergents to prevent carbon and varnish deposits on engine parts
Dispersants to keep engine parts clean
Pour-point depressants to enable oil flow at cold temperatures
Viscosity index improvers to provide uniform flow properties over a wide range
of temperatures
Specialty oils Antioxidants to resist high-temperature degradation
(automatic Anti-wear agents to protect metal surfaces from abrasion
transmissions, Corrosion inhibitors to protect metal parts
hydraulics) Detergents to prevent carbon and varnish deposits on engine parts
Friction reducers to facilitate movement

TABLE 4.15
Chronology of Lead Usage in Gasoline
Date Significant Changes in Lead Usage in Gasoline
1923 Tetraethyl lead marketed by Refiner’s Oil Company, Dayton, OH

1924 General Motors and DuPont Corp. form Ethyl Corp. to market and produce
tetraethyl lead
1926 The U.S. Surgeon General recommends 3.17 g/gal as the maximum allowable
concentration of tetraethyl lead per an agreement with Ethyl Corp.
1927/8 Approximate time for the introduction of lead scavengers (EDB and EDC)
1959 Maximum permitted lead in gasoline increased to 4.23 g/gal
1960 Trimethyl and tetramethyl lead introduced; tetraalkyl lead (TAL) added to
commercial gasoline in the U.S. (Messman and Rains, 1981)
1969 Tertiary butyl alcohol (TBA) introduced
1970 Low-leaded gasoline introduced by Gulf Oil Company (now Chevron)
1974 The U.S. Environmental Protection Agency (EPA) requires major gasoline
retailers to sell one grade of unleaded gasoline by July 1, 1974
1975 EPA calls for the reduction of lead in automobile gasoline to 1.7 g/gal in 1975,
1.4 g/gal in 1976, 1.0 g/gal in 1977, 0.8 g/gal in 1978, and 0.5 g/gal in 1979
1980 EPA established the overall lead for large refiners at 0.5 g of lead per gallon
1982 EPA set the average lead concentration for leaded gasoline at 1.10 g of lead per
gallon for large refiners
1983 EPA established the average lead content for leaded gasoline of [how much?]
lead per gallon for all refiners; lead credits were established
1985 EPA limited the concentration of lead to 0.50 g per gallon in June; lead credits
were allowed; many states began phasing out lead in the gasoline during the
middle to late 1980s
1986 EPA limited lead content to 0.10 g per gal in January; lead credits were allowed;
decrease to 0.10 was scaled from 1986 to 1988
1987 EPA eliminated lead credits
1995 Over 50 countries (20 in Africa) permitted lead in gasoline at concentrations up
to 0.8 g/L; maximum concentration in Europe was 0.15 g/L
1996 EPA eliminated lead in all U.S. gasoline per Section 211(n) of the Clean Air Act
after 1995
4.8.3 ANTI-KNOCK ADDITIVES (ALKYL LEADS)

Chronologies based on gasoline additives and characteristics of gasoline blending are
usually useful in providing an age-dating resolution of 5 to 10 years. In many cases,
this resolution is sufficient. Alkyl leads, the most frequently encountered anti-knock
additives, were added to gasoline to suppress “spark knock” and to increase the
octane number. On December 9, 1921, Thomas Midgley and Tom Boyd of General

Motors Research Corporation discovered that tetraethyl lead (Pb(C2H5)4) was an
effective anti-knock additive. Gasoline with tetraethyl lead (also referred to as lead
tetraehide, tetraethyllead, and tetraethylplumbane) was first marketed on February 1,
1923, at a service station of the Refiners Oil Company in Dayton, OH (Nickerson,
1980; Rhue et al., 1992). In August of 1924, General Motors and Standard Oil
Company of New Jersey (now Exxon Corporation) formed a partnership to create
Ethyl Gasoline Company (now Ethyl) to market tetraethyl lead. Ethyl Corporation
began marketing TEL at the end of 1947, and DuPont Corporation began marketing
TEL in 1948. By 1950, most gasoline in the United States contained lead.
In 1960, tetramethyl and trimethyl lead (marketed by Standard Oil Company of
California, now Chevron Corporation) were introduced (Stormant, 1960). Consump-
tion of all lead alkyls peaked in 1969 and declined through the 1970s as improve-
ments in catalytic reforming, hydrocracking, and hydrotreating occurred which
further improved base gasoline octane levels (Global Geochemistry Corp., 1991; Lee
et al., 1992). For premium-grade gasoline, these concentrations were as much as 2.9
g/gal. Subsequent reductions in lead concentrations in gasoline occurred due to
regulatory concerns in the late 1970s until 1985. Tetraethyl lead was reportedly the
only alkyl lead additive added to leaded fuels after 1980. Only tetraethyl lead is
currently used as an additive in leaded gasoline in amounts up to two orders of
magnitude less than added before 1980. The history of lead additives in gasoline
frequently provides a basis for bracketing the age of the gasoline in the soil or
groundwater. Table 4.15 is a chronology of significant changes in the use of lead in
blended fuels (Gibbs, 1990; Harvey, 1998; Morrison, 1999b).
Tetraethyl, triethylmethyl, and methyldiethyl tetramethyl lead are the most com-
mon organic lead alkyl additives. Lead additive packages often contain multiple
combinations of these lead additives as well as redistribution reaction mixtures of
tetraethyl and trimethyl lead. Redistribution reactions of equimolar amounts of
tetraethyl and tetramethyl leads can also produce trimethyl, trimethylethyl,
dimethyldiethyl, and methyltriethyl lead (Christensen and Larsen, 1993). Reacted
mixtures of leads are typically marketed as RM25, RM50, and RM75, with the
number designating the molar percent of trimethyl lead present in the mixture (Sout
et al., 1999b). A typical commercial reaction mixture from the use of equimolar
amounts of tetraethyl lead and trimethyl lead is 3.8% trimethyl lead, 23.4%
trimethylethyl lead, 42.4% dimethyldiethyl lead, 25.6% methyltriethyl lead, and
4.8% triethyl lead (Kaplan et al., 1997). Physical mixtures of unreacted combinations
of tetraethyl and tetramethyl leads are described in percentages, such as 20:80, 50:50,
80:20, etc.
Tetraethyl lead is a historical gasoline additive used to suppress pre-ignition and
to improve the octane rating of the fuel. Older gasoline included tetraethyl lead along
with lead scavengers such as ethylene dibromide and ethylene dichloride (1,2-
dichloroethane). Tetraethyl lead is usually clear, unless red, orange, or blue dyes are
added. Tetraethyl lead was blended with gasoline prior to 1985 at about 400 to 500
mg/L. The presence of organic lead in free product is therefore indicative of a pre-
1985/86 release. Tetraethyl lead is currently being phased out of gasoline. Given that
tetraethyl lead has a low water solubility and high organic solubility, it can reside in

FIGURE 4.6 Lead pool standard at a refinery from 1965 to 1991.
soil after the fuel has evaporated and/or biodegraded. Conversely, tetraethyl lead can
be remobilized and dissolved by a subsequent gasoline release migrating through the
same soil. Tetraethyl lead is not present in condensate, distillates, or naphtha (Bruce
and Schmidt, 1994).
The presence and concentration of organic lead in soil or groundwater samples
has been argued as a means by which to determine when the fuel was released into
the subsurface. In 1982, the maximum lead concentration in gasoline was 4.2 g/gal.
In 1984, the U.S. Environmental Protection Agency (EPA) set a maximum of 0.1 g/
gal. This concentration applies to the average quarterly production from a refinery or
pool standard. The pool standard is the total grams of lead used by a refinery in a
given time period divided by the total amount of gasoline manufactured in the same
time frame. As a result, individual batches of gasoline can contain 4.2 g/gal per EPA
requirements and 0.8 g/gal in California. It has been argued that these guidelines can
be used to predict the time frame during which the product was manufactured or how
long the gasoline has been present in the subsurface. This approach is illustrated in
Figure 4.6, in which the lead pool standard for a refinery is plotted from 1965 to 1991.
A soil sample with a lead concentration of 0.5 g/gal is argued as being representative
of a highly weathered gasoline that was released prior to 1985.
A challenge to this argument is that lead results of an individual sample are not
conclusive because the lead content for any point in time is based on the pool
standard. The consequence of this practice is that individual gasoline samples vary
from batch to batch and cannot be used to date the year of manufacture. The pool
standard may also not reflect any true refinery amount due to lead accounting
practices (lead credits are bought or sold) and the fact that they are usually averaged
quarterly. In addition, multiple releases of gasoline from 1985 to 1991 with low
concentrations could result in an accumulated lead concentration of 0.5 g/gal rather
than providing evidence of a pre-1985 gasoline release.
Other anti-knock ingredients used in fuels include nickelcarbonyl and iron-
based compounds such as dicyclopentadienyl iron and iron pentacarbonyl; the latter

TABLE 4.16
Chronology of MMT Usage
Date MMT Usage
1953–58 Ethyl Corporation discovered and introduced MMT as an anti-knock compound for
gasoline; marketed it as a performance additive under the trade name HiTec 3000
1959 MMT/lead additive package marketed by Ethyl as AK-33X; not widely used
1974 MMT first used independently, without lead, in concentrations up to 0.125 g/gal
1978–79 MMT banned from unleaded gasoline per the Clean Air Act amendments in Octo-
ber; temporarily reinstated in the summer of 1979 during the peak summer driving
months to help extend crude oil due to the Arab oil embargo; ban on MMT was
reimposed in 1979, and MMT is still used in leaded gasoline
1995 On July 11, the EPA administrator granted Ethyl Corporation’s application for a
fuel additive waiver for MMT use in unleaded gasoline; on October 20, a three-
judge panel of the U.S. Court of Appeals ruled that MMT could be used in unleaded
gasoline; in December, Ethyl began shipping MMT to oil company customers
1996 EPA eliminated leaded gasoline, including those that contained MMT
1997 MMT banned in Canada
compound was marketed in Germany in the 1930s at concentrations of less than 0.5%
by volume (Calingaert, 1938). Iron pentacarbonyl is a common metal compound that
was marketed in the 1930s. Another anti-knock compound is the manganese additive,
methylcyclopentadienyl manganese tricarbonyl (MMT; CH3C5H4Mn(CO3)), which
was introduced in the U.S. in 1957 and used as an anti-knock and lead alkyl
supplement until 1978. MMT was later commercialized as a supplement to tetraethyl
lead (Ethyl Corporation, 1996; Gibbs, 1990; Hurst et al., 1996). Between 1976 and
1990, nearly 70 million pounds of MMT were blended with gasoline sold in the U.S.
Table 4.16 is a chronology of the use of MMT usage in the U.S. (Ethyl Corporation,
1998; Gibbs, 1990a,b, 1993; Harvey, 1998; Stout et al., 1998a,b).
MMT synonyms and trade names include CL-2, Combustion Improver-2, man-
ganese tricarbonyl-methylcyclopentadientyl, and 2-methylcyclopentadientyl. Al-
though MMT can be age diagnostic, its absence in gasoline does not necessarily
indicate a basis for age-dating, as it was not routinely added by all manufacturers.
It is currently an additive in Canadian gasoline. Analytical techniques are not readily
available to test for MMT and usually require a specialty laboratory to perform the
analyses.
4.8.4 LEAD SCAVENGERS

The initial use of tetraethyl lead as an anti-knock compound resulted in metal
corrosion caused by lead oxide formation in the combustion chamber which damaged
spark plugs and exhaust valves. The lead scavengers ethylene dibromide (EDB) and
ethylene dichloride (EDC) were first introduced in 1928 to alleviate this problem

(Kaplan et al., 1997). These lead scavengers minimized the precipitation of lead
oxide formation within automobile engines. During engine combustion, the ethylene
dibromide or ethylene dichloride forms lead bromide or lead chloride, both of which
are relatively volatile and pass through the engine with the exhaust. EDB and/or EDC
in a lead package is determined by the amount of alkyl lead present. A sufficient
amount of scavenger is added to react theoretically with all the lead, which is termed
“one theory”. Typically, 1.0 to 1.5 theories were used. A typical mixture for automo-
tive gasoline in the 1980s consisted of about 62% tetraethyl lead, 18% ethylene
dibromide, 18% ethylene dichloride, and 2% inactive ingredients such as dyes,
antioxidants, petroleum solvent, and stability improvers (Galerpin, 1997). EDB is
currently used in aviation piston engines.
Ethylene dibromide and EDC are moderately soluble (4321 mg/L and 8.69 g/L,
respectively, at 20∞C) and quickly dissolve into groundwater. Given that lead alkyls
are strongly adsorbed to soil and tend to be hydrolyzed with water, the presence of
lead scavengers may be the only evidence regarding the release of a leaded gasoline
at a site. For phase-separate gasoline in groundwater, the longer that the gasoline is
in contact with water, the more EDB or EDC will solubilize into the water, thereby
providing a relative basis to compare the length of time that the gasoline has been in
contact with the groundwater.
The ratio of total alkyl lead and EDB and/or EDC concentrations present in
phase-separate gasoline in groundwater can be used to identify multiple gasoline
releases. Figure 4.7 illustrates the measurement of this ratio in 1980 and 1984; the
lower figure indicates both the presence of the initial and subsequent release and the
approximate location of the second spill relative to the first release.
4.8.5 OXYGENATES
Oxygenates are blended with gasoline for the purpose of increasing the oxygen
content and reducing carbon monoxide emissions. The American Society of Testing
for Testing Materials defines an oxygenate as “an oxygen-containing, ashless, or-
ganic compound, such as an alcohol or ether, which can be used as a fuel or fuel
supplement” (Gibbs, 1998). Numerous oxygenates have been used; ethanol, for
example, dates back to antiquity, while the tertiary alkyl ethers were first produced
in 1907. Table 4.17 lists various oxygenates blended with gasoline (Gibbs, 1998;
Davidson and Creek, 1999). Selected chemical and physical properties of these
oxygenates at 25∞C can be found in Table 4.18 (Gibbs, 1998; Harvey 1998; Mont-
gomery, 1991), and a more complete list of physical properties is provided in
Appendix C.
Ethanol was first blended with gasoline in the U.S. in the 1930s and 1940s,
although its widespread use did not occur until after 1978. The purpose of blending
ethanol with gasoline was to increase the octane quality and to act as a fuel extender.
Ethanol has historically been produced via the fermentation of corn or sugar cane.
Ethyl-tertiary-butyl-ether (ETBE) was available in 1969 and was blended with
methanol in 1981, although methanol blends are no longer used (Gibbs, 1998).

FIGURE 4.7 Use of the total alkyl lead to EDB concentration ratio to identify multiple
releases and approximate locations.
TABLE 4.17
Acroymns and Chemical Formulas for Oxygenates
Compound Acronym Chemical Formula
Methanol MeOH CH4O

Ethanol (ethyl alcohol) EtOH C2H5OH
Methyl-tertiary-butyl-ether MTBE (CH3)3COCH3
Tertiary-butyl alcohol TBA C(CH3)3OH
Tertiary-amyl-methyl-ether TAME C(CH3)2(C2H5)OCH3
Ethyl-tertiary-butyl-ether ETBE C(CH3)3OC2H5
Diisopropyl ether DIPE (CH3)2CHOCH(CH3)2

TABLE 4.18
Selected Chemical and Physical Properties of Oxygenates
Specific Gravity Henry’s Law Constant Water Solubility
Oxygenate (atm m–3)/mol (mg/L = ppm)
Methanol 0.796 4.4 ¥ 10–6 Infinitely soluble

Ethanol 0.794 5.1–6.2 ¥ 10–6 Infinitely soluble
MTBE 0.744 1.1 ¥ 10–3–5.8 ¥ 10–4 43,000–54,3000
TBA 0.791 1.04–1.4 ¥ 10–5 Infinitely soluble
ETBE 0.73 2.6 ¥ 10–3 76,500
TAME 0.77 1.2 ¥ 10–3 20,000
DIPE 0.73 4.7-9.9 ¥ 10–3 9000 (20∞C)
Tertiary-butyl formate (TBF) 1.07 2.7 ¥ 10–4 40,000
Atlantic Richfield Company (ARCO) began using methyl-tertiary-butyl alcohol

in 1979 via the catalytic reaction of isobutylene (CH3)2C=CH2) and methanol (CH3OH).
MTBE usage increased rapidly in the 1980s at a rate of about 40% per year (Steffan
et al., 1997; Suflita and Mormile, 1993). In 1992, the production capacity and actual
production of MTBE in the U.S. were 11.6 and 9.1 billion pounds, respectively. By
1993, MTBE was the most widely used oxygenate and was the second most produced
organic compound in the U.S. (Reisch, 1994). In 1997, approximately 8 billion kg
of MTBE were produced in the U.S. (Hitzig et al., 1998). MTBE is currently the most
widely used oxygenate, although TAME, ETBE, and DIPE are also blended with
gasoline There are currently 27 companies in the U.S. that produce MTBE. MTBE
is also imported into the U.S. from Alberta Envirofuels in Canada and from Citgo in
Argentina.
Methyl-tertiary-butyl-ether was initially added as an octane-enhancing replace-
ment for tetraethyl lead, which was being phased out; it was later used as a fuel
oxygenate to decrease the amount of carbon monoxide in automobile emissions and
to improve the tolerance for moisture in gasoline (Chapelle, 1999). MTBE is not,
however, contained in all post-1980 gasoline. MTBE is blended with reformulated
gasoline that is required for severe ozone non-attainment areas that do not meet
federal ozone ambient air quality standards. Current unleaded gasoline contains as
much as 15% (Oxy-fuels) while many states use MTBE as an octane booster at up
to 8% by volume. MTBE was introduced into east coast, gulf, and midwest gasoline
after 1979/80 and into west coast gasoline after 1990. Its documented use on the east
coast was from 1979, and in California after 1986 (Davidson and Creek, 1999;
Squillance et al., 1996). Since the 1990s, it has been used in gasoline in over 15 states
to meet federal Clean Air Act of 1990 requirements for oxygenates in wintertime
oxygenated gasoline (starting in 1992) and in federal reformulated gasoline in 1995
to meet carbon monoxide ambient air quality standards (CEPA, 1996). As this
chapter was being written, Chevron, Tosco, and other oil companies are phasing out
MTBE from unleaded gasoline. Tosco, for example, plans to replace MTBE with

TABLE 4.19
Chronology of Oxygenate Use
Date Usage
1907 First TAME produced; agrol, alkylgas, ethanol fuels used in Nebraska
1934 First tertiary alkyl ether synthesis patent in the U.S. issued; methanol fuels used in
Germany due to World War II; Alkyl-Gas (ethanol blend) marketed in Nebraska
1968 Chevron taxicab field test of MTBE/TAME; ARCO first used tertiary butyl alcohol in
gasoline
1977 Clean Air Act Amendment required waivers; MTBE first used by ARCO; Nebraska
gasohol (ethanol blend) program began; EPA waiver issued for 10% by volume for ethanol
Late 1970s EPA waiver issued for 7% volume for MTBE; MTBE use began; EPA waiver issued for
2.5% each for methanol and tertiary butyl alcohol; MTBE included in gasoline in the
eastern seaboard from 1979 to the mid-1980s (Garrett et al., 1986; McKinnon and Dyksen,
1984)
1980s Experimentation with MTBE, methanol (M85), and ethanol as octane boosters; east coast
transmission lines pumped MTBE; EPA “substantially similar” rule issued with 2% by
weight oxygen maximum limit (11% by volume for MTBE)
1987 Denver began wintertime oxygenated gasoline program using MTBE (ethanol subse-
quently used); Colorado required oxygenates
1988 EPA waiver issued for 15% by volume for MTBE as the maximum amount
1989 Phoenix, Las Vegas, Reno, and Albuquerque began wintertime oxygenated gasoline pro-
gram using MTBE (ethanol used later); Clean Air Act Amendments enacted; “substantially
similar” maximum oxygen limit increased to 2.7% by weight (15% by volume for MTBE)
1992 Oxygenates required during the winter in carbon monoxide non-attainment areas; ethanol
used where economical; federal wintertime oxygenated gasoline program required 2.7% by
weight minimum oxygen in 39 carbon monoxide non-attainment areas
1994 Tertiary-methyl-ether and ETBE usage became limited; reformulated gasoline ozone non-
attainment areas; federal reformulated gasoline program required 2.0% by weight mini-
mum oxygen content; California Phase 2 required reformulated gasoline by requiring 1.8–
2.2% by weight oxygen; 95% of all gasoline sold in California contained MTBE (Davidson
and Creek, 1999)
1998 California Health and Environmental Assessment of MTBE report recommended the
gradual phase-out of MTBE in California gasoline (Keller et al., 1998)
1999 Chevron and Tosco begin gradual phase-out of MTBE in unleaded gasoline; town of South
Lake Tahoe, CA, banned MTBE because of concerns about its potential impact on the
town’s drinking water supply
ethanol. Table 4.19 is a chronology of oxygenate usage from 1907 to 1999 (Gibbs,
1998; Harvey, 1998).
Methyl-tertiary-butyl-ether is about 25 time more soluble than benzene (approxi-
mately 42,000 mg/L) and is not retarded by soil as it travels in groundwater. As a
result, MTBE is frequently encountered in post-1980 gasoline releases. Of 5738 sites
in California in 1988 that were being monitored by the California State Water
Resources Control Board because of groundwater contamination from gasoline, 3180

(55%) detected MTBE (ranging from 0.5 to 20 mg/L). MTBE plumes in groundwater
are longer than BTEX plumes due to the absence of MTBE retardation. In field
studies of unconfined, sandy aquifers, MTBE migrated at the same rate as ground-
water, while benzene, toluene, and ethylbenzene/xylene migrated at about 90%,
75%, and 67% of the groundwater velocity, respectively (API, 1994). At a site in
South Carolina, gasoline containing MTBE was transported at the same rate as
groundwater, while benzene was transported about 80% of the same distance
(Landmeyer et al., 1998). This retardation factor of 0.8 with respect to groundwater
is consistent with observations at other sites. As a result, MTBE is often found at the
leading edge of a groundwater plume without the presence of the other BTEX
compounds; in these situations, its presence can be used qualitatively as an indicator
of the length of the downgradient plume.
Methyl-tertiary-butyl-ether and other fuel oxygenated can be determined using
purge and trap gas chromatography methods such as EPA Method 502.2 or ASTM
D481.5 using gas chromatography with multiple columns (Draper et al., 1998). If
EPA Method 8020 is used, there is a 1 to 3% probability of a false positive test result
as various methyl pentanes and methyl pentenes often co-elute with MTBE. ETBE,
TAME, and DIPE can also be reliably determined using EPA Method 524.2 with low
detection limits and high accuracy. MTBE concentrations are reliably determined
with mass spectrometry, which bases MTBE identification on the retention time and
the mass spectral features of the gas chromatograph peak.
When using MTBE and other oxygenated additives in forensic evaluations for
age-dating, identify the potential sources of bias impacting the interpretation of
MTBE data. Examples include the following (Davidson and Creek, 1998; Hitzig et
al., 1998):
• Potential false positives from laboratory testing

• Additives from non-point sources
• Incidental blending and/or mixing of additives in gasoline supplies
• Cross-contamination from one fuel to another, especially in pipelines and tanker
trucks
• Differences due to seasonal reformulations
• Product swapping by the gasoline jobbers or in exchange agreements between
refineries and bulk storage facilities (Davidson and Creek, 1998; Hitzig et al., 1998)
Given the high volatilization potential and solubility of MTBE in water, its presence
in groundwater may not be indicative of a liquid release. The presence of MTBE in
groundwater may be from a non-point source, especially at concentrations <10 ppb
(Pankow et al., 1997). Nonpoint sources include stormwater runoff (0 to 15 mg/L) and
surface water sources, such as watercraft (0 to 40 mg/L) (Davidson, 1999).
Methyl-tertiary-butyl-ether can cross-contaminate non-gasoline products due to
shipping and storage in pipelines, tankers, above-ground storage tanks, and trucks.
MTBE has been detected in the presence of jet fuel, diesel fuel, heating oil, aviation
gas, and waste oil (Hitzig et al., 1998). In Connecticut, for example, 27 of 37 heating
oil spill sites detected MTBE in groundwater at concentrations from 1 to 4100 mg/L

(Davidson, 1999). The classic example of an indirect source of MTBE is its detection
in groundwater under an underground storage tank containing gasoline with MTBE
that has not leaked. The transport mechanism of MTBE from the tank is usually via
vapor leakage from the tank, movement of the vapor cloud through the vadose zone
as a function of density and convection, and resolubilization of the MTBE into the
groundwater (Hartman, 1998b). This transport mechanism occurs because of the high
solubility of MTBE relative to its equilibrium concentration in air. If this transport
scenario is suspected, test the soil vapor with a flame ionization detector for the lower
alkanes (C4 through C8), as they tend to remain in the vapor phase. In addition, soil
and/or groundwater samples should be tested for MTBE with a photoionization
detector. Benzene may also be present in the soil vapor and water but not present at
significant concentrations in either phase.
Field studies of MTBE biodegradation in shallow aquifers indicate that while
MTBE is biodegradable, it is low relative to BTEX compounds (Landmeyer et al.,
1998). MTBE degrades anaerobically under iron and sulfate reducing (Mormile et
al., 1994). Potential biotransformation intermediates of MTBE include tertiary-butyl
formate (TBF) and tertiary-butyl alcohol. As a result, it may be useful to perform
analysis for tertiary-butyl formate and/or tertiary-butyl alcohol concentrations along
with MTBE as an additional confirmation of the presence of MTBE.
4.8.6 TRACE INORGANICS

Trace metal analysis can be useful in providing additional information regarding the
type of hydrocarbon or fuel. Trace metals include barium, cadmium, copper, lead,
mercury, silver, arsenic, cyanide, iron, selenium, nickel, vanadium, cobalt, beryl-
lium, antimony, and zinc. Nickel, vanadium, and sulfur are present in low-gravity
crude oils but are absent or present in minimal quantities in refined products. Waste
oil is more likely to contain lead, zinc, chromium, copper, or aluminum from the
abrasion of an engine than is a fuel or pristine oil. For example, the concentrations
of vanadium and nickel are often several thousand times higher in a crude oil and can
thereby be used as a marker to identify a crude oil. Vanadium-nickel ratios are used
in oil field exploration to identify similar crude oil reservoirs (Potter, 1990).
Metals are also fuel additives; the inclusion of barium and zinc to motor oil is one
example. Calcium, phosphorous, and zinc are common additives to lube oils but are
not predominant in crude oil. While not a trace metal, boron was a common gasoline
additive in use from 1956 to 1981 and, if detected with gasoline, may provide an
indicator of a pre-1981 formulation. Another example is the addition of borate to
gasoline in the 1960s by ARCO.
4.8.7 PETROLEUM DYES

Gasoline and other fuels can contain dyes used to distinguish between the fuels. The
use of dyes in gasoline was the result of an agreement concerning tetraethyl lead

between Ethyl Corporation and the U.S. Surgeon General in 1926. The agreement
required that a sufficient amount of dye be added to impart staining qualities to
leaded gasoline to deter its usage for cleaning or other purposes. Dyes are also used
by some states to identify that no highway tax has been paid or that the gasoline is
used for non-highway (agricultural) applications.
An impurity in a commercial dye may be measurable and thereby provide a
means by which to distinguish between products with different dyes. For example,
yellow gold and pink/red dyes are added to gasoline to distinguish among different
grades of gasoline. Blue, yellow, and red dyes are used to differentiate octane ratings
in aviation gasoline (Ward, 1984). Typical concentrations for a dry dye range from
0.7 to 1.3 g/100 gal (Youngless et al., 1985). Plate 4.2* shows dye additives for
different gasoline brands obtained via thin layer chromatography.
Commercial dyes used as gasoline additives (approximately 1 to 5 ppm) are
usually part of a lead anti-knock package containing lead scavengers that are added
at the refinery at the in-line blender or the finished fuel-blending tank. Common dyes
include (Kaplan et al., 1996a, 1997):
• Red (alkyl derivative of azobenzene-4-azo-2-naphthol)

• Orange (benzene-azo-2-naphthol
• Yellow (para-diethyl aminoazobenzene)
• Blue (1,4-diisopropyl-aminoanthraquinone).
The high-resolution mass spectral chromatograms for 21 commercial dyes were

examined by Youngless et al. (1985). The empirical formulas of the dyes suggested
azo-, diazo-, and anthraquinone-type structures. In some cases, the dye was multi-
component, such as in the case of a bronze dye. Dyes in gasoline are analyzed with
either thin layer chromatography or by ultraviolet-visible absorption spectrometry
(Touchstone, 1992). Specialty analytical laboratories that have experience in this
analysis are recommended if this analysis is to be performed and relied upon as
evidence.
While dyes have been used for more than 55 years in gasoline, there is little
information on dyes other than in patent disclosures. Furthermore, the movement of
gasoline with dyes through the soil can result in contamination by polar compounds
that can obscure the dye bands. For example, red and orange dyes can assume a dark
brown color (Kaplan and Galperin, 1996a,b). Other challenges include (Galperin,
1997):
• The difficulty in distinguishing among dyes when several gasoline blends have co-
mingled (red and orange dyes become dark brown)
• The rapid biodegradation of the dyes in the subsurface (probably due to hydroge-
nation and subsequent destruction of the conjugated structure)
• The high solubility of the dyes
* Plate 4.2 appears at the end of the chapter.

4.8.8 OCTANE RATING
Petroleum refineries boost the octane rating or content of a gasoline via alkylation.
The alkylation process involves the heating of volatile olefins with sulfuric or
hydrofluoric acid to produce branched-chain alkanes. During the alkylation process,
the content of the major isoalkane generated is 2,2,4-trimethylpentane (TMP), which
increases relative to the content of methylcyclohexane (MCH), which is present in
crude oil and refined volatile fuels. Low-octane (87) fuels exhibit a TMP/MCH ratio
less than 2.5, while high-octane (92 or 93) gasolines have TMP/MCH ratios of 2.5
to 5.0 (Kaplan et al., 1997). If the octane rating of gasoline in a co-mingled plume
is known, these ratios may provide a means to distinguish between the gasoline
sources.
4.9 RADIOACTIVE ISOTOPE DATING
Radioactive isotopes are used to identify the origin of petroleum hydrocarbons and
chlorinated solvents and as well as for estimating contaminant transport travel times.
Isotopes (Greek isos, meaning equal, and topos, meaning place) are atoms that differ
in mass due to different numbers of neutrons in the nucleus of the atom. Most
isotopes are stable (i.e., not radioactive). Those that are radioactive emit particles and
energy from the nucleus that eventually produce a stable isotope of a different
element.
Radioactive isotope dating relies upon isotope ratios for various atoms that are
used to distinguish among elements. Isotopes for age-dating are less affected by
weathering than many chemical ratios, although isotope ratios of lighter fractions are
more heavily altered by weathering than heavier fractions. This dating technique is
based on the concept of half-life, which is the time required for half of an original
isotope mass to decay. The half-life of carbon-14 (14C), for example, is 5730 years
which means that a gram of (14C) decays to .5 g in 5730 years. Half-lives for various
radioisotopes range from less than a second to billions of years. Radioisotope units
are reported in picoCuries.
Tritium (3H) is a short-lived isotope of hydrogen with a half-life of 12.43 years.
Tritium concentrations are expressed as absolute concentrations using tritium units
(TU). One TU corresponds to 1 3H atom per 1018 atoms of hydrogen, or 3.2
picoCuries per kilogram (pCi/kg) of water (Mann et al., 1982; Taylor and Roether,
1982). Most groundwater has TU concentrations in the <1 to 10 TU range (Clark and
Fritz, 1997). These ratios, such as 13C/12C, are denoted as d13C. Isotopic results are
usually expressed in standard d-‰ fashion against the Vienna Standard Mean Ocean
Water (VSMOW) (d2H) or the Vienna PeeDee belemnite (VPDB) (d13C), according
to the following relationship for (13C) (Cane et al., 1999):
d13Csample = (Rsample/RVPDB – 1)103 ‰ VPDB (Eq. 4.3)
where R = 13C/12C.

The analytical equipment used for analyses is either gas chromatography/com-
bustion/isotope ratio mass spectrometry (GC/C/IRMS) or compound-specific isotope
analysis (CSIA). GC/C/IRMS provides rapid, cost-effective analysis with four to five
orders of magnitude more sensitivity than conventional techniques. GC/C/IRMS also
permits determination of the isotopic composition of individual compounds in com-
plex mixtures. GC/C/IRMS provides a rapid and cost-effective analysis with four to
five times orders of magnitude more sensitivity than conventional techniques. This
equipment provides the ability to perform d13C analysis on dissolved organic con-
taminants present at concentrations of parts per million to parts per billion. The
sample volumes required for this analysis range from tens to hundreds of millimeters.
For samples with dissolved contaminants, such as BTEX, a comparison of d13C
values for pure-phase BTEX compounds are identical to d13C values of the com-
pounds after pentane extraction from groundwater with dissolved BTEX (Dempster
et al., 1997). In the case of distinguishing multiple sources of crude oil that have
undergone extensive weathering and water washing, GC/C/IRMS can complement
traditional gas chromatography (GC) or gas chromatography/mass spectrometry
(GC/MS). Severe biodegradation of the crude oil can result in the loss of biomarkers
(C27 to C29) and demethylation of others (C27 to C35 hopanes) that are often used to
distinguishing among different crude oil sources. In addition, the refining process can
affect the use of biomarkers for source identification. In straight-run distillate prod-
ucts, biomarkers are affected only by the distillation temperature; while in cracked/
hydrotreated products, biomarkers can be affected by temperature, catalysts, and
hydrogen. In cases where the crude oil has lost all of its normal alkanes, isolation and
pyrolysis of the asphaltenes followed by GC/C/IRMS of the individual pyrolysis
products can be used (Mansuy et al., 1997). For refined products, the correlation of
refined products dominated by the normal alkanes in the C10 to C20 region that do not
contain biomarkers are especially conducive to GC/C/IRMS analysis and interpreta-
tion.
When examining pre- and post-1995 isotope values, realize that environmental
isotope geochemistry requires standardization between laboratories. Reporting pro-
tocols and the use of different reference standards in the analysis may therefore be
different between the pre- and post-1995 data. The current organizations providing
isotope standards are the National Institute of Standards and Technology
(Gaithersburg, MD) and the International Atomic Energy Agency (Vienna, Austria).
Since 1995, the isotope community has adopted reporting and calibration standards
proposed by the Commission on Atomic Weights and Isotopic Abundances of the
International Union of Pure and Applied Chemistry (Coplen 1996; Coplen et al.,
1983; IAEA, 1995).
4.9.1 DATING GROUNDWATER WITH ISOTOPES

The two common radioactive isotopes used for age-dating groundwater are tritium
(3H), which is an isotope of hydrogen and cesium-137 (137Cs) (Aeschbach-Hertig et
al., 1998; Clark and Fritz, 1996; Ekwurzel et al., 1994; Fritz, et al., 1991). The half-

FIGURE 4.8 Tritium chart for Ottawa, Canada, and Waco, TX.
life for cesium is 30.2 years. Tritium- and cesium-dating relies on the assumption that
the presence of tritium and cesium above background levels is the result of their
introduction from the atmospheric testing of thermonuclear devices. After 1953/54,
the amount of tritium in rainfall increased until about 1963, when it began to decline.
Secondary peaks were observed in 1973 and 1975 due to atmospheric testing by
China and France. The majority of tritium in the atmosphere has therefore been
removed. The presence of cesium in sediments was first observed in about 1954,
which is the earliest date that this technique was used. Cesium concentrations peaked
in 1963 and decreased with the exception of minor increases in 1971 and 1974
(Ritchie and McHenry, 1990). Other isotopes used for this purpose include 39Ar with
a half-life of 268 years and 14C with a half-life of 5730 years. In practice, it may be
possible to date the age of a groundwater sample relative to the 1963 tritium peak,
as shown in Figure 4.8 for Ottawa, Canada, and Waco, TX.
Age-dating groundwater is accomplished by computing the early and late ratio
of tritium according to Equation 4.4:
3 Hearly sample ¥ elDt/3Hlater sample (Eq. 4.4)
where
l = 0.0565 yr–1 (tritium decay constant).
Dt = the time between samples in years.
A ratio greater than 1 indicates that the tritium peak has been passed (later than 1963),
while a ratio less than 1 indicates that the peak has not yet arrived (earlier than 1963).

Another means for dating the age of groundwater is through the measurement of
tritium’s decay product, helium (3He). If tritium and helium concentrations are
measured, the tritium/helium age can be calculated according to Equation 4.5
(Aeschbach-Hertig et al., 1998):
tgroundwater = t1/2/ln2 ¥ ln [1 + (3He/3H)] (Eq. 4.5)
where
t = 12.3 years (half-life of tritium).
3He/3H = helium/tritium concentration ratio (tritium units).
The conversion of concentration units needed to evaluate Equation 4.5 is given by 1

cm3 STP g–1 @ 4.019 ¥ 1014 tritium units (for freshwater). This technique can be used
in conjunction with the tritium peak method as another method of verification.
Carbon-14 and tritium can also be used to date the age of methane gas (Lundegard
et al., 1999). Methane produced by the bacterial degradation of organic matter in the
1950s and 1960s contains elevated 14C concentrations greater than 100% modern
carbon (pMC). Typical landfill and sewer gases contain 14C concentrations greater
than 100 pMC, as they are typically produced from organic material less than several
decades old. The presence of elevated tritium concentrations in methane indicates
that it was produced from organic matter only several decades old. The tritium concen-
tration in methane from some landfill gases is very high (Coleman et al., 1995).
4.9.2 ISOTOPIC ANALYSIS FOR

Numerous opportunities exist to date and distinguish among multiple sources of
petroleum hydrocarbons with isotope analysis (Murphy, 1998). An advantage to
using isotope analysis for petroleum hydrocarbon fingerprinting is that asphaltene
pyrolysis results in an isotopic fingerprint similar to the original hydrocarbon (Mansuy
et al., 1977). The most widely reported include:
• Lead isotopes
• Crude oil and BTEX dating
• Age-dating gas samples
Stable carbon isotope compositions are used to distinguish among natural gas samples.
This application provides differentiation of gases from different sources and of
different ages and whether or not they are of microbial or thermogenic origin (Philip,
1988).
4.9.3 LEAD ISOTOPE ANALYSIS

A common isotope ratio used for identifying the origin of gasoline-impacted soil or
water is lead isotope analysis. Lead naturally occurs as one of five isotopes, of which

four are stable isotopes (204Pb, 206Pb, 207Pb, and 208Pb). These naturally occurring lead
isotopes are the result of the following decays: 208Pb is a decay product of thorium
(232Th); 207Pb is a decay product of uranium (235U), and 206Pb is a decay product of
uranium (238U); however, 204Pb is not a product of radioactive decay. 210Pb is a
radioactive form of lead which has a half-life of 22.6 years. 210Pb dating is used for
sediment dating during the past 100 years. The decay sequence is from natural 238Ur
(found in bedrock and soil) to radon-222 (222Rn), which decays in the atmosphere
through a series of isotopes to 210Pb, which then precipitates from the atmosphere
onto sediments.
Lead radioactive isotopes are usually reported as ratios of 206Pb/204Pb, 206Pb/207Pb,
or as a delta notation (d). Based on international standards, the isotope ratio is usually
expressed in d notation. Isotope ratios are given a negative notation if the sample
value is lower than the standard value (arbitrarily given as 0%) or as a positive value
if the sample ratio is greater than the standard value. An example of delta notation
is shown below (Hurst, 1998):
d206Pb = 1000[(206Pb/207Pb)sample – (206Pb/207Pb)standard]/

(Eq. 4.6)
(206Pb/207Pb)standard
The stable isotopes of lead occur in different ratios, depending on the geologic
formation from which they were mined. American ores, for example, have ratios of
206Pb/207Pb as high as 1.31, while Australian and Canadian ores have ratios of
approximately 1.04 and 1.06, respectively.

The most frequently used lead ratios for this purpose are 206Pb/207Pb and 206Pb/
204Pb (Hurst, 1996). High-precision lead isotope ratio analysis is used to calibrate
these changes in the lead isotope ratios as a function of time. This method is usually
based on 206Pb/207Pb ratios; when plotted as a function of time between the late 1960s
and the late 1980s as tetraethyl lead, a systematic trend is observed as a result of
manufacturers shifting their source of lead supply. Hurst et al. (1996) plotted 206Pb/
207Pb ratios between 1960 and 1990 and observed that distinct differences were
observed for different years.
4.9.4 LEAD ISOTOPE ANALYSIS FOR

GASOLINE FINGERPRINTING
The key article introducing the use of the anthropogenic (i.e., gasoline derived) lead
archeostratigraphy (ALAS) model to distinguish among multiple sources of dis-
pensed gasoline was authored by Hurst et al. in 1996. The method is predicated on
analysis of the lead isotope ratios of 206Pb/207Pb and lead concentration. This ap-
proach is based on the observation that the average stable isotope ratios of leaded
gasoline were relatively uniform over intervals of one year. From 1964 to 1990, the
206Pb/207Pb ratios in U.S. gasoline and aerosols were measured, thereby providing a
characteristic isotopic signature (Rosman et al., 1994). In addition to noting differ-

ences in the isotope ratios of the ores used for gasoline lead packages, this information

provides a standard from which to compare lead isotope ratios from environmental
samples
From 1902 to about 1968, most industrial lead emissions in the atmosphere
originated from geologically old lead ores with 206Pb/207Pb ratios between about
1.141 and 1.167 (Erel and Patterson, 1994). From 1968 to 1978, an abrupt change in
these ratios occurred because the major lead source in the U.S. shifted to younger
ores mined in Missouri which possessed anomalous high 206Pb/207Pb ratios of about
1.35. These ores constituted about 9% of the total industrial consumption in 1962 but
increased to 27% in 1968, to 57% in 1971, and to 82% by 1976. After 1984, the 206Pb/
207Pb ratios dropped to values of about 1.18 to 1.2 in 1989/90 (Sturkes and Barrie,
1987). A similar pattern reflecting the changes in the isotopic composition of lead in
Arctic snow revealed that, between 1960 and 1980, the composition of lead in
Greenland snow changed, which was consistent with the unique signature of U.S.
lead. Lead in the snow since the mid-1970s reflected a reduction in the isotopic lead
ratios which was attributed to the use of unleaded gasoline for motor vehicles in the
U.S. (Boutron et al., 1991). Lead concentrations and 206Pb/207Pb ratios in tree rings
in Croxteth, England, indicated a similar change believed to be due to vehicle
emissions (Watmough et al., 1999).
Analysis of the different lead isotope ratios with the lead concentration provides
the basis for comparing these results with the ALAS model calibration curve. This
relationship is defined as:
D206Pb = K[(206Pb/207Pb)sample – (206Pb/207Pb)standard] (Eq. 4.7)
where K is a constant. By plotting one isotope ratio against the other or a lead isotope
ratio vs. the lead concentration, alleged patterns of data arise to distinguish among
multiple sources. Other interpretations include observing a single cluster of data if
from one source, multiple clusters if from multiple sources, or mixtures if the sources
are linear to one another. It is reported that this technique allows one to establish the
time of formulation to within 1 to 5 years. Examples of the degree of resolution for
different time periods using this analysis include (Cline et al., 1991; Hurst 1998b,
1999c):
• Pre-1965
• ±1 year for 1965 to 1980
• ±1.5–2 years for 1980 to 1990, with the larger errors occurring after 1985
After 1990, when gasoline became unleaded, age estimates can only be stipulated
to be post-1990. Part-per-billion levels of lead observed in unleaded gasoline post-
1990 are assumed to be attributable to inherited lead from the crude-oil and refining
process (Hurst, 1998). In instances where 206Pb/207Pb ratios are indistinguishable, the
use of 206Pb/204Pb ratios may provide the necessary discrimination (Hurst, 1999a,b).
Unleaded gasoline can contain lead concentrations in the parts-per-billion range
which are amenable to lead isotopic testing. The concentrations detected are assumed
to be reflective of both the geologic information from which the lead was obtained

that is contained within an additive package as well as the refinery where the gasoline
was produced (Hurst et al., 1996).
This approach to date a contaminant release assumes that the lead additive
producers, Ethyl Corporation and E.I. DuPont de Nemours, used similar ore feed-
stocks for their alkyl lead additive packages. The method also assumes that the same
proportions were similar for any given year and that the sample is not reflective of
co-mingled or multiple releases of gasoline with different lead additives (Hurst
1996). Other potential challenges include whether the standard used in the ALAS
model can discriminate between industrial lead originating from unleaded gasoline
and lead from other industrial sources. For example, lead concentrations in organic
industrial sewage particles range from 500 to 1200 mg/kg (dry weight) for lead
introduced into sediments in addition to lead originating from automobile exhaust
and are used as standards for dating a gasoline release (Patterson et al., 1976). The
analytical techniques employed should be carefully examined to determine whether
natural vs. industrial lead that is indicative of leaded gasoline is discriminated and
that no lead artifacts have been introduced.
The stable isotope ratio of sulfur can identify source relationships between
samples contaminated with heavy hydrocarbons. This information can be combined
with other geochemical evidence to differentiate between hydrocarbon plumes and
to identify where the plumes co-mingle in the soil and/or ground
An interesting application of lead isotope ratios is a case in Benicia, CA, where
about 40 horses died from chronic lead poisoning over a 20-year period (Rabinowitz
and Wetherwill, 1972). Potential lead sources were a lead smelter, particles from
exhaust from leaded gasoline, sandblasting of a lead-painted bridge across Carquiez
Straight, and sandblasting of ships. Refineries in the area were believed to emit lead
as a tetraethyl vapor. Lead ratios of 206/204Pb and 206/207Pb were used to evaluate the
contribution of these sources, along with information such as the distance of these
sources from the pasture land used by the horses for grazing and wind direction.
The lead content of the horses’ kidneys and livers revealed concentrations of 9
to 16 mg/g on a fresh weight basis. The isotopic composition of the lead from the
horseflesh did not coincide with the lead associated with the pasture grasses. Plotting
of the 206/204Pb and 206/207Pb ratios for the various samples showed three distinct
isotopic groupings: lead from gasoline, lead from the smelter and pasture grass, and
the lead isotopic composition of the horse organs. Based on the isotopic ratios, it was
concluded that the horses were poisoned from chronic lead poisoning from equal
parts of smelter and gasoline lead.
4.9.5 ISOTOPE ANALYSIS OF CRUDE OIL AND BTEX

Isotopic analysis has been used for both crude oil and for the aromatic compounds
(BTEX) as a means to identify the origin of the petroleum hydrocarbon. Carbon and
hydrogen isotopes are most commonly used for this purpose. The low 13C values of
fuels and chlorinated solvents manufactured from fossil fuels can differ with the
dissolved inorganic carbon in natural groundwaters. The d13C of the dissolved

organic and inorganic carbon may thereby provide a basis of contrast in areas
impacted by chemicals produced from fossil fuels.
On a global scale, isotopic analyses of carbon and hydrogen are used to distin-
guish among crude oils produced from different oil reservoirs in the world. If one
assumes that each refinery processes crude oil from a particular geographic area or
oil basin for an extended period of time, the isotope ratios for the corresponding
refined product are expected to be similar to that found in the crude oil. This approach
is compromised if refined products from different crude oil stocks are blended at the
refinery; small changes in the carbon isotope ratios of refined fuels can also result
during the production of very light gases which tends to concentrate heavy isotopes
in the product (Kaplan and Galperin, 1996).
Another opportunity for distinguishing between different sources of a refined
product or crude oil is to examine differences in sulfur isotopes (32S, 33S, 34S, and 36S).
The 32S and 34S isotopes are the most commonly used for this purpose. This ratio
analysis in conjunction with a peak-to-peak polynuclear aromatic (PNA) analysis, for
example, could provide the basis for clearly distinguishing between different crude
or refined products.
Isotopic analysis of the BTEX compounds presents a promising opportunity for
identifying discrete releases of gasoline from multiple sources. These approaches
assume that hydrocarbons enter the subsurface with a distinct isotopic composition,
or 13C/12C ratio, that is characteristic of their source. If this isotopic composition is
conserved, stable carbon isotopic analysis can be used to identify different sources
as well as natural background sources of hydrocarbons.
The use of pentane to extract the sample and subsequent analysis of the d13C via
GC/C/IRMS has been reported as a means to use isotopic analysis for BTEX in
groundwater (Dempster et al., 1997). The authors discovered that the isotope ratios
of d13C do not change as a function of the concentration of the BTEX in dissolved
or free product samples. GC/C/IRMS analysis of pure phase BTEX indicated that
different manufacturers produce chemical with distinct d13C compositions, probably
attributable to different raw products and manufacturing processes for a discrete time
interval. Cross-plots of deuterium and hydrogen ratios may similarly provide a means
to distinguish among multiple BTEX sources. This technique may also be used to
distinguish among different sources as function of the enriched d13C values of the
BTEX compounds in a co-mingled gasoline plume.
A case study of a site with groundwater contamination located at the Naval
Construction Battalion Center, Port Hueneme, CA, illustrates the merit of acquiring
multiple groups of independent forensic evidence to discriminate among sources
(Kelley et al., 1997). In this case, these lines of evidence included:
• The stable isotope ratio of 13C/12C reported as d13C

• A comparison of degradation patterns of BTEX compounds
• The presence or absence of MTBE in the groundwater samples
A full BTEX suite was analyzed before each set of isotope samples. d13C analysis was
performed on groundwater samples with BTEX concentrations greater than about

200 ppb. The d13C values were determined using a GC/C/IRMS system. Samples
were analyzed in either duplicate or triplicate, resulting in four to six isotope numbers
for each reported BTEX data point. Standard deviations were less than 0.5%. In some
wells, a heavier d13C value was observed, indicating another BTEX source or a higher
degradation rate and subsequent isotopic fractionation. It is expected that with
normal isotopic fractionation, molecules with the lighter isotope (12C) react at a
slightly faster rate, resulting in the enrichment of the residual molecules (i.e., 13C).
Given the observation that a consistent degradation pattern was not observed in all
of the compounds to account for the heavier d13C values, the d13C results indicated
the potential for multiple sources of gasoline.
The second group of evidence was the apparent difference between the ratio of
BTEX compounds in samples for groundwater samples collected from different
monitoring wells. Changes in the BTEX data through time revealed little change in
concentrations. Given that toluene is the easiest BTEX compound to degrade, fol-
lowed by xylene, benzene, and ethylbenzene, the presence of this degradation pattern
was investigated. Among the individual BTEX compounds, toluene generally had the
highest concentration, followed by benzene, para- and meta-xylene, ortho-xylene,
and ethylbenzene. One well, however, revealed a BTEX pattern with the para- and
meta-xylenes having the highest concentrations followed by benzene, toluene,
ethylbenzene, and ortho-xylene. Assuming that similar degradation environments
existed for the site, the difference in degradation patterns suggested the potential for
multiple sources.
Methyl-tertiary-butyl-ether analysis of groundwater samples when compared
with samples with heavy d13C values indicated a second source of gasoline. The
MTBE data also indicated the release of a leaded and unleaded fuel. These three
groups of evidence were therefore corroborative and indicated a source of leaded and
unleaded gasoline contamination from two sources. Another option is the use of
206Pb/207Pb as a potential tracer of MTBE sources. Studies in New Jersey and
California indicate that shifts in 206Pb/207Pb ratios in groundwater occur with the entry
of MTBE into the groundwater (Hurst, 1999a). This approach assumes that MTBE
acts as a carrier of lead into the groundwater (Hurst, 1999b)
When reviewing d13C values for BTEX compounds used to identify discrete
source areas, examine the overall pattern of isotopic variation (e.g., individual BTEX
plots) to ascertain if a clear pattern emerges among samples. A particular manufac-
turer, for example, may not have a single characteristic d13C signature for benzene
throughout a given time period. Compound-specific isotope analysis for all of the
BTEX compounds may therefore provide a quantifiable means to distinguish among
multiple sources (Dempster et al., 1997).
4.9.6 ISOTOPE ANALYSIS OF GAS SAMPLES

Isotopic analysis of gas samples (carbon 13C/12C and deuterium hydrogen 2H/1H) can
be used to discriminate between landfill and non-landfill gas sources (Baedecker and
Back, 1979; Games and Hayes, 1974, 1977). The former technique is based on the

TABLE 4.20
Differences in Landfill and Non-Landfill d13C
Compound Landfill d13C Non-Landfill d13C
Methane (CH4) –42 to –61‰ –60 to –95‰

Carbon dioxide (CO2) –7 to +18‰ –47 to –63‰
differences in 13C concentrations in carbon dioxide (CO2) and methane (CH4).

Reported differences in landfill and non-landfill methane and carbon dioxide in units
of permills (‰) are shown in Table 4.20 (Hackley et al., 1996; Hoefs, 1997).
While the presence of methane (CH4) in groundwater is not conclusive that
landfill leachate has entered the groundwater, the d13C in the dissolved inorganic
carbon can provide additional evidence, as 13C and 2H in the CH4 are indicators of
biogenic methane. Landfills with robust methane production often have co-existing
carbon dioxide (CO2) or dissolved inorganic carbon that is enriched in 13C due to
methanogenesis (Clark and Fritz, 1997). d13C values for carbon dioxide as low as –
25‰ have been reported for some landfills; these results are believed to be due to
either bacterial preference for light methane (12CH4) or maturity of the landfill from
which the sample was collected. Isotopic analysis of deuterium (2H) in landfill
leachates can be combined with isotopic analysis of landfill gases to identify the
source of both the leachates and gases. Values of d2H have been observed to be
enriched 30 to 60% as compared to local precipitation. For example, by plotting the
differences in d2H vs. d13C for methane, for either gases or leachates, clustering of
the data relative to different sources may become apparent (Murphy and Katz, 1998).
The origin of nitrogen and sulfur species associated with groundwater contaminated
by landfill leachates can be identified by using d2N, d34S, and d18O. The presence of
high concentrations of tritium in groundwater may provide another opportunity to
confirm the introduction of landfill leachates into an aquifer. In landfills in Illinois,
tritium concentrations in landfill leachates were measured at up to 8000 tritium units
which were believed to have originated from tritium leaching from luminescent
paints containing titrated hydrocarbons (Clark and Fritz, 1997).
Sources of methane other than from gasoline degradation include underlying
sediments and or decaying organic matter (biogenic) as distinguished from ther-
mogenic (e.g., from natural gas pipeline) gases. Plotting the stable isotope ratios of
carbon and deuterium hydrogen can provide a means to differentiate between bio-
genic and thermogenic gases. Carbon-14 concentration analysis, for example, is used
to distinguish between methane associated with spilled gasoline from that associated
with other sources (Lundegard et al., 1998). The stable carbon isotope ratios of
biogenic vs. thermogenic gases range from –45 to –100 and –15 to 50 permills,
respectively. Deuterium hydrogen ranges for biogenic and thermogenic gases range
from –150 to –350 and 90 to 400 permills, respectively (Schoell, 1998; Whiticar et
al., 1986).

An example of the application of the isotopic analysis of methane gas in
groundwater for source identification was performed at the Beare Road landfill in
Toronto, Canada. Isotope analysis was used to isolate sources of methane detected
in the shallow groundwater under the landfill (Descrocher and Lollar, 1998). It was
argued that the results of the isotopic analysis indicated that transport of leachates
from the landfill to the deeper groundwater did not occur. The carbon isotopic
analysis of the dissolved and gas phase methane concluded that it originated from
naturally occurring microbial methanogenesis in the native formation rather than
from the landfill.
In another example of isotopic analysis, the source and movement of carbon
dioxide in soil gas directly above an aquifer contaminated with organic solvents from
a disposal site in southeast Phoenix, AZ, were used as indicators of in situ biodeg-
radation of organic solvents in the subsurface (Suchomel et al., 1990). The carbon
dioxide concentrations in the contaminated soil significantly exceeded the concentra-
tions in uncontaminated areas and correlated with the volatile organic compound
concentrations measured in soil cores collected in contaminated areas. The d13C
values were also indicative of contamination and in situ aerobic biodegradation of the
chlorinated solvents (TCE, DCE isomers, and 1,1,1-TCA).
In the investigation of sites located at Hill Air Force Base in Utah, the Patuxent
River Naval Air Station in Maryland, and Tyndall Air Force Base in Florida, carbon
dioxide concentrations and stable carbon isotope ratios in soil gas provided a basis
for identifying the contaminant source (Aggarwal et al., 1991). Both the carbon
dioxide concentrations and d13C values were used to discriminate between areas of
contamination. Carbon dioxide concentrations in soil gas in uncontaminated and
contaminated areas ranged from 0.2 to 2.2% and 0.6 to 13%, respectively. Average
d13C values as parts per thousand for uncontaminated vs. contaminated locations at
each site were as follows: Hill Air Force Base, 23.6 vs. 28.4; Patuxent River Naval
Air Station, 24.5 vs. 28.4; and Tyndall Air Force Base, 18.4 vs. 23.3.
In addition to developing an isotopic line of evidence, the content of higher
molecular weight hydrocarbon gases (e.g., ethane, propane, butane, and pentane)
relative to methane can be used (Lundegard et al., 1999). Biogenic gases consist
predominately of methane and carbon dioxide and do not typically contain signifi-
cant concentrations of C2 to C5 hydrocarbons (C1/[C1 – C5] > 0.98) (Rice and
Claypool, 1981). Natural gas from pipelines, in contrast, contain significant concen-
trations of C2 to C5 hydrocarbons (C1/[C1 – C5] = 0.6 to 1.0).
4.9.7 ISOTOPIC ANALYSIS OF CHLORINATED SOLVENTS

The use of isotopes to differentiate manufacturers of chlorinated solvents has been
proposed as a means to distinguish sources contributing to a co-mingled groundwater
plume. Fractionation of 37Cl occurs during the manufacturing of chlorinated solvents
(Tanaka and Rye, 1991). A significant difference in the d13C and d37C values is
apparent for a single compound, suggesting variations in the manufacturing process.

FIGURE 4.9 d37Cl vs. d13C of PCE, TCE, and TCA from four different chlorinated solvent
manufacturers. (From Van Warnerdam, E. et al., Applied Geochemistry, 10, 550, 1995. With
permission.)
The low abundance of 37Cl isotope fraction in organic solvents is bound

more tightly to carbon than are 35Cl atoms (Bartholomew et al., 1954). The differ-
ence in bond strength results in chlorine isotope fractionation due to temperature
and pressure differences during the manufacturing of the chlorinated solvents
(Tanaka and Rye, 1991). In one case, the isotopic ratios for 13C/12C and 37Cl/35Cl
were used to distinguish among three chlorinated solvent manufacturers. The
three chlorinated solvents were PCE, TCE, and 1,1,1-TCA, as shown in Figure 4.9,
with the 13C percentage in Standard Mean Ocean Chloride (SMOC) and the 37Cl in
the international standard of PeeDee belemnite (PDB) (Van Warnerdam et al.,
1995).
In a similar application, 13C and 37Cl were used to discriminate between two
different pure phase chlorinated solvent batches obtained from various manufactur-
ers using GC/C/IRMS (Beneteau et al., 1996). Data interpretation may also be biased
due to the potential for isotopic fractionation in the subsurface and the precision of
the GC/C/IRMS measurements (Stout et al., 1998c). The use of this method as
evidence in litigation requires that a pure free phase product is available for extrac-
tion and testing. The cost of extracting a pure product of the solvent from the
environmental sample and concerns about the validity of the subsequent test results
should be carefully considered. Additional difficulties in the use of this technique in
litigation include being able to find a laboratory that can perform the analysis and
identifying an witness who is expert in this area of expertise (K. Beneteau, personal
communication, 1999).

An indirect technique for identifying the distribution and contaminant transport
rate is to use a radioactive isotope as an indicator of the transport of a non-isotope
contaminant. One example is the use of tritium measurements combined with
contaminant transport calculations specific to liquid transport in fractures such as
joints or slickensides. For example, based upon transport calculations through a
fractured Gulf Coast clay, in addition to the contaminant transport results, it was
argued that a dense non-aqueous phase liquid (DNAPL) had not moved through the
fracture system and into the groundwater. Samples were collected throughout the
several hundred feet of overburden, and the presence or absence of tritium in water
within the fractured clay was used to demarcate the vertical extent of the tritium.
The tritium values were then argued to be consistent with the slow movement of
infiltrating water through the clay which would preclude the movement of a DNAPL
that was released subsequent to 1954 into the underlying aquifer.
The effects of volatilization on the isotopic composition of TCE for free product
and as a dissolved solution at different concentrations were studied (Slater et al.,
1998). The stable carbon isotope concentrations were examined and indicated that,
while volatilization and dissolution of the TCE did not result in isotopic fractionat-
ing, fractionating occurred due to abiotic dechlorination.
4.10 CHEMICAL AND BIOLOGICAL

DEGRADATION MODELS:
The degradation of specific petroleum fractions in a fuel has been proposed as a

means to age-date a hydrocarbon (Faggan et al., 1975). Forensic techniques used to
date the age of a petroleum hydrocarbon release include the degree of weathering,
half-lives, pristane and phytane ratios, and BTEX ratios.
4.10.1 WEATHERING AND BIOMARKERS

Weathering of a petroleum hydrocarbon includes processes such as evaporation,
water washing, adsorption and/or sequestration, chemical precipitation, biodegrada-
tion, and advective transport. One advantage of the examination of weathering
patterns is that it may provide a basis to (1) associate products or fuels from a similar
origin, and (2) to provide a qualitative basis for age-dating.
The presence of gaseous hydrocarbons, isobutane, n-butane, isopentane, and n-
pentane in a sample contaminated with gasoline, for example, is used to determine
whether a gasoline released into the subsurface is “fresh” or “weathered”. Fresh
gasoline normally contains n-hexane and n-heptane in higher concentrations than
methylcyclohexane (MCH) and n-octane. After the gasoline weathers in the subsur-
face, the MCH concentration increases relative to n-hexane and n-heptane and
carbon-7 (C7) normal paraffins. It is common to plot chromatograms showing the
different hydrocarbons and weathering correlations on a base map. Testimony is then

offered regarding chromatograms representing “fresh” vs. “weathered” crude or
refined product. The difficulty with this analysis and testimony is that the terms
“fresh” and “weathered” are relative terms that allow a wide range of interpretations
by forensic geochemists.
“Biomarkers” are commonly introduced as evidence to distinguish among sources
of a petroleum hydrocarbon. Biomarkers are complex markers that are resistant to
weathering and biodegradation. Biomarkers have been defined as “organic com-
pounds present in oils and source rocks having carbon skeletons related to their
functionalized precursors which occur in the original source material” (Philip, 1998).
As a result, they are used to determine the source of a petroleum hydrocarbon even
if it has been present in the environment for a significant period of time. Most crude
oil and Bunker C fuel, for example, contain biomarkers such as terpanes and steranes
which are highly resistant to biodegradation (Walker et al., 1976). Terpanes and
steranes are high-molecular-weight hydrocarbons originating from the polycyclic
lips present in plants and bacteria. Because of their particular structure, these biomarkers
represent a large number of different chemical compounds as well as a set of isomers
of the same compound (Kaplan et al., 1995). Because of their stability, they are useful
in comparing fuel patterns between samples.
Specific biomarkers used to identify the source of a release include the following:
C2-dibenzothiophenes/C2-phenanthrenes; C3-dibenzothiophene/C3-chrysene; C29-a,b-
pentacyclic hopanes/C30-a,b-pentacyclic hopanes; C23-tricyclic hopane/C24-tricyclic
hopane; and 4-methyldibenzothiophene/2-/3-methyldibenzothiphenes ratios (Dou-
glas et al., 1996; Wang et al., 1994; Wang and Fingas 1995). The C30-pentacyclic
terpane (hopane) and certain tricyclic terpanes are among the most stable biomarkers
in crude oil (Peters and Moldowan, 1993). Of the tetracyclic steranes, the diasteranes
are the most stable. In environmental litigation, pentacyclic triterpanes (C27 to C35)
and steranes (C27 to C30) are used, although they are relegated to use for distinguish-
ing between crude oil or heavy distillate fuels due to their high molecular weight
(Stout et al., 1999). For middle distillate fuels, biomarkers using GC/MS-selected ion
monitoring techniques can be used to distinguish among different fuels. Biomarkers
that can be identified using this technique include bicyclic sesquiterpanes (C14 to
C16), acyclic regular isoprenoids (C13 to C25), tricyclic diterpanes (C17 to C20), aro-
matic diterpenoids (C18 to C20), tricyclic terpanes (C19 to C25), and various polycyclic
aromatic hydrocarbons (PAHs) such as naphthalenes and phenanthrenes (Stout et al.,
1999a). Dibenzothiophenes are associated with the sulfur content of the fuel and can
vary significantly between sources.
Crude oil and most mid-range distillates such as coal-derived liquids, coke
production plants, creosote, and manufactured gas plant residues contain an abundant
number of PAHs. Manufactured gas plant residues containing PAHs include lampblack,
tar, and spent oxides (usually composed of sulfur, cyanide, and ammonia compounds
bound with iron). The presence or absence of a PAH may, therefore, provide an
indication of a distillation or pyrogenic process unique to the material as well as a
means to distinguish among residue materials containing the PAHs (coal tar, lampblack,
etc.). One analysis of PAHs, for example, provided the basis for distinguishing

TABLE 4.21
Polyaromatic Hydrocarbons Used To Identify Multiple Sources
Acenaphthenea Dibenzo(a,h)anthraceneb
Acenaphtylene a Dibenzofuran
Benzo(a)anthraceneb Dibenzothiophene
Benzo(a)pyreneb C1-dibenzothiophene
Benzo(b)fluorantheneb C2-dibenzothiophene
Benzo(b)thiophenes C3-dibenzothiophene
C2-benzo(b)thiophenes C4-dibenzothiophene
C3-benzo(b)thiophenes Fluoranthenea and pyrenea
C4-benzo(b)thiophenes C1-fluoranthenes/pyrenes
Benzo(e)pyrene C2-fluoranthenes/pyrenes
Benzo(g,h,i)perylenea C3-fluoranthenes/pyrenes
Benzo(k)fluorantheneb C4-fluoranthenes/pyrenes
Biphenyl Fluorenesa
Chrysenesb C1-fluorenes
C1-chrysenes C2-fluorenes
C2-chrysenes C3-fluorenes
C3-chrysenes Indeno(1,2,3-c,d)pyreneb
C4-chrysenes Perylene
Decalins Phenanthrenesa and anthracenesa
C1-decalins C1-phenathrenes/anthracenes
a Non-carcinogenic compound.
b Carcinogenic compound.
Adapted from Stout, S. et al., Soil and Groundwater Cleanup, October, 1998, p. 25.
With permission.
between PAH contamination that originated from manufactured gas plants and
atmospheric deposition that was released into the atmosphere by various pyrolysis
sources (Haeseler et al., 1999).
In order to examine differences in PAHs from a number of possible sources, an
extended list of PAHs is required, beyond the standard EPA Priority List that
contains 16 PAH compounds or only carcinogenic PAHs (i.e., benzo(a)anthracene,
benzo(a)pyrene, benzo(b)fluoranthene, benzo(k)fluoranthene, chrysene, dibenzo(a,h)
anthracene, and indeno(1,2,3-c,d)pyrene) (Haeseler et al., 1999). A recommended
list of PAHs that can be used to identify different types of hydrocarbons are summa-
rized in Table 4.21 (Stout et al., 1998b). These results can be plotted and compared.
Figure 4.10 shows bar charts of the concentrations of PAHs in crude oil, gasoline,
Bunker C, and creosote samples (Stout et al., 1998b).

FIGURE 4.10 Polyaromatic hydrocarbons (PAHs) associated with four petroleum hydrocar-
bons. (From Stout, S. et al., Soil and Groundwater Cleanup, October, 1998, p. 26. With
permission.)
Because polyaromatic hydrocarbons are some of the compounds least affected by

weathering, selected PAHs may be identified from the type of analysis shown in
Figure 4.10 and used as target compounds for further delineation between hydrocar-
bons. For example, phenanthrene and dibenzothiophene isomers may be altered in a
manner that provides a relative basis to compare weathering rates between samples.

TABLE 4.22
Polycyclic Aromatic Hydrocarbon Ratios in a Diesel No. 2
C4-Alkylbenzenes/ C1-Naphthalenes/
Sample C2-Phenanthrenes C2-Phenanthrenes
New diesel (gw)a 1.6 4.3

Degraded diesel (gw) 1.2 3.4
Severely degraded diesel (gw) 1.0 2.2
Degraded diesel (soil) 1.7 3.2
Severely degraded diesel (soil) 0.3 1.7
a gw = groundwater.
Examples include C4-alkylbenzenes/C2-phenanthrenes and C1-naphthalenes/C2-

phenanthrenes, which can be useful in determining alteration changes in free phase
diesel floating on groundwater and in soil (Kaplan et al., 1995). Table 4.22 lists
selected PAH ratios for a diesel No. 2 present as free phase product floating on the
groundwater and present in soil (Kaplan et al., 1995).
Polycyclic aromatic hydrocarbons can be analyzed from tissue samples of crus-
taceans and bivalves to identify the origin of the oil in the tissue sample (Douglas,
1988). Organisms conducive to this type of testing include bivalves and crustaceans;
fish are generally not well suited unless they have been exposed to extremely high
dosages. Birds and mammals are least suited due to the metabolism of many poly-
cyclic aromatic hydrocarbons by the animals. The procedure for this analysis in-
cludes collection of the tissue sample and extraction of the tissue with CH2Cl2 and
Na2SO4 using a tissumizer. The extractant is then passed through an alumina clean-
up column, followed by gel permeation high-pressure liquid chromatography (HPLC)
with an optional silica gel HPLC, and finally analysis via gas chromatograph/mass
spectrometry/selected ion monitoring (GC/MS/SIM).
4.10.2 BIODEGRADATION MODELS

A popular petroleum degradation model is based on the biodegradation half-life of
hydrocarbon compounds in the soil or groundwater, the estimated half-life being the
time required for one half of the compound to biodegrade. The two approaches most
often encountered are the modeled half-life BTEX concentrations in support of a
release date or the use of published half-life values. Table 4.23 summarizes biodeg-
radation rates of selected BTEX and PAH compounds (API, 1994; Raymond et al.,
1976; Walker et al., 1976).
Numerous models exist for calculating the degradation rate of BTEX and other
compounds. Assumptions routinely used in first-order biodegradation models for
BTEX include the following (Odermatt, 1999):

TABLE 4.23
Biodegradation Rates of BTEX and PAH Compounds
Biodegradation Half-Life (hr)a
Compound Soil Groundwater
Acenaphthene (C12H10) 299–2448 590–4896

Anthracene (C14H10) 1200–11,040 2400–22,080
Benzene (C6H6) 120–384 240–17,280
Benzo(a)pyrene (C20H12) 1368–12,720 2736–25,440
Chrysene (C18H12) 8904–24,000 17,808–48,000
Ethylbenzene (C6H5C2H5) 72–240 144–5472
Fluoranthene (C10H10) 3360–10,560 6720–21,120
Fluorene (C13H10) 768–1440 1536–2880
Naphthalene (C10H8) 398–1152 24–6192
Phenanthrene (C14H10) 384–4800 768–9600
Pyrene (C16H10) 5040–45,600 10,080–91,200
Toluene (C6H5CH3) 96–528 168–672
o-, m-, p-Xylene (C6H4(CH3)2 168–672 336–8640
a Measured at 25∞C.
• The degradation rate is uniform in time and space.

• First-order degradation rates do not depend on the status of the in situ microbial
population.
• Contaminant loading rates and the toxic effects of contaminants are ignored (e.g.,
first-order degradation rates may only be valid over a portion of a concentration
range).
• The first-order biodegradation process is instantaneous and 100% effective, regard-
less of location in the soil or aquifer.
Given these assumptions, techniques have been proposed to estimate the transforma-
tion rate of a chemical downgradient of a source and for estimating the date of a
release. An example of a method to estimate the degradation rate (l) of a compound
in a one-dimensional idealization is described in Equation 4.8 (Brown et al., 1997;
Buscheck and Alcantar, 1995; Westervelt et al., 1997).
l = vc/4ax([1 + 2ax(k/vx)]2 – 1) (Eq. 4.8)
where
l = degradation rate.
vc = contaminant velocity along the x-axis adjusted for retardation).
ax = longitudinal dispersivity.
k = attenuation rate.
vx = groundwater linear velocity.

The term (k/vx) is the slope of the regression line fit to the log contaminant
concentration data as a function of distance along the centerline of the contaminant
plume (McNab and Dooher, 1998). The difficulty in relying on this inverse solution
relationship is that dispersive processes can produce concentration distributions that
decline with distance from a continuous source. In many instances, especially when
analyzing a small number of data points, it is often possible to fit a straight line
through log concentration vs. distance data with a high degree of correlation even
when degradation is insignificant or absent. A linear trend in log concentration values
as a function of distance from the contaminant source does not constitute proof of the
existence of transformation processes. Other factors that can introduce bias into this
approach include (McNab and Dooher, 1998):
• An assumption that steady-state conditions exist

• Fluctuations in source strength with time
• Non-Fickian dispersion of solutes
• Strongly heterogeneous flow and transport
• Well locations not aligned with the contaminant plume centerline
• Dilution effects due to well-screen length
• Sampling and analytical bias
• Non-uniform degradation rate distribution
Many of these factors are universal to inverse or reverse types of modeling due in part
to the non-uniqueness of the problem and mathematical instabilities resulting from
small variations in the input data; therefore, it is possible to derive misleading
degradation rates in support of reverse modeling or contaminant source identification
models. The use of sensitivity analysis can be performed through Monte Carlo
simulations using a range of physical parameter values and biodegradation rates to
generate a large number of simulations for the purpose of producing confidence
levels for the various input parameters.
Realize that the use of first-order reaction rates to describe hydrocarbon biodeg-
radation may not be universally appropriate. In a study of 1029 leaking underground
storage tank sites in California, the applicability of first-order degradation rates was
concluded to be appropriate in about 625 instances, due primarily to the observation
that these degradation rates were valid for only a portion of the BTEX concentration
range. In general, the authors recommended questioning first-order approximations
if the maximum concentration of benzene is ≥1 ppm or if the total BTEX is >5 ppm
(Bekins et al., 1998; McNab and Dooher, 1999).
4.10.3 PRISTANE/PHYTANE RATIOS

Pristane and phytane are isoparaffins known as isoprenoids. They are present to the
right of C17 and C18 peaks on chromatograms of crude oils, middle distillates, and
lubricating oils. In fresh crude, middle distillates, or lubricating oils, the n-paraffin
C17 and C18 peaks are more prominent than the pristane and phytane peaks. As the

petroleum hydrocarbon is biodegraded, the bacteria preferentially consume the C17
and C18 which results in the pristane and phytane peaks becoming more pronounced
on the chromatogram. Examination of the C17/pristane and C18/phytane ratios is
therefore argued as a qualitative basis for determining the degree of degradation and,
hence, weathering (Kaplan and Galperin, 1996). A linear relationship extending for
about 20 years is approximated by Equation 4.9 (Kaplan et al., 1995, 1997):
T (yr) = –8.4[n – C17/Pr] + 19.8 (Eq. 4.9)
where an average initial value for the [n – C17/Pr] ratio is about 2.3 for a No. 2 diesel
fuel.
The genesis of the pristane/phytane approach is described in an article by
Christensen and Larsen (1993), who evaluated changes in the composition of diesel
No. 2 as a function of time in Denmark and the Netherlands. The authors analyzed
11 diesels from five different oil companies and concluded that the average C17/
pristane ratios was 1.98 (2.0) with a standard deviation of 0.83. The authors con-
cluded that an analysis of the C17/pristane ratios provided a means to estimate the
length of time that the diesel had been in the environment. The ratios for 26 refined
and “fresh” distillates and motor oils from the U.S. were also examined; these C17/
pristane ratios were found to be 1.95 (2.0) with a standard deviation of 0.29. As a rule
of thumb, a C17/pristane ratio of a fresh diesel is >2.0.
Because crude oil is the parent of refined products, the C17/ pristane ratios of 2509
crude oils from ten states in the U.S. and crude oils from Mexico and Canada were
examined; the ratio for these crude oils was 2.1. Crude oils from 14 countries
representing 1420 crude oils were also examined and resulted in a C17/pristane ratio
of 2.0. Fresh refined products were found to have a C17/pristane ratio of between 1.8
and 2.2. The C17/pristane ratios of refined distillate products in the U.S. are shown
in Table 4.24. These ratios have also been promoted as a means to evaluate the
relative weathering and, hence, age of hydrocarbons. The C17/pristane and C18/
phytane ratios of a diesel No. 2 and Bunker C soil extract are summarized on Table
4.25 to illustrate this approach.
4.10.4 BTEX RATIOS

Benzene, toluene, xylene, and ethylbenzene (BTEX) ratios in groundwater have been
proposed and used as a qualitative indicator of the time that the product has been in
the subsurface and, therefore, to date the age of a release (Kaplan et al., 1997; Luhrs
and Pyott 1992; Odermatt, 1994). These results can be combined graphically with the
results of a pristane/phytane analysis. These methods are based on the sequence of
BTEX volatilization and biodegradation. The sequence of BTEX loss in groundwater
begins with benzene because it diffuses most rapidly out of free phase gasoline and
partitions into groundwater followed by toluene, ethylbenzene, and xylene. The
reverse sequence often occurs with BTEX in soils; toluene, ethylbenzene, and
xylenes are preferentially retained by soil relative to benzene, and ethylbenzene and

TABLE 4.24
C17/Pristane Ratios of Refined Products in the U.S.
Geographic Location Product C17/Pristane Ratio
West Texas Diesel 2.1

Minnesota Diesel 1.9
Tennessee Kerosene 2.0
Colorado Diesel 2.5
New York Diesel 2.6
New England Diesel 1.9
Western U.S. (Chevron) Diesel 1.6
Western U.S. (Amoco) Diesel (summer) 1.4
Jet-A fuel 1.8
Refinery tank (diesel) 1.7
Reduced oil 1.6
Kerosene 1.8
Heating oil 1.8
Diesel No. 1 1.9
Diesel No. 2 1.5
Gas oil 1.8
Residual oil 2.2
Fuel oil 2.2
Heavy fuel oil 2.2
Oklahoma Diesel 2.2
Indiana Motor oil (30W) 1.9
Diesel 1.8
Kerosene 2.1
Jet-A fuel 2.1
Middle distillate 2.0
Cracked distillate 1.9
Average 2.0
From Schmidt, G., in International Business Conference Environmental

Forensics: Determining Liability through Applied Science, September 24–
25, International Business Communications, Southborough, MA, 1998, p.
13. With permission.)
xylenes are also more resistant to degradation than benzene or toluene. Chemists
reviewing hydrocarbon chromatograms often observe that ortho-xylene is removed
first in hydrocarbon-contaminated soils, followed by ethylbenzene, toluene, meta-
and para-xylene, and finally benzene. BTEX degradation at each site is therefore
unique due to different biological populations and original composition of the BTEX
compounds in the gasoline.
Calculating ratios between these four compounds is used in environmental cases
to identify the relative age of a hydrocarbon release. Because the relative content of
BTEX compounds in gasoline has changed, initial BTEX ratio values are rarely

TABLE 4.25
C17/Pristane and C18/Phytane Ratios of a Diesel No. 2 and Bunker C
Sample C17/Pristane Ratio C18/Phytane Ratio
New diesel No. 2a 2.6 3.6

Degraded diesel No. 2a 1.2 1.4
Severely degraded diesel No. 2a 0 0
Degraded diesel No. 2 (soil) 1.1 0.8
Severely degraded diesel No. 2 (soil) 0 0
New Bunker C (soil) 2.2 2.6
Degraded Bunker C (soil) 1.6 2.0
Severely degraded Bunker C (soil) 0 0
a Free-floating diesel No. 2 on groundwater.
Adapted from Kaplan, I. et al., Pattern of Chemical Changes in Fugitive Hydrocarbon Fuels in
the Environment, SPE 29754, Society of Petroleum Engineers, Houston TX, 1995, p. 601. With
permission.)
available, thereby limiting the value of the technique to estimate the timing of a
release. One method proposed to smooth out the variations in the composition of
manufactured gasoline and to accommodate processes that preferentially remove
benezene from the groundwater is to use a cumulative (B + T)/(E + X) ratio (Kaplan,
et al., 1996).
The cumulative BTEX ratio is defined as Rb = (B + T)/(E + X) and is assumed
to decrease exponentially with the time since a spill occurred (t) according to
Equation 4.10 (Kaplan et al., 1995, 1997; Montgomery, 1991):
Rb = 6.0 exp(–0.308t) (Eq. 4.10)
Given that this empirical relationship is only valid for initial (B + T)/(E + X) ratios
of 6.0, it may only represent a small percentage of gasoline formulations. BTEX
partitioning studies indicate that immediately after a spill, Rb values range from 1.5
to 6, depending on the amount of gasoline in contact with groundwater. If this ratio
falls to between 1.5 and 6.0, the spill probably occurred within the last 1 to 5 years
(Kaplan and Galperin, 1997). The ratio of benzene plus toluene to ethylbenzene plus
xylenes decreases with time as a result of the higher solubility of the benzene and
toluene to water. This ratio decreases as a function of time, with values below 0.5
indicative of a gasoline residence longer than 10 years.
The accuracy of this technique may be improved by using a best-fit regression
line from historical site data collected over an extended time interval. An exponential
approximation of changes in Rb is also reasonable for a dissolved hydrocarbon plume
near a floating gasoline layer. An exponential regression function assumes that the
Rb decreases with time near the source of a sudden gasoline release. An example of
an exponential approximation of the BTEX-monitored data from an actual case study

FIGURE 4.11 BTEX ratio curve used for dating a gasoline where Rb = 6 exp(–0.308T).
reported by Galperin 1997 is shown in Figure 4.11. The high Rb value at the time of
the initial measurement is indicative of free phase gasoline that occurred approxi-
mately 4 years prior to the initial measurement. The extrapolation curve shows that at
the time of the gasoline release, Rb = 6, confirming the presence of a thick free-product
layer, while a twofold decrease in Rb occurred in about 2.3 years (Kaplan et al., 1997).
A technique used to present BTEX ratios includes multivariate plotting such as
trilinear and star diagrams. Examples are shown in Figure 4.12 (Kaplan et al., 1996;
Lesage and Lapcevic, 1990; Morrison, 1999a). For star diagrams, the “rays” of each
star are usually logged so that a single component with a high concentration does not
overwhelm the lower concentration components of the fuel. A multicolor plot or
different line types can be created for diagnostic purposes or for the trial exhibit.
These techniques are also useful in that they allow for the simultaneous plotting of
several data sets.
4.10.5 CHALLENGES TO BTEX RATIO METHODS

Numerous challenges to using BTEX ratios for age-dating are available (Alvarez et
al., 1998; Landmeyer et al., 1998). Most challenges to this method argue that
transformation of BTEX compounds in the subsurface are impacted by many vari-
ables, including but not limited to the following: soil texture, composition, microbial
diversity, electron acceptor availability, volume of the release, groundwater chemis-
try, and hydrodynamic characteristics (Landmeyer et al, 1998). Rarely are these
variables quantified.

FIGURE 4.12 Examples of trilinear and star diagrams.
The most commonly encountered challenges to BTEX ratios as a means to age-

date a release include:
• Uncertainty regarding the initial gasoline composition

• Uncertainty regarding the volume of the release
• Variability in the subsurface chemical and biological system
• Chromatographic separation
The composition of gasoline varies considerably with the octane rating, changes in
seasonal composition, the geographic area, and time of formulation. In colder cli-
mates in the U.S., the composition of gasoline can change up to four times a year to
accommodate the Reid vapor pressure which is high in wintertime to provide easy
startup and low in summertime to prevent vapor lock. Premium gasoline with an anti-
knock additive package generally has a higher fraction of benzene, as it has a higher
octane rate (115) than other BTEX or alkane species. Changes in the composition in
gasoline have also occurred due to regulatory changes. The Clean Air Act Amend-
ments of 1990, for example, restricted benzene concentrations in gasoline to 1.6% by
volume. Gasoline blended prior to 1990, therefore, generally has a higher benzene
content (6% by volume) (Johnson et al., 1990). Because other non-benzene com-
pounds are not similarly restricted, (B + T)/(E + X) ratios are generally lower for
groundwater equilibrated with post-1990 gasoline. Table 4.26 summarizes BTEX
ranges in different grades of dispensed gasoline (Kaplan et al., 1995). There is a
common misconception that BTEX is only associated with gasoline and not diesel or
other types of products. The BTEX ranges for a diesel No. 2, Jet-A, and gasoline fuel
are shown on Table 4.27 (Harvey, 1997; Kaplan et al., 1995).
The initial composition of the gasoline is the major variable in the interpretation
of gasoline weathering in the subsurface. The BTEX composition detected in the
groundwater depends on the initial gasoline composition and the relative volume of
the equilibrated water, as well as the total time during which contact between the
gasoline and water has occurred. The importance of this relationship is illustrated
with a mass balance equation such as that described by Equation 4.11 (Landmeyer
et al., 1998):

TABLE 4.26
BTEX Ranges in Dispensed Gasoline
Gasoline Grade Benzene Toluene Ethylbenzene Xylene
Leaded gasoline 6.6–14.8 18.6–64.4 6.2–14.0 32.1–77.4

Regular unleaded 5.0–19.4 17.9–56.6 5.8–15.4 27.1–76.6
Unleaded plus 7.1–18.2 21.6–62.8 6.0–15.1 28.6–81.5
Super unleaded 6.6–18.9 22.4–72.2 6.6–19.1 33.4–90.8
a To convert to mg/L, multiply by 1000.
Adapted from Kaplan, I. et al., Pattern of Chemical Changes in Fugitive Hydrocarbon

Fuels in the Environment, SPE 29754, Society of Petroleum Engineers, Houston TX, 1995,
p. 601. With permission.)
Ciw(n) = Cif(∞)/K fw w f fw –n
i [1 + V /V K i ] (Eq. 4.11)
where
Ciw(n) = the aqueous phase concentration after leaching with n batches of water.
Cif(∞) = the initial concentration of the particular BTEX compound (i) in the fuel.
K fw
i = the partition coefficient.
Vw = the volume of n batches of water.
Vf = volume of gasoline.
This relationship assumes that the dissolution process does not significantly affect
the total volume of the gasoline.
Figure 4.13 is an example of the BTEX ratios for unweathered gasoline blends
equilibrated with water to illustrate the wide range of BTEX ratios between gasoline
TABLE 4.27
BTEX Range for Selected Fuels
Compound Diesel No. 2a Jet-Aa Gasolinea
Benzene 1–50 20–350 4000–30,000

Toluene 10–250 100–2500 40,000–150,000
Ethylbenzene 50–350 50–1500 4000–50,000
Xylenes 25–100 100–2500 40,000–50,000
a mg/L = parts per million (ppm).
Adapted from Kaplan, I. et al., Pattern of Chemical Changes in Fugitive

Hydrocarbon Fuels in the Environment, SPE 29754, Society of Petroleum
Engineers, Houston TX, 1995, p. 601. With permission.)

FIGURE 4.13 Variation in BTEX ratios for equilibrated water and brands of gasoline.
(Adapted from Alvarez, P. et al., in Ground Water Monitoring and Remediation, Fall, 69,
1998. With permission.)
grades and the importance of knowing the initial composition of the gasoline
(Landmeyer et al., 1998). BTEX ratios are also affected by the volumes of water to
fuel that have equilibrated. With greater volumes of water, leaching of the BTEX
constituents can be significant, resulting in a change in the composition of the
gasoline. The preferential leaching of benzene and toluene from spilled gasoline
always results in a decrease value of the B/X and (B + T)/(E + X) ratios in free
product relative to its presence in groundwater. For example, given the higher
solubility of benzene relative to xylene, benzene is preferentially leached from the
fuel, resulting in decreasing B/X ratios with increasing volumes of water. Reported
B/X ratios of 0.2 to 0.9 for water equilibrated with “weathered” gasoline, for
example, are lower than the majority of the B/X ratios shown in Figure 4.13 (Hinchee
and Reisinger, 1987; Luhrs and Pyott, 1992).
The biodegradation of BTEX in the subsurface environment is highly variable,
and abrupt changes in rates can occur on both a micro- and macro-scale. Under
anaerobic conditions, toluene may be more rapidly degraded than benzene. These
uncertainties result in a wide range of ratios for identically aged spills, especially in
different soils. Another potential issue associated with BTEX ratio analysis is the
case when BTEX compounds are a component of numerous contaminants, some of
which may impact the BTEX degradation rates. For example, no benzene or
ethylbenzene degradation was detected in a landfill-contaminated anaerobic aquifer
in Denmark (Berg, et al., 1999; Johnston et al., 1996). It is also reasonable that
variations in the organic substrates in an aquifer will result in variations regarding the
degradation rates of BTEX compounds and therefore the legitimacy of a BTEX ratio
analyses.
The transport of BTEX compounds through this changing setting results in
differences in biodegradation kinetics that are rarely quantified in a field setting. In
aquifers, BTEX biodegradation rates are assumed to occur via first-order kinetics

FIGURE 4.14 Hypothetical example of the impact on aerobic and anaerobic degradation on
B/X ratios. (Adapted from Alvarez, P. et al., in Ground Water Monitoring and Remediation,
Fall, 69, 1998. With permission.)
where the rate (dC/dt) is proportional to the contaminant concentration and where
–lC = dC/dt. BTEX degradation rates also vary based on whether they are measured
in situ or in the laboratory (Chapelle et al., 1996). Laboratory-measured biodegra-
dation rate estimates are highly sensitive to ambient redox conditions and must be
carefully matched to field conditions to obtain reliable results. The assumption that
BTEX components degrade via first-order kinetics may be inappropriate when
extrapolating laboratory-derived degradation rates to field-scale BTEX degradation
(Bekins et al., 1998).
Figure 4.14 is a hypothetical example where aerobic biodegradation depletes the
available oxygen in 10 weeks. First-order decay coefficients used in Figure 4.14 for
benzene and xylene are 0.040 day–1 and 0.025 day–1, respectively (Howard et al.,
1991). Changes in the B/X ratio change dramatically, especially for anaerobic
conditions where benzene degrades slowly, which is consistent with the literature
(Alvarez and Vogel, 1995; Lovely et al., 1989).
Another impact on the BTEX ratio analysis is the chromatographic separation
of the BTEX compounds as they are transported in both the soil and groundwater
(i.e., the individual BTEX compounds are transported at different velocities). Where
the sample is collected will, therefore, affect the concentration of the individual
BTEX compounds as a function of chromatographic separation of the individual
compounds and due to the age of the release. Figure 4.15 illustrates the situation
where three samples are collected at different distances from the source of the
gasoline release.
An evolving isotopic variation to the BTEX ratio analysis is the extraction of a
BTEX-impacted sample with pentane for which the 13C concentration is then mea-
sured (Dempster et al., 1997; Kelley et al., 1997). This technique has been used to
distinguish the origin of BTEX from three different sources.
In some instances there may be a need to discriminate between “natural” gasoline
and refined gasoline. BTEX-to-TPH ratios are lower in natural gasoline than in
refined gasoline. Refined gasoline contains olefins, which are not found in natural
gasoline, as well as additives such as MTBE. Natural gasoline contains polyaromatics
(multi-ring aromatic compounds) that are not found in refined gasoline.

FIGURE 4.15 Hypothetical example of the impact of the sampling location on the B/X ratio
due to chromatographic separation of the BTEX compounds in soil (upper) and groundwater
(lower) at various distances from the source of the release.
4.11 CHEMICAL DEGRADATION MODELS:

CHLORINATED SOLVENTS
The presence of chlorinated solvents and their breakdown products has been pro-
posed as a means of identifying how long a chemical has been in the subsurface. This
approach is based on the measured degradation rates of chlorinated solvents, prima-
rily of the parent compounds tetrachloroethylene (PCE), trichloroethane (TCA), and
carbon tetrachloride (PCM) into their respective daughter products. The presence or
absence of a particular breakdown product is argued as evidence that the parent
compound was present for a particular period of time. For example, the compound
1,1-dichloroethene (1,1-DCE) is a breakdown of both TCA and PCE, while
chloroethane is a degradation product of TCA or 1,2-dichloroethane. The presence
of 1,1-DCE and chloroethane is evidence that PCE, TCA, and possibly 1,2-DCA
were present (Feenstra et al., 1996). Another example is the presence of chloroform
which can indicate the presence of carbon tetrachloride as its parent compound (see
Figure 1.5 in Chapter 1)

A variation to this dating approach assumes that if the original concentration of
a chlorinated solvent introduced into the subsurface is known, then a knowledge of
the half-life for that chemical can provide a basis for estimating the time that the
chemical was released into the subsurface. One reported method uses the ratio of the
rate constant for the hydrolysis of 1,1,1-trichloroethane (TCA) to 1,1-dichloroethene
and acetic acid to estimate the time when 1,1,1-TCA enters groundwater according
to the following relationship: TCA fi 1,1-DCE (22%) + CH3CO2H (78%). This
method assumes that the groundwater temperature (yearly average), the concentra-
tion of TCA in the sample, and the amount of 1,1-DCE in the sample are known
(Smith, 1999). The method also assumes that the TCA and 1,1-TCA in the ground-
water are known with an excellent degree of accuracy and precision. The age of the
TCA in the groundwater (T) is then approximated by Equation 4.12 (Smith and Eng,
1997):
T = ln ([TCA]o/[TCA]t)/k (Eq. 4.12)
where
T = age of the TCA in groundwater.
[TCA]o = initial concentration of TCA (assumes 1000 molecules).
[TCA]t = TCA concentration at time t.
k = pseudo first-order rate constant (0.097 yr–1).
The contaminant migration rate is then determined by dividing the horizontal dis-
tance to each well by the age of the 1,1,1-TCA in the well. The following factors may
result in inaccurate age estimations (Smith and Eng, 1997):
• Chemical results may be more qualitative than quantitative.

• The number of samples and the test results may be inadequate.
• A 1,1-DCE/TCA ratio exceeds 0.50 — given that the ratio curve is exponential,
when the ratio approaches 1.0 the error in the age prediction increases. An age
estimate in warmer climates is not advised when the ratio approaches 1.0.
• Significant transformation of TCA to 1,1-dichloroethane — the ratio of 1,1-DCE
to TCA will be lower than if the ratio is the result of the hydrolysis reaction; the
age prediction will, therefore, be older.
• When TCE biodegradation is significant and the cis-1,2-dichloroethene (cis-1,2-
DCE) concentration is approximately two orders of magnitude greater than the 1,1-
DCE concentration — because some amount of TCE biodegrades to 1,1-DCE
relative to the concentration of cis-1,2-DCE, this reaction will affect the 1,1-DCE/
TCA ratio by resulting in a higher 1,1-DCE concentration than what is attributable
to TCA due to hydrolysis of TCA.
Several challenges to this dating approach have been made. One challenge is the
reasonableness of selecting one retardation value for an entire well field. Site-specific
information may also be unavailable for comparison with laboratory-derived degra-
dation rates. Wide ranges of half-lives are also reported in the published literature.
For example, published half-lives for PCE at 10 to 25∞C range from 0.7 to 1.3 ¥ 106

TABLE 4.28
Reported Half-Lives for Selected
Compound Half-Life (yr)a
Dichloromethane 704
Dibromomethane 180
Chloroethane 0.12
1,1-Dichloroethane 61
1,2-Dichloroethane (72) (1–30)
1,1,1-Trichloroethane (1.1) (1.7) (2.5)
1,1,2-Trichloroethane (140) (170)
1,2-Dibromomethane 2.5
1,1-Dichloroethylene 1.2 ¥ 108
Trichloroethylene (0.9) (1.3 ¥ 106)
Tetrachloroethylene (0.7) (1.3 ¥ 106)
1,2-Dichloroethylene 2.1 ¥ 1010
a Numbers in parentheses represent different
reports of rates by various authors.
yr (Luhrs et al., 1992; Pankow and Cherry, 1996). A more specific half-life for PCE
in groundwater is between 8640 and 17,280 hours based on estimated aqueous
aerobic biodegradation rates (Pankow and Cherry, 1996). For surface waters, the
half-life of PCE based on aerobic river die-away test data and saltwater grab sample
data is between 4320 and 8640 hours. For 1,1,1-trichloroethane (1,1,1-TCA), pub-
lished half-lives at 10 to 25∞C range from 1.1 to 12 years (Haag and Mill, 1988).
Published half-lives for selected chlorinated solvents at 10 to 25∞C are summarized
in Table 4.28 (Cline and Delfino, 1989; Dilling et al., 1975; Howard et al., 1991;
Jeffers et al., 1989; Mabey and Mill, 1989).
The half-life for the dechlorination of TCE, for example, proceeds at different
rates between the daughter products; therefore, each half-life must be examined when
developing a model for the mass balance between daughter products to develop a
degradation model to support the timing of a chlorinated solvent. An example is the
range of half-lives for the degradation of TCE to ethene as shown in Table 4.29
(Woodbury and Li, 1998).
In addition, the media through which the compound is migrating can impact the
half-life of the model. When evaluating a half-life model, confirm that the half-live
used is representative of the model in which the compound is detected. Table 4.30
lists selected half-lives of organic compounds in soil and groundwater (Montgomery
et al., 1991).
Furthermore, the heterogeneity of the physical and chemical systems at a site
introduces tremendous uncertainty into degradation rates. An example is whether
site-specific information is available to determine if soils are anaerobic or aerobic;

TABLE 4.29
Half-Lives of Trichloroethylene (TCE)
Degradation Products
Transformation Half-Life Range
TCE to DCE 2.4 days to 0.9 years

cis-1,2-DCE to vinyl chloride 7.2 to 140 days
trans-1,2-DCE to vinyl chloride 6.2 to 244 days
1,1-DCE to vinyl chloride 53 to 132 days
Vinyl chloride to ethene 56 days to 7.92 years
Ethene 10 years
this determination is significant for determining whether the biological environment

exists for the degradation of the chlorinated solvent and its rates of degradation. TCA,
for example, degrades to 1,1-DCE abiotically, while TCE degrades to 1,2- and 1,1-
DCE anaerobically. Another aspect associated with the impact of the subsurface
environment on the degradation rate is whether the apparent biodegradation rate is
actually an artifact of the distance from the contaminant source, the monitoring well-
screen length, and/or the degree of well desaturation that occurred during purging
(Martin-Hayden and Robbins, 1997).
In 1995, in Carroll v. Litton Systems, Inc., the plaintiff’s chemodynamics expert
used the concept of half-lives to develop information regarding the origin of trichlo-
roethylene in water wells prior to 1986. The lead author of the article used to
determine the half-life values submitted an affidavit stating that the approach was
imprudent and prone to enormous error. The plaintiff’s expert furthermore conceded
that the rate of error of his approach could not be reduced to below 1400%. The court
found the testimony unreliable and therefore inadmissible under Federal Rules of
Procedure, 702.
The presence of solvents can potentially inhibit their microbial degradation
(Barker, 1996). These complications introduce significant uncertainty in the use of
degradation rates as an indicator of the timing of a release (Vogel and McCarty,
1987).
TABLE 4.30
Half-Lives of Selected Compounds in Soil and Groundwater
Compound Half-Life in Soil Half-Life in Groundwater
DDT 2 to 15.6 years 15 days to 31.3 years

Carbon tetrachloride 6 to 12 months 7 to 365 days
Methyl ethyl ketone 1 to 7 days 2 to 14 days
Vinyl chloride 4 weeks to 6 months 8 weeks to 85 months
1,2-Dichlorobenzene 4 weeks to 6 months 8 weeks to 12 months

Impurities present in the original product can similarly introduce uncertainty in
the reliance of degradation rates for chlorinated solvents as an age-dating technique.
Based on data from chemical manufacturers, individual compounds present as impu-
rities can range from 0.1 to 25% (may be greater for recycled solvents). Industrial-
grade PCE can contain up to 1 to 3% impurities, including degradation products
(TCE; 1,2-DCE; etc.). If 10,000 ppb of PCE are detected in a groundwater sample,
the impurities could range from 1 to 25 parts per billion. The presence of high
chloride concentrations may provide insight as to whether the chlorinated solvents
detected originated as impurities or from degradation. The presence of these impu-
rities and/or additives may provide an opportunity for source identification.
Half-lives are used in developing natural degradation half-lives to support natural
attenuation remediation. This information in addition to hydraulic data can be used
to estimate the time required for the contaminant plume to be flushed with water to
a particular concentration for a given compound.
4.12 RAPID OPTICAL SCREENING

TOOL™ TESTING
The Rapid Optical Screening Tool (ROST™) is an in situ screening used in conjunc-
tion with a cone penetrometer to provide a continuous record of fluorescence in the
soil. ROST™ testing provides a rapid technique to determine qualitatively whether
petroleum hydrocarbons are present. This method is conducive to on-site sampling
during discovery when site access or availability does not allow extended time for
more traditional sampling and testing approaches (Lieberman et al., 1991). ROST™
techniques characterize petroleum hydrocarbons in real time from the fluorescence
response induced in the polycyclic aromatic hydrocarbon compounds present in
soil. Fluorescence intensity is measured at 340, 390, 440, and 490 nm and is
assumed to be generally proportional to the concentration of hydrocarbons present
in the soil. Laser-induced fluorescence (LIF) spectroscopy is used to excite the
petroleum hydrocarbons; the intensity and duration of the fluorescence as well as
the spectrum of wavelengths of light emitted by the petroleum hydrocarbon are
recorded. In some cases, a qualitative determination of the type of petroleum
hydrocarbon present is possible by comparing the waveform signatures of common
petroleum hydrocarbon products with those encountered with the ROST™ (Taer and
Liberman, 1998). Figure 4.16 is an example of the waveform log produced by
ROST™.
A demonstration project was performed at the Naval Construction Battalion
Center located at Port Hueneme, CA, to evaluate the ability of ROST™ to define a
petroleum hydrocarbon plume (Bujewski and Rutherford, 1997). Figure 4.17 illus-
trates the results of this evaluation when soil samples were used for comparison.
False-positive and false-negative values were generally located along the contami-
nant plume boundaries.
Sources of potential fluorescence from non-petroleum analytes include fluores-
cent minerals, naturally occurring organic material, de-icing agents, antifreeze additives,

FIGURE 4.16 Fluorescence vs. depth waveform log produced with Rapid Optical Screening
Tool (ROST™) testing. (From Taer, A. and S. Liberman, in National Environmental Forensic
Conference: Chlorinated Solvents and Petroleum Hydrocarbons, August 27–28, Department
of Engineering and Engineering Professional Development, University of Wisconsin, Madi-
son, 1998. p. 7. With permission.)

FIGURE 4.17 Comparison of ROST™ laser-induced fluorescence (LIF) detections and labo-
ratory results for petroleum hydrocarbons in soil at Port Hueneme, CA.
and detergent products (Bujewski and Rutherford, 1997). Background sources of

interferences that may contribute to the total intensity include window fluorescence,
cladding/bugger fluorescence, Raman signals generated within the fiber and stray
monochromator light. Appropriate control experience can be performed to distin-
guish these potential biases from true fluorescence signals.
While a screening tool, the combination of a ROST™ and cone penetrometer
testing technology provides the ability to perform several hundred feet of pushes in
a single day, depending on soil depth and number of individual pushes. Such a day
can be quickly mapped three-dimensionally to identify locations from which to
collect samples. Targeted geochemical testing can then be performed on these
samples. This technology also offers the ability to identify discrete horizons of
petroleum hydrocarbon contamination and therefore additional sources that may not
be identified by soil samples collected at 5- or 10-ft intervals.
REFERENCES
Aeschbach-Hertig, W., Schlosser, P., Stute, M., Simpson H., Ludin, A., and J. Clark, 1998. A
3H/3He study of ground water flow in a fractured bedrock aquifer, Ground Water,
36(4):661–670.

Aggarwal, P. and R. Hinchee, 1991. Monitoring in situ biodegradation of hydrocarbons by
using stable carbon isotopes, Environmental Science and Technology, 25(6):1178–1180.
Alexander, M., 1985. Biodegradation of organic chemicals, Environmental Science and Tech-
nology, 18:106–111.
Alvarez, P. and T. Vogel, 1995. Degradation of BTEX and their aerobic metabolites by
indigenous microorganisms under nitrate reducing conditions, Water Science Technol-
ogy, 31:15–28.
Alvarez, P., Heathcote, R., and S. Powers, 1998. Caution against interpreting gasoline release
dates based on BTEX ratios in ground water, Ground Water Monitoring and Remediation,
Fall:69–76.
Baedecker, M. and W. Back, 1979. Hydrogeological processes and chemical reactions at a
landfill, Ground Water, 17(5):429–437.
Barker, J., 1996. Intrinsic plume remediation: chlorinated solvents and selected pesticides, in
Dissolved Organic Contaminants in Groundwater, University Consortium Solvents-in-
Groundwater Research Program, San Francisco, CA, May 13–16, 1996, p. 29.
Bartholomew, R., Brown, F., and M. Lounsbury, 1954. Chlorine isotope effect in reactions of
tertbutyl chloride, Canadian Journal of Chemistry, 25:1173–1180.
Bekins, B., Warren, E., and E. Goody, 1998. A comparison of zero-order, first-order, and
monod biotransformation models, Ground Water, 36(2):261–268.
Beneteau, K., 1999. Personal communication, 1999. Golder Associates, Calgary, Alberta, Canada.
Beneteau, K., Aravena, R., Frape, S., Abragano, T., and R. Drimmie, 1996. Chlorinated
Solvent Fingerprinting Using 13C and 37Cl Stable Isotopes, presented at the Section 121,
H31B-12, American Geophysical Union Spring Meeting, Baltimore, MD.
Berg, P., Rugge, K., Corsen, J., Nielsen, P., and T. Christensen, 1999. Degradation of aromatic
and chlorinated aliphatic hydrocarbons in the anaerobic part of the Grinsted Landfill
leachate plume: in situ microcosm and laboratory batch experiments, Ground Water,
37(1):113–121.
Boutron, C., Gorlach, U., Candelone, J., Bolshov, M., and R. Delmas, 1991. Decrease in
anthropogenic lead, cadmium and zinc in Greenland snows since the late 1960s, Nature,
356:153–156.
Brothers, K., and K. Zikmund, 1998. Perchlorate: The Las Vegas Valley experience, in Proc.
of the Southwest Focused Ground Water Conference: Discussing the Issue of MTBE and
Perchlorate in Ground Water, June 3–4, National Ground Water Association, Anaheim,
CA, pp. 85–109.
Brown, A. and J. Clark, 1999. MTBE: air today, gone tomorrow, California Environmental
Law and Remediation Reporter, 9(2):21–30.
Brown, K., Sererka, P., Thomas, M., Perina, T., Tyner, L., and B. Sommer, 1997. Natural
attenuation of jet-fuel impacted groundwater, in In-Situ and On-Site Bioremediation, Vol.
1, Battelle Press, Columbus, OH, pp. 83–88.
Bruce, L. and G. Schmidt, 1994. Hydrocarbon fingerprinting for application in forensic
geology: review with case studies, American Association of Petroleum Geologists Bul-
letin, 78(11):1692–1710.
Bruya, J., 1999. Friedmand & Bruya, Inc., 3012 16th Avenue West, Seattle, WA 98119.
Bruya, J., 1992. Petroleum Hydrocarbons: Analysis of Sample and Degradation in the Envi-
ronment, a workshop presented at R&D, San Francisco, CA, p. 123.
Bujewski, G. and B. Rutherford, 1997. The Rapid Optical Screening Tool (ROST™) Laser-
Induced Fluorescence (LIF) System for Screening of Petroleum Hydrocarbons in Subsur-
face Soils, Innovative Technology Verification Report, EPA/600/R-97/020, U.S. Envi-
ronmental Protection Agency, Las Vegas, NV, p. 57.

Buscheck, T. and C. Alcantar, 1995. Regression techniques and analytical solutions to dem-
onstrate intrinsic bioremediation, in Hinchee, R., Wilson, J., and D. Downey (Eds.),
Intrinsic Bioremediation, Battelle Press, Columbus, OH, pp. 109–116.
Butler, E., 1999. Forensic applications of petroleum hydrocarbon fingerprinting at a wood
treating site, in Proc. of Environmental Forensics: Integrating Advanced Scientific Tech-
niques for Unraveling Site Liability, International Business Communications, Washing-
ton, D.C., June 24–25, p. 1.
Calingaert, G., 1938. Anti-knock compounds, in The Science of Petroleum, Vol. 4, Oxford
University Press, pp. 3024–3029.
Cane, G. and I. Clark, 1999. Tracing ground water recharge in an agricultural watershed with
isotopes, Ground Water, 37(1):133–139.
Carrol v. Litton Systems, Inc., 1995. 47 F.3d 1164 4th Circuit.
CEPA, 1996. Draft Policy for Cleanup of Petroleum Discharge, letter dated October 29, 1996,
from Harry Schueller to Regional Water Quality Control Board Executive Officers, State
Water Resources Control Board Resolution No. 1021b, California Environmental Protec-
tion Agency, Sacramento, CA, p. 4.
Chapelle, F., 1999. Bioremediation of petroleum hydrocarbon contaminated groundwater: the
perspective of history and hydrology, Ground Water, 37(1):122–132.
Chapelle, F., Bradley, P., Lovley, D., and D. Vroblesky, 1996. Measuring rates of biodegra-
dation in a contaminated aquifer using field and laboratory methods, Ground Water,
34(4):691–698.
Christensen, L. and T. Larsen, 1993. Method for determining the age of diesel oil spills in the
soil, Ground Water Monitoring and Remediation, 23(4):142–149.
Clark, I. and P. Fritz, 1997. Environmental Isotopes in Hydrogeology, Lewis Publishers, Boca
Raton, FL, p. 328.
Cline, P. and J. Delfino, 1989. Transformation kinetics of 1,1,1-trichloroethane to the stable
product 1,1-dichloroethene, in Larson, R.A. (Ed.), Biohazards of Drinking Water Treat-
ment, Lewis Publishers, Chelsea, MI, pp. 47–56.
Cline, P., Delfino, J., and S. Rao, 1991. Partitioning of aromatic constituents into water from
gasoline and other complex solvent mixtures. Environmental Science and Technology,
25:914–920.
Coleman, D., Liu, C., Hackley, K., and S. Pelphrey, 1995. Isotopic identification of landfill
methane, Environmental Geosciences, 4:95–103.
Coplen, T., 1996. New guidelines for reporting stable hydrogen, carbon and oxygen isotope-
ratio data, Geochimica et Cosmochimica Acta, 60:3359–3360.
Coplen, T., Kendall, C., and J. Hopple, 1983. Comparison of isotope reference samples,
Nature, 302:236–237.
Davidson, J., 1999. The study of MTBE in forensic environmental investigations, in Proc.
of Environmental Forensics: Integrating Advanced Scientific Techniques for Unravel-
ing Site Liability, International Business Communications, Washington, D.C., June 24–
25, p. 6.
Davidson, J. and D. Creek, 1999. Using the gasoline additive MTBE in forensic environmental
investigations, International Journal of Environmental Forensics, 1(1):57–67.
Davidson, J. and D. Creek, 1998. Using MTBE and other gasoline additives in forensic
environmental investigations, in Proc. of the 14th Annual Conference on Contaminated
Soils (abstract), University of Massachusetts at Amherst, p. 1.
Dempster, H., Lollar, B., and S. Feenstra, 1997. Tracing organic contaminants in groundwater:
a new methodology using compound-specific isotopic analysis, Environmental Science
and Technology, 31(11):3193–3197.

Desrocher, S. and S. Lollar, 1998. Isotopic constraints on off-site migration of landfill CH4,
Ground Water, 36(5):801–809.
Dilling, W., Tefertiller, N., and G. Kallos, 1975. Evaporation rates and reactivities of methyl-
ene chloride, chloroform, 1,1,1-trichloroethane, trichloroethylene, tetrachloroethylene,
and other chlorinated compounds in dilute aqueous solutions, Environmental Science and
Douglas, G., 1988. Approaches to chemical fingerprinting of fossil fuels with tissue analysis,
in Forensics in Environmental Science Technical Applications, U.S. Environmental
Protection Agency, Region 5, Chicago, IL, p. 38.
Douglas, G., Bence, A., Prince, R., McMillen, S., and E. Butler, 1996. Environmental stability
of selected petroleum hydrocarbon source and weathering ratios, Environmental Science
and Technology, 30:2332–2339.
Draper, W., Remoy, J., and S. Perera, 1998. Getting reliable data from water labs testing for
MTBE (or any other volatile contaminant), in Proc. of the Southwest Focused Ground
Water Conference: Discussing the Issue of MTBE and Perchlorate in Ground Water
(suppl.), National Ground Water Association, Anaheim, CA, pp. 19–52.
Ekwurzel, B., Schlosser, P., Smethie, W., Plummer, N., Busenberg, R., Michel, R., Weppering,
R., and M. Stute, 1994. Dating of shallow groundwater: comparison of the transient
tracers 3H/3He, chlorofluorocarbons and 85Kr, Water Resources Research, 30:1693–1708.
Erb, P., Philipson, W., Tent, W., and T. Liang, 1981. Analysis of landfills with historic
airphotos, Photogrammetric Engineering and Remote Sensing, 15(5):1009–1018.
Erel, Y. and C. Patterson, 1994. Leakage of industrial lead into the hydrocycle, Geochimica
et Cosmochimica Acta, 58(15):3289–3296.
Ethyl Corporation, 1998. www.ethyl.com/products.html, p. 2.
European Chlorinated Solvent Association (ECSA), 1997. Methylene chloride: an update on
human and environmental effects, Solvents Digest, March:12.
Faggan, J., Bailie, J., Desmond, E., and D. Lenane, 1975. An evaluation of manganese as an
anti-knock in unleaded gasoline, in Proc. of the SAE Meeting, October 13–17, Society of
Automotive Engineers, Detroit, MI, p. 21.
aqueous phase liquids (DNAPLs) in the subsurface, in Pankow, J. and Cherry, J. (Eds.),
Dense Chlorinated Solvents and Other DNAPLs in Groundwater, Waterloo Press, Port-
land, OR, p. 80.
Fisher, B., 1998. Fingerprinting techniques for dioxins, PCBs and other persistent organic
pollutants (POP), in Proc. of Environmental Forensics: Determining Liability through
Applied Science, September 24–25, International Business Communications,
Southborough, MA, p. 22.
Frame, G., 1997. A collaborative study of 209 PCB congeners and 6 Aroclors on 20 different
HR GC columns. 1. Retention and coelution database, Fresenius Journal of Analytical
Chemistry, 357:701–713.
Frame, G., Wagner, R., Carnahan, J., Brown, J., May R., Smullen, L., and D. Bedard, 1996.
Comprehensive, quantitative, congene-specific analysis of eight Aroclors and complete
PCB conger assignments on DB-1 capillary GC columns, Chemosphere, 33:603–623.
Fritz, R. and J. Fritz, 1991. Characterizing shallow aquifers using tritium and 14C: periodic
sampling based on tritium half-life, Applied Geochemistry, 6:17–33.
Galperin, Y., 1997. Application of Forensic Geochemical Methods for Hydrocarbon Fuels
Fingerprinting and Age-Dating. Section 2. Hydrocarbon Pattern Recognition and Dat-
ing, University of Wisconsin, Department of Engineering and Engineering Professional
Development, Madison, p. 41.

Games, L. and J. Hayes, 1977. Carbon isotopic study of the fate of landfill leachate in
groundwater, Journal of Water Pollution Control Federation, 49(4):668–677.
Games, L. and J. Hayes, 1974. Carbon in groundwater at the Columbus, Indiana, landfill, in
Waldrip, D. and R. Ruhe (Eds.), Solid Waste Disposal by Land Burial in Southern
Indiana, Indiana University Water Resources Research Center, Bloomington, IN, pp. 81–
110.
Garrett, P., Moreau, M., and J. Lowry, 1986. MTBE as a ground water contaminant, in Proc.
of the Petroleum Hydrocarbons and Organic Chemicals in Ground Water; Prevention,
Detection, and Restoration Conference, National Water Well Association, Dublin, OH,
pp. 227–238.
Garrity, K., 1996. Underground storage tank cathodic protection design, in Krause, D. and J.
Lehmann (Eds.), Storage Tank ASTs and USTs, National Association of Corrosion
Engineers, Houston, TX, pp. 255–260.
Gibbs, L., 1998. Oxygenate use in gasoline: when, what, and why, in Proc. of the Southwest
Focused Ground Water Conference: Discussing the Issue of MTBE and Perchlorate in
Ground Water (suppl.), National Ground Water Association, Anaheim, CA, p. 17.
Gibbs, L., 1993. How Gasoline Has Changed, SAE Technical Paper Series No. 932828,
Society of Automotive Engineers, Detroit, MI, p. 17.
Gibbs, L., 1990. Gasoline Additives: When and Why?, SAE Technical Paper Series #902104,
Society of Automotive Engineers, Detroit, MI, pp. 618–638.
Global Geochemistry Corp., 1991. Characterizing Petroleum Contaminants in Soil and Water
and Determining Source of Pollutants, Canoga Park, CA, p. 37.
Grip, W., 1998. Using historical aerial photography to identify probable contaminant sources,
in Proc. of Environmental Forensics: Determining Liability through Applied Science,
International Business Communications, Southborough, MA, p.5.
Haag, W. and T. Mill, 1988. Effect of subsurface sediment on hydrolysis of haloalkanes and
epoxides, Environmental Science and Technology, 22:658–663.
Hackley, K., Liu, C., and D. Coleman, 1996. Environmental isotope characteristics of landfill
leachates and gases, Ground Water, 34(5):827–836.
Haeseler, F., Blanchet, D., Druelle, V., Werner, P., and J. Vandecasteele, 1999. Analytical
characterization of contaminated soils from former manufactured gas plants, Environ-
mental Science and Technology, 33(6):825–830.
Halogenated Solvents Industry Alliance, 1994. Perchloroethylene, White Paper, February:7.
Hartman, B., 1998a. Applications and interpretation of soil vapor data, in Petroleum Hydro-
carbon Contamination: Legal and Technical Considerations, Argent Communications
Group, Foresthill, CA, pp. 81–110.
Hartman, B., 1998b. The Great Escape (From the UST), LUSTLine Bull. No. 30, New
England Interstate Water Pollution Control Commission, Wilmington, MA, pp. 19–23.
Harvey, E., 1998. Changes in the composition of gasoline and blended products, in Proc. of
Environmental Forensics: Determining Liability through Applied Science, International
Business Communications, Southborough, MA, p. 16.
Harvey, E., 1997. Interpretative considerations for pattern matching refined petroleum prod-
ucts, in Proc. of Hydrocarbon Pattern Recognition and Dating, Program No. 7675,
Department of Engineering and Engineering Professional Development, University of
Hinchee, R. and H. Reisinger, 1987. A practical application of multiphase transport theory to
ground water contamination problems, Ground Water Monitoring Review, 7:84–92.
Hitzig, R., Kostecki, P., and D. Leonard, 1998. Study reports LUST programs are feeling
effects of MTBE releases, Soil & Groundwater Cleanup, August/ September:15–19.

Hoefs, J., 1997. Stable Isotope Geochemistry, Springer Publishing, Berlin, p. 201.
Howard, P. et al., 1991. Handbook of Environmental Degradation Rates, Lewis Publishers,
Boca Raton, FL, p. 725.
Huntzinger, O., Safe, S., and V. Zitko, 1974. The Chemistry of PCBs, CRC Press, Boca Raton, FL.
Hurst, R., 1999a. Lead isotopic forensics of crude oil, unleaded gasoline and MTBE. Session
2. Environmental forensics, in Conference Abstracts, 9th Annual West Coast Conference
on Contaminated Soils and Water, Association for the Environmental Health of Soils,
Oxnard, CA, p. 1.
Hurst, R., 1999b. If all MTBE is created equally, can its source(s) be identified? Session 2.
Environmental forensics, in Conference Abstracts, 9th Annual West Coast Conference on
Contaminated Soils and Water, Association for the Environmental Health of Soils,
Oxnard, CA, p. 1.
Hurst, R., 1999c. Applications of anthropogenic lead archaeostratigraphy (ALAS model) to
hydrocarbon remediation, International Journal of Environmental Forensics, 1(1):33–56.
Hurst, R., 1998a. Estimating ages of hydrocarbon releases using lead isotopes, in Proc. of
Environmental Forensics: Determining Liability through Applied Science, International
Business Communications, Southborough, MA, p. 14.
Hurst, R., 1998b. Applications of anthropogenic lead archaeostratigraphy to hydrocarbon
remediation, in Proc. of the 14th Annual Conference on Contaminated Soils (abstract),
University of Massachusetts at Amherst, p. 1.
Hurst, R., Davis, T., and B. Chinn, 1996. The lead fingerprints of gasoline contamination,
Environmental Science and Technology, 30(6):304–307.
Hwang, S., Gensburg, L., Fitzgerald, E., Herzfeld, P., and B. Bush, 1993. Fingerprinting
sources of contamination: statistical techniques for identifying point sources of PCBs,
Journal of Occupational Medical Toxicology, 2:365–382.
IAEA, 1995. Reference and intercomparison materials for stable isotopes of light elements, in
Proc. of Consultants Meeting, held in Vienna, Austria, December 1–3, 1995, IAEA-
TECDOC-825, International Atomic Energy Agency, Vienna, p. 165.
IARC, 1979. Monographs on the Evaluation of the Carcinogenic Risk of Chemicals to
Humans: Halogenated Hydrocarbons, Vol. 20, International Agency for Research into
Cancer, Switzerland, p. 593.
Jarman, W., Hilkbert, A., Bacon, C., Collister, J., Ballschmitter, K., and R. Risebrough, 1998.
Compound-specific carbon isotopic analysis of aroclors, clophens, kaneclors, and
phenoclors, Environmental Science and Technology, 32:833–836.
Jeffers, P., Ward, L., Woytowitch, L., and L. Wolfe, 1989. Homogeneous hydrolysis rate
constants for selected chlorinated methanes, ethanes, ethenes, and propanes, Environ-
Johnson, G., 1999. Unmixing polychlorinated biphenyl fingerprints in surface waters of San
Francisco Bay, in Proc. of Environmental Forensics: Integrating Advanced Scientific
Techniques for Unraveling Site Liability, International Business Communications, Wash-
ington, D.C., June 24–25, p. 34.
Johnson, P., Kemblowski, M., and J. Colthart, 1990. Quantitative analysis for the cleanup of
hydrocarbon-contaminated soils by in-situ soil venting, Ground Water, 28:413–429.
Johnston, J., Borden, R., and M. Barlaz, 1996. Anaerobic degradation of alkylbenzenes and
trichloroethylene in aquifer sediment down gradient of a sanitary landfill, Journal of
Contaminant Hydrology, 23(4):263–283.
Kannan, K., Maruya, K., and S. Tanabe, 1997. Distribution and characterization of polychlo-
rinated biphenyl congeners in soil and sediments from a Superfund site contaminated
with Aroclor 1268, Environmental Science and Technology, 31:1483–1488.

Kaplan, I. and Y. Galperin, 1996. How to recognize a hydrocarbon fuel in the environment and
estimate its age of release, in Bois, T. and B. Luther (Eds.), Groundwater and Soil
Contamination: Technical Preparation and Litigation Management, John Wiley & Sons,
Somerset, NJ, pp. 145–200.
Kaplan, I., Galperin, Y., Lu, S., and R. Lee, 1997. Forensic environmental geochemistry:
differentiation of fuel-types, their sources and release time, Organic Geochemistry, 27(5/
6):289–317.
Kaplan, I., Galperin, Y., Alimini, R., and S. Lu, 1996. Patterns of chemical changes during
environmental alteration of hydrocarbon fuels, Groundwater Monitoring and Remediation,
16(4):113–124.
Kaplan, I., Alimi, M., Galperin, Y., Lee, R., and S. Lu, 1995. Pattern of Chemical Changes
in Fugitive Hydrocarbon Fuels in the Environment, SPE 29754, Society of Petroleum
Engineers, Houston TX, pp. 601–617.
Kelley, C., Hammer, B., and R. Coffin, 1997. Concentrations and stable isotope values in BTEX
contaminated groundwater, Environmental Science and Technology, 31:2469–2472.
Kram, M., 1988. Use of SCAPS petroleum hydrocarbon sensor technology for real time
indirect DNAPL detection, Journal of Soil Contamination, 17(1):73–86.
Kroon, D. and M. Baach, 1996. Minimizing liability by properly planning UST system
upgrades, in Krause, D. and J. Lehmann (Eds.), Storage Tank ASTs and USTs, National
Association of Corrosion Engineers, Houston, TX, pp. 325–335.
Landmeyer, J., Chapelle, F., Bradley, P., Pankow, J., Church, C., and P. Tratnyek, 1998. Fate
of MTBE relative to benzene in a gasoline-contaminated aquifer (1993–98), Ground
Water Monitoring and Remediation, Fall:93–102.
Lee, L., Hagwell, M., Delfino, J., and S. Rao, 1992. Partitioning of polycyclic aromatic
hydrocarbons from diesel fuel into water, Environmental Science and Technology, 26:2104–
2110.
Lesage, S. and P. Lapcevic, 1990. Differentiation of the origin of BTX in ground water using
multivariate plots, Ground Water Monitoring Review, Spring:102–105.
Lieberman, S., Therlault, G., Cooper, S., Malone, P., Olsen, R., and P. Lurk, 1991. Rapid
subsurface, in-situ field screening of petroleum hydrocarbon contamination using laser
induced fluorescence over optical fibers, in Symp. Proc., Second Int. Symp., Field
Screening Methods for Hazardous Waste and Toxic Chemicals, February 12–14, Las
Vegas, NV, pp. 57–63.
Liebert, B., 1990. Corrosion phenomena related to steel tanks, in Underground Storage Tank
Management, Leak Detection and Corrective Action, Department of Engineering and
Engineering Professional Development, University of Wisconsin, Madison, p. 30.
Lovely, D., Baedecker, M., Lonergan, D., Cozzarelli, I., Phillips, E., and D. Siegel, 1989.
Oxidation of aromatic contaminants coupled to microbial iron reduction, Nature, 339:297–
300.
Luhrs, R., Pyott, C., and N. Stewart, 1992. Graphical evaluation of gasoline contaminated
water: a powerful new approach, in Proc. of the National Groundwater Water Associa-
tion Focus Conference on Eastern Regional Ground Water Issues, October 13–15,
Newton, MA, p. 15.
Lundegard, P., Sweeney, R., and G. Ririe, 1999. Soil gas methane at petroleum contaminated
sites: forensic determination of origin and source, International Journal of Environmen-
tal Forensics, 1(1):19–32.
Lundegard, P., Brearley, M., and R. Haddad, 1998. Methane associated with a large gasoline
spill-forensic determination of origin and source, Proc. of the 14th Annual Conference on
Contaminated Soils (abstract), University of Massachusetts at Amherst, p. 1.

Lyon, J., 1987. Use of maps, aerial photographs and other remote sensor data for practical
evaluations of hazardous waste sites, Photogrammetric Engineering and Remote Sensing,
53(5):515–519.
Mabey, W., 1995. Survey of chemicals encountered in investigation/remediation, Section 6,
in Environmental Chemistry for Investigating and Remediating Soil and Groundwater
Contamination, Department of Engineering and Engineering Professional Development,
University of Wisconsin, Madison, p. 4.
Mabey, W. and T. Mill, 1989. Critical review of hydrolysis of organic compounds in water
under environmental conditions, Physical Chemistry Reference Data, 7:383–415.
Mann, W., Unterweger, M., and B. Coursey, 1982. Comments on the NBS titriated-water
standards and their use, International Journal of Applied Radioactive Isotopes, 33:383–386.
Mansuy, L., Philip, P., and J. Allen, 1997. Source identification of oil spills based on the
isotopic composition of individual components in weathered oil samples, Environmental
Science and Technology, 31(12):3417–3425.
McCan, M., 1996. Spill containment and overfill prevention requirements for underground
storage tanks, in Krause, D. and J. Lehmann (Eds.), Above Ground Tanks and Under-
ground Storage Tanks, National Association of Corrosion Engineers, Houston, TX, pp.
337–346.
McKinnon, R. and J. Dyksen, 1984. Removing organics from groundwater through aeration
plus GAC, Journal American Water Works Association, May:42–47.
McNab, W. and B. Dooher, 1999. Discussion of papers, Ground Water, 37(2):167–168.
McNab, W. and B. Dooher, 1998. A critique of a steady-state analytical method for estimating
contaminant degradation rates, Ground Water, 36(6):983–987.
Messman, J. and T. Rains, 1981. Determination of tetraalkyllead compounds in gasoline by
liquid chromatography-atomic absorption spectrometry, Analytical Chemistry, 11(11):
1632–1636.
Monsanto Corp. (undated). Polychlorinated biphenyls. A report on uses, environmental and
health effects and disposal, White Paper, p. 18.
Montgomery, J. 1991. Groundwater Chemicals Field Guide, Lewis Publishers, Chelsea, MI,
p. 271.
Mormile, M., Liu, S., and J. Suflita, 1994. Anaerobic biodegradation of gasoline oxygenates:
extrapolation of information to multiple sites and redox conditions, Environmental Sci-
ence and Technology, 28:1727–1732.
Morrison, R., 1999a. Forensic techniques for establishing the origin and timing of a contami-
nant release, in Meyer, C. (Ed.), Expert Witnessing: Explaining and Understanding
Science, CRC Press, Boca Raton, FL, pp. 145–172.
Morrison, R., 1999b. Use of proprietary additives to date petroleum hydrocarbons, Environ-
mental Claims Journal, 11(3):81–90.
Morrison, R., 1999c. Forensic techniques for establishing the origin and timing of a contaminant
release, Environmental Liability, Enforcement and Penalties Reporter, 9(5):109–116.
Morrison, R., 1998a. Determining surface release sources from soil and groundwater contami-
nation, in Proc. of Environmental Forensics: Determining Liability through Applied
Science, International Business Communications, Southborough, MA, p. 44.
Morrison, R., 1998b. Overview of forensic techniques used in environmental litigation, in
Proc. of the National Environmental Forensic Conference: Chlorinated Solvents and
Petroleum Hydrocarbons, Program No. 8451, Department of Engineering and Engineer-
ing Professional Development, University of Wisconsin, Madison, p. 45.

Morrison, R., Hartman, B., Jones, J., Beers, R., and R. Erickson, 1999. Chlorinated Solvent
Contamination: Legal and Technical Considerations, Argent Communications Group,
Forresthill, CA, p. 235.
Murphy, B., 1998. Use of isotopes to identify and date chlorinated solvents and petroleum
hydrocarbon releases, Section 8, in Proc. of the National Environmental Forensic Con-
ference: Chlorinated Solvents and Petroleum Hydrocarbons, Program No. 8451, Depart-
ment of Engineering and Engineering Professional Development, University of Wiscon-
sin, Madison, p. 32.
Odermatt, S., 1999. Discussion of papers, Ground Water, 37(2):166–167.
Odermatt, S., 1994. Natural chromatographic separation of benzene, toluene, ethylbenzene,
and xylenes (BTEX compounds) in a gasoline contaminated ground water aquifer,
Organic Geochemistry, 41:1141–1150.
Pankow, J., Thompson, N., Johnson, R., Baehr, A., and J. Zogorski, 1997. The urban atmo-
sphere as a non-point source of the transport of MTBE and other volatile organic
compounds (VOCs) to shallow ground water, Environmental Science and Technology,
31:2821–2828.
Pankow, J., Feenstra, S., Cherry, J., and C. Ryan, 1996. Dense chlorinated solvents and other
DNAPLs in groundwater: history, behavior, and remediation, in Pankow, J. and J. Cherry
(Eds.), Dense Chlorinated Solvents and other DNAPLs in Groundwater, Waterloo Press,
Portland, OR, p. 80.
Patterson, C., and D. Settle, 1976. The reduction of orders of magnitude error in lead analyses
of biological materials and natural waters by evaluating and controlling the extent and
sources of industrial lead contamination introduced during sample collecting and analy-
sis, in LaFleur, P. (Ed.), Accuracy in Trace Analysis: Sampling, Sample Handling, and
Analysis, National Bureau of Standards Special Publication, Washington, D.C., pp. 321–
351.
Peters, K., and J. Moldowan, 1993. The Biomarkers Guide, Prentice-Hall, Englewood Cliffs,
NJ, p. 363.
Philip, R., 1988. Forensic geochemistry, natural resources, and environment, Energy and
Environmental Law, 12(3):212–229.
Pickering, H., and R. Frankenthal, 1974. Mechanism of pit and crevice propagation on iron and
stainless steels, in Staehle, R. et al. (Eds.), Localized Corrosion, International Corrosion
Conference Series, National Association of Corrosion Engineers, Houston, TX, pp. 261–
269.
Plummer, L., Michel, R., Thurman, E., and P. Glynn, 1993. Environmental tracers for age-
dating young groundwater, in Alley, W. (Ed.), Regional Ground-Water Quality, Van
Nostrand-Reinhold, New York, pp. 255–294.
Pope, P., Eeckhour, E., and C. Rofer, 1996. Waste site characterization through digital analysis
of historical aerial photographs, Photogrammetric Engineering and Remote Sensing,
62(12):1387–1394.
Potter, T., 1990. Fingerprinting petroleum products: unleaded gasolines, in Kostecki, P. and
E. Calabrese (Eds.), Petroleum Contamination Soils, Vol. 3, Lewis Publishers, Boca
Raton, FL, pp. 83–92.
Pourbax, M., 1971. The electrical basis for localized corrosion, in Staehle, R. et al. (Eds.),
Localized Corrosion, International Corrosion Conference Series, National Association of
Corrosion Engineers, Houston, TX, pp. 12–33.
Rabinowitz, M. and G. Wetherill, 1972. Identifying sources of lead contamination by stable
isotope techniques, Environmental Science and Technology, 6(8):705–709.

Rachdawong, P. and E. Christensen, 1997. Determination of PCB sources by a principal
component method with nonnegative constraints, Environmental Science and Technol-
ogy, 31:2686–2691.
370.
Rawson, J., May, R., and J. Guswa, 1998. Remediation of multi-component PCB-containing
DNAPL reservoirs in fractured rock, in Wickramanayake, G. and R. Hinchee (Eds.),
Nonaqueous Phase Liquids: Remediation of Chlorinated and Recalcitrant Compounds,
Battelle Press, Columbus, OH, pp. 1–6.
Raymond, R., Hudson, J., and V. Jaminson, 1976. Oil degradation in soil, Applied and
Environmental Microbiology, 31(4):522–535.
Reisch, M., 1994. Top 50 chemicals production rose modestly last year, Chemical and
Engineering News, 72(15):12–15.
Rhue, R., Mansell, R., Ou, L., Cox, R., Tang, S., and Y. Ouyang, 1992. The fate and behavior
of lead alkyls in the environment: a review, Critical Reviews in Environmental Control,
22(3/4):169–193.
Rice, D., and G. Claypool, 1981. Generation, accumulation, and resource potential of biogenic
gas, American Association of Petroleum Geologists Bulletin, 65:5–25.
Ritchie, J. and J. McHenry, 1990. Application of radioactive fallout cesium-137 for measuring
soil-erosion and sediment accumulation rates and patterns: a review, Journal of Environ-
mental Quality, 19:215–233.
Rosman, K., Chisholm, W., Boutron, C., Candelone, J., and S. Hong, 1994. Isotopic evidence
to account for changes in the concentration of lead in Greenland snow between 1960 and
1988, Geochimicia et Cosmochimica Act, 58(15):3265–3269.
Russell, T., 1988. Petrol and diesel additives, Petroleum Review, October:35–42.
Schmidt, G., 1998. The effect of petroleum weathering on pattern recognition and dating, in
Proc. of Environmental Forensics: Determining Liability through Applied Science, Inter-
national Business Communications, Southborough, MA, p. p. 13.
Schoell, M., 1998. Multiple origins of methane in the earth, Chemical Geology, 71:1–10.
Shifrin, N. and A. Toole, 1998. Historical perspective on PCBs, Environmental Science and
Slater, G., Dempster, H., Sherwood, B., Lollar, J., Spivack, M., and P. Mackenzie, 1998.
Isotopic tracers of degradation of dissolved chlorinated solvents, in Wickramanayake, G.
and R. Hinchee (Eds.), Nonaqueous Phase Liquids: Remediation of Chlorinated and
Recalcitrant Compounds, Battelle Press, Columbus, OH, p. 379.
Smith, J., 1999. The determination of the age of 1,1,1-trichloroethane in groundwater, in
Conference Abstracts, Second Executive Forum on Environmental Forensics, Interna-
tional Business Communications, Southborough, MA, p. 1.
Smith, J. and L. Eng, 1997, Groundwater Sampling: A Chemist’s Perspective, Trillium, Inc.,
Coatesville, PA, p. 13.
Soby, M., Connolly, K., and R. Folsom, 1992. Waste Site Characterization and Prioritization
Using a Geographic Information System, Geographic Information (GIS), and Mapping
Practices and Standards, American Society for Testing and Materials, Philadelphia, PA,
pp. 280–294.
Squillance, P., Pankow, N., and J. Zogorski, 1996. Environmental Behavior and Fate of
Methyl Tert-Butyl Ether (MTBE), Fact Sheet FS-203-96, U.S. Department of the Interior,
U.S. Geological Survey, U.S. Government Printing Office, Washington, D.C.

Steffan, R., McClay, K., Vainberg, S., Condee, C., and D. Zhang, 1997. Biodegradtion of the
gasoline oxygenates methyl-tert-butyl ether, ethyl-tert-butyl ether and tert-amyl-methyl
ether by propane oxidizing bacteria, Applied Environmental Microbiology, 63:4216–4222.
Stewart, P., Lee, J., Marano, D., Spirtas, R., Forbes, C., and A. Blair, 1991. Retrospective
cohort mortality study of workers at an aircraft maintenance facility. II. Exposure and
their assessment, British Journal of Internal Medicine, 48:531–537.
Stormant, D., 1960. SOCAL jilts ethyl for methyl, Oil and Gas Journal, 58(18):74.
Stout, S., 1999. Use of biomarkers in assessing liability for fugitive petroleum products and
crude oil, in Proc. of Environmental Forensics: Integrating Advanced Scientific Tech-
niques for Unraveling Site Liability, International Business Communications, Washing-
ton, D.C., June 24–25, pp. 58–59.
Stout, S., Seavey, J., Dahlen, D., McCarthy, K., and A. Uhler, 1999a. Application of low
boiling biomarkers in assessing liability for fugitive middle distillate petroleum products.
Session 2. Environmental forensics, in Conference Abstracts, 9th Annual West Coast
Conference on Contaminated Soils and Water, Association for the Environmental Health
of Soils, Oxnard, CA, p. 1.
Stout, S., Davidson, J., McCarthy, K., and A. Uhler, 1999b. Gasoline additives: usage of lead
and MTBE, Soils and Groundwater Cleanup, February/March:36–37.
Stout, S., Uhler, A., and K. McCarthy, 1999c. Biomarkers — underutilized components in the
forensic tool kit, Soil and Groundwater Cleanup, June/July:58–59.
Stout, S., Uhler, A., Naymik, T., and K. McCarthy, 1998a. Environmental forensics: unrav-
eling site liability, Environmental Science and Technology News, June 1:260–264.
Stout, S., Uhler, A., and K. McCarthy, 1998b. PAH can provide a unique forensic “fingerprint”
for hydrocarbon products, Soil and Groundwater Cleanup, October:25–29.
Stout, A., Uhler, M., Philip, P., Allen, J., and A. Uhler, 1998c. Source differentiation of
individual chlorinated solvents dissolved in groundwater using compound specific car-
bon isotopic analyses, Extended Abstracts from 216th American Chemical Society
National Meeting, Environmental Chemistry Division, p. 6.
Stukas, W. and L. Barrie, 1987. Lead 206/207 isotope ratios in the atmosphere of North
America as tracers of U.S. and Canadian emission, Nature, 239:144–146.
Suchomet, K., Kreamer, D., and A. Long, 1990. Production and transport of carbon dioxide
in a contaminated vadose zone: a stable and radioactive carbon isotope study, Environ-
Suflitia, J. and M. Mormile, 1993. Anaerobic biodegradation of known and potential gasoline
oxygenates in the terrestrial subsurface, Environmental Science and Technology, 27:976–
978.
Taer, A. and S. Liberman, 1998. Use of rapid optical screening tool technology to identify the
distribution and composition of petroleum hydrocarbons, in Proc. of the National Envi-
ronmental Forensic Conference: Chlorinated Solvents and Petroleum Hydrocarbons,
Department of Engineering and Engineering Professional Development, University of
Wisconsin, Madison, p. 7
Tanaka, N., and D. Rye, 1991. Chlorine in the stratosphere, Nature, 353:707.
Taylor C. and W. Roether, 1982. A uniform scale for reporting low-level tritium measurements
in water, International Journal of Applied Radioactive Isotopes, 33:377–382.
Touchstone, J., 1992. Practice of TLC, John Wiley & Sons, New York, p. 337.
Uhler, A., Stout, S., and K. McCarthy, 1998a. Fingerprinting of light refined petroleum
products, in Proc. of the National Environmental Forensic Conference: Chlorinated
Solvents and Petroleum Hydrocarbons, Department of Engineering and Engineering
Professional Development, University of Wisconsin, Madison, p. 24.

Uhler, A., Stout, S., and K. McCarthy, 1998b. Increase success of assessments at petroleum
sites in five steps, Soil and Groundwater Cleanup, January/February:13–19.
Unocal, 1989. Material Safety Data Sheet for 1,1,1-Trichloroethane, Unocal Chemicals Divi-
sion, Petrochemical Groups, Schaumburg, IL, p. 2.
U.S. EPA, 1997. Environmental Technology Verification Program, Cone Penetrometer-De-
ployed Sensor, Rapid Optical Screening Tool (ROST), EPA/VSSCM/01, U.S. Environ-
mental Protection Agency, Washington, D.C., p. 3.
U.S. EPA, 1990. Standard Test Procedures for Evaluating Leak Detection Methods: Entire Set,
EPA/530/UST-90/004–010, U.S. Environmental Protection Agency, Cincinnati, OH, p. 6.
U.S. EPA, 1989. Volumetric Tank Testing: An Overview, EPA/625/9/89/009, U.S. Environ-
mental Protection Agency, Washington, D.C., p. 37.
U.S. EPA, 1988a. Tank Corrosion Study, EPA/510/K-92/802, U.S. Environmental Protection
Agency, Cincinnati, OH, p. 44.
U.S. EPA, 1988b. Musts for USTs: A Summary of the New Regulations for Underground
Storage Tank Systems, EPA/530/UST-89/011, U.S. Environmental Protection Agency,
U.S. EPA, 1988c. Evaluation of Volumetric Leak Detection Methods for Underground Storage
Tanks, EPA/600/2-88/68a, U.S. Environmental Protection Agency, Washington, D.C., p.
19.
U.S. EPA, 1988d. Analysis of manual inventory reconciliation, EPA/510-S/92-802, U.S.
Environmental Protection Agency, Cincinnati, OH, p. 5.
U.S. EPA, 1987. Causes of Release from UST Systems: Report and Attachments, EPA/510-R/
920702, U.S. Environmental Protection Agency, Cincinnati, OH, p. 76.
Van Warnerdam, E., Frape, S., Aravena, R., Drimmie, R., Flatt, H., and J. Cherry, 1995. Stable
chlorine and carbon isotope measurements of selected chlorinated organic solvents,
Applied Geochemistry, 10:547–552.
Vogel, T. and P. McCarty, 1987, Abiotic and biotic transformations of 1,1,1-trichloroethane
under methanogenic conditions, Environmental Science and Technology, 21:1208–1213.
Vogel, T., Criddle, C., and P. McCarty, 1987. Transformation of halogenated aliphatic
compounds, Environmental Science and Technology, 21:722–736.
Wait, A., 1999. Evolution of organic analytical methods in environmental forensic chemistry,
International Journal of Environmental Forensics, 1(1):68–86.
Walker, J., Colwell, R., and L. Petrakis, 1976. Biodegradation rates of components of petro-
leum, Canadian Journal of Microbiology, 22:1209–1213.
Wang, Z. and M. Fingas, 1995. Use of methyldibenzothiophenes as markers for differentiation
and source identification of crude and weathered oils, Environmental Science and Tech-
nology, 29:2842–2849.
Wang, Z., Fingas, M., and G. Sergy, 1994. Study of 22-year-old Arrow Oil samples using
biomarker compounds by GC/MS, Environmental Science and Technology, 29:1733–
1846.
Ward, C., 1984. Gasoline, in Holland, D. (Ed.), Encyclopedia Americana, Grolier, Danbury,
CT, pp. 337–338.
Warren Rogers & Associates, 1981. Report on the Statistical Analysis of Corrosion Failures
Unprotected Underground Steel Tanks, American Petroleum Institute, Washington, D.C.,
p. 145.
Warren Rogers & Associates (undated). Predicting and Detecting Tank Leaks: The Economics
of UST Integrity, Middletown, PA, pp. 14.
Watmough, S., Hughes, R., and T. Hutchinson, 1999. 206Pb/207Pb ratios in tree rings as monitors
of environmental changes, Environmental Science and Technology, 33(5):670–673.

Weil, G., Graf, R., and L. Forister, 1994. Investigations of hazardous waste sites using thermal
IR and ground penetrating radar, Photogrammetric Engineering and Remote Sensing,
60(8):999–1005.
Westervelt, W., Lawson, P., Wallace, M., and F. Fosbrook, 1997. Intrinsic remediation of
arctic diesel fuel near drinking water wells, in In Situ and On-Site Bioremediation, Vol.
1, Battelle Press, Columbus, OH, pp. 61–66.
Whiticar, M., Faber, J., and M. Schoell, 1986. Biogenic methane formation in marine and
freshwater environments: CO2 reduction vs. acetate fermentation —isotopic evidence,
Geochimica et Cosmochimica Acta, 50:693–709.
Woodbury, A. and H. Li, 1998. The Arnoldi-finite element method for solving transport of
reacting solutes in porous media, in Wickramanayake, G. and R. Hinchee (Eds.), Non-
aqueous Phase Liquids: Remediation of Chlorinated and Recalcitrant Compounds, Battelle
Press, Columbus, OH, pp. 97–106.
Younglass, T., Swansinger, J., Danner, D., and M. Greco, 1985. Mass spectral characterization
of petroleum dyes, tracers and additives, Analytical Chemistry, 57:1894–1902.
Zemo, D. and T. Graf, 1993. The importance and benefit of fingerprint characterization in site
investigation and remediation focusing on petroleum hydrocarbons, in Proc. of the 1993
Conference on Petroleum Hydrocarbons and Organic Chemicals in Ground Water:
Prevention, Detection, and Restoration, National Ground Water Association, Houston,
TX, pp. 39–54.

Plate 4.1 Photograph of petroleum-impacted soil in a trench excavation.
Plate 4.2 Dye additives in different gasoline brands. (From Kaplan, I. et al.,
Organic Geochemistry, 27(5), 289–317, 1997. With permission.)

5 Contaminant
Transport Modeling
A useful approximation of realty or an intellectual toy?
5.1 INTRODUCTION
A contaminant transport model is a work-in-progress hypothesis. Contaminant trans-

port models are useful because they simplify reality for the purpose of predicting
outcomes. In environmental litigation, contaminant transport models are used to
confirm or challenge the allegation that a contaminant release occurred at a discrete
point in time based on the observed presence of a contaminant some distance from
the source. This opinion is usually based on knowledge of the location of the release,
chemical test results, and a contaminant transport model.
When evaluating contaminant transport models, examine the modeling results by
dividing the subsurface into the following discrete zones: (1) the surface (paved and
unpaved), (2) the soil and capillary fringe, and (3) the groundwater. This division is
necessary because each zone requires different governing assumptions and math-
ematics that cumulatively determine the time required for a contaminant to travel
from the ground surface to groundwater.
The ability to reliably model contaminant transport is directly proportional to the
representativeness of the input parameters. Given uncertainties associated with these
input parameters, a range of values should be used that produces a range of contami-
nant transport probabilities. Practical inversion tools now allow for rigorous determi-
nation of optimal parameter values and what the data do and do not support. A key
theme of this chapter is that a unique solution for contaminant transport models does
not exist (see Figure 5.1).
5.2 LIQUID TRANSPORT

THROUGH PAVEMENT
A frequent inquiry is the determination of whether a solvent migrated through a

paved surface such as asphalt, concrete, crushed rock, or compacted soil and, if so,

FIGURE 5.1 Concept of a unique solution vs. a range of probable solutions.
the time required. Ideally, direct measurements are performed to answer this question
by collecting a representative pavement core sample, ponding the liquid of interest,
and recording the time required for the liquid to drip from the bottom of the sample.
Absent direct measurement, contaminant transport equations are used. In order to
select the correct equation(s), identification of the most likely transport mechanism
— such as liquid advection (Darcy flux; see Equation 2.8 in Chapter 2), gas diffusion,
liquid diffusion and evaporation — is required.
The transport of dense non-aqueous phase liquids (DNAPLs) via liquid advec-
tion through pavement is commonly believed to be a rapid process. This assumption
is true if the pavement is cracked, allowing unrestricted flow, or if the spill occurs
over an expansion/control or isolation joint filled with permeable wood, oakum, or
tar. Expansion joints are placed at the junction of the floor with walls, foundation
columns, and footings. Given the sorptivity of the material used to fill expansion
joints, sampling and testing of these materials are often useful to establish whether
a contaminant was transported into the underlying soil via an expansion joint.
Isolation joints are used to separate a concrete slab from other parts of a structure
to permit horizontal and vertical movement of the concrete slab. Isolation joints
extend the full depth of the slab and include pre-molded joint fillers (Kosmatak et
al., 1988).
In the absence of direct measurements or the presence of cracks or expansion
joints or direct measurements with a pavement core, quantifiable transport variables
can be identified that determine if and when a liquid permeated a paved surface.
Variables used in calculating the time required for a liquid to infiltrate through a
paved surface include:

• The temporal nature of the release (steady state or transient)
• The saturated and unsaturated hydraulic conductivity of the pavement
• Physical properties of the contaminant (density, viscosity, vapor pressure)
• Chemical properties of the liquid (pure phase, mixed solvents, or dissolved in
water) which affect the evaporation rate
• Liquid thickness and the length of time that the liquid was present on the paved
surface
• Volume of the release
• Evaporative flux
• Pavement thickness, porosity, composition and slope
The circumstances of a contaminant release and pavement composition are key

variables. Variables regarding the circumstances of the release include whether the
liquid was in contact with the pavement for a sufficient time to allow transport
through the pavement to occur. If the model does not account for evaporation and/
or assumes that the liquid thickness on the pavement is constant, the model will
overestimate the rate of transport. If clean-up activities were performed coincident
with the release (e.g., sawdust, green sand, absorbent socks, crushed clay, etc.) or if
the spill occurred in a building with forced air, these activities and evaporative loss
will compete for the solvent available for transport through the pavement.
Noting the physical condition of the paved surface is needed for its incorporation
into the model. Such observations would include:
• Is the surface treated with an epoxy coating to prevent corrosion from acid releases
(common in plating shops)?
• Was the concrete mixed with an additive to reduce its permeability to chemicals
(e.g., addition of Dow Latex No. 560 to the concrete)?
• What was the nature of the surface prior to the release (e.g., impregnated with oils
and dirt, smooth or pitted, sloped toward a drain, etc.)?
Once this specific information is collected, a conceptual model can be constructed.

The saturated hydraulic conductivity or permeability value of the paved surface
is a key variable. The terms hydraulic conductivity (K) and permeability (k) are
associated with the ability of a porous media to transmit a fluid. While permeability
and hydraulic conductivity are often used interchangeably, they are not synonymous.
Permeability refers to properties associated with the media through which the con-
taminant is migrating, such as the distribution of the grain sizes, the sphericity and
roundness of the grains, and the nature of their packing (Freeze and Cherry, 1979).
Fluid properties such as density and viscosity are not included. The saturated hydrau-
lic conductivity of a material is a measurement of the ability of a fluid to move
through the material (Lohman et al., 1972). Hydraulic conductivity accounts for fluid
density and viscosity.
The release of a DNAPL compound such as tetrachloroethylene (PCE) (1.63 g/
cm3 at 20∞C) requires that the water-saturated hydraulic conductivity be adjusted to
account for the differences in density and viscosity of PCE relative to water (Pankow
and Cherry, 1996). As an example, the saturated hydraulic conductivity of water

TABLE 5.1
Saturated Hydraulic Conductivity of Concrete for Non-Water Liquids
Compound Saturated Hydraulic Conductivity (K) for Concrete
(cm/sec)
Water 1 ¥ 10–10
Trichloroethane (TCA) 6 ¥ 10–9
Trichloroethylene (TCE) 4 ¥ 10–9
Tetrachloroethylene (PCE) 6 ¥ 10–9
Freon-111 3 ¥ 10–9
Freon-113 (1,1,2-trichlorotrifluoroethane) 4 ¥ 10–9
Methylene chloride 3 ¥ 10–9
Methylethyl ketone (MEK) 5 ¥ 10–9
Xylene 9 ¥ 10–9
Toluene 7 ¥ 10–9
Phenol 1.15 ¥ 10–7
through a mature, good-quality concrete is about 10–10 cm/sec. (Norton et al., 1931;
Whiting et al., 1988). This value is corrected using the following definition of
hydraulic conductivity:
K = krwg/mw (Eq. 5.1)
where
K = intrinsic permeability.
rw = fluid density.
g = gravitational constant (980.7 cm/sec2).
mw = fluid viscosity.
and
k = K (mw/rwg) (Eq. 5.2)
Table 5.1 lists conversions for non-water liquids assuming a saturated hydraulic
conductivity of concrete to water of 10–10 cm/sec. The liquid thickness on the
pavement and the duration of time that the liquid is in contact with the pavement are
additional model variables. If a trichloroethylene release occurs on a warm sunny day
or in a building with forced air, evaporation is rapid. As a consequence, little liquid
is available to initiate movement into the pavement. If trichloroethylene accumulates
in a blind concrete sump/neutralization pit or clarifier, the trichloroethylene (TCE)
may reside for a sufficient period of time with a significant DNAPL hydraulic head
to allow penetration into concrete.
Numerous models are available to calculate the rate of transport of a liquid
through pavement. For saturated flow, a one-dimensional expression for the vertical

FIGURE 5.2 Difference between saturated and unsaturated hydraulic conductivity values.
transport of the liquid using Darcy’s Law is available. This expression defines the
downward velocity (v) of the liquid as being equal to the downward flux (q) divided
by the porosity of the pavement. The downward flux is the saturated hydraulic
conductivity multiplied by the vertical gradient. Porosity values for paved materials
are measured directly or obtained from the literature. This calculation results in a
value in units of length over time that is divided into the pavement thickness to
estimate the transport time. This approach does not consider the transient nature of
the spill in which liquid thickness is changed due to evaporative loss.
Pavement transport models that use Darcy’s Law assume that the pavement is
saturated with liquid prior to the release. If the pavement is unsaturated, liquid
transport is dominated by unsaturated flow resulting in contaminant velocities sev-
eral times slower than for saturated flow. The importance of moisture content on
unsaturated hydraulic conductivity relative to saturated flow conditions (100% satu-
rated) is shown in Figure 5.2.
For unsaturated flow, an equation analogous to Darcy’s equation called the Richard’s
equation is used (Richards, 1931). A one-dimensional expression of this equation is
C(∂y/∂t) = ∂/∂z(K∂y/∂z) + ∂K/∂z (Eq. 5.3)
where
C = the specific water capacity or change in water content in a unit volume of soil per
unit change in the moisture content.
y = suction head (i.e., matric potential).
K = unsaturated hydraulic conductivity.

TABLE 5.2
Vapor Density of Selected Compounds
Compound Vapor Density Relative to Air
Gasoline 4.0
Benzene 3.0
Xylene 4.0
Vinyl chloride (VC) 3.0
Methyl-tertiary-butyl-ether (MTBE) 3.0
If the pavement is partially or fully water saturated and a hydrophobic fluid such as
trichloroethylene is released, the pore water in the pavement will repel the trichloro-
ethylene. While the extent of repulsion is difficult to quantify, the net result is some
degree of trichloroethylene retardation.
5.3 VAPOR TRANSPORT

THROUGH PAVEMENT
Gaseous diffusion through pavement can be more rapid than liquid transport,
assuming that no cracks or preferential pathways are present. The development of
a model to estimate vapor velocity through pavement requires the following infor-
mation:
• Vapor density and pressure of the contaminant

• Whether the vapor source is constant or transient above the pavement
• Henry’s Law constant of the contaminant
• Pavement thickness, porosity, and moisture content
• Concentration of the vapor above the pavement
• Concentration of the vapor within and below the pavement prior to the spill
The vapor density of the compound diffusing through the pavement is a key variable.
The vapor density is approximately equal to the molecular weight (MW) of the
compound divided by the molecular weight of air (29). The molecular weight of PCE
is about 166 g/mol, so the vapor density is 166/29 = 5.7. Table 5.2 lists vapor
densities of common compounds relative to air (Montgomery 1991; Pankow and
Cherry, 1996).
The value in knowing the vapor density of a volatile compound is that it provides
a qualitative basis to determine if a sufficient period of time has occurred to allow
the vapor to permeate through a paved surface; therefore, the topography of the paved

surface is required to determine if features exist to allow accumulation of the vapor.
Vapor degreasers, for example, are often set in a concrete catch basin to capture any
liquid spills. While cement catch basins are effective at mitigating liquid spills, they
exacerbate the potential for vapor transport through the concrete because they act as
an accumulator for the solvent vapor. The catch basin also minimizes the dilution of
the vapor with the atmosphere. Soil samples collected under degreaser catch basins
are often non-detect for chlorinated solvents while soil vapor concentrations are high.
An explanation for this observation is the presence of a vapor cloud in the soil
(Hartman 1999). The significance of vapor clouds is that they migrate through the
subsurface and can potentially contribute to groundwater contamination. Using the
effective diffusion coefficient for the compound approximates the transport rate of
a vapor cloud through soil. For many vapors, this value is about 0.1 cm2/sec. A
general approximation is that the soil porosity reduces the gaseous diffusivity by a
factor of 10. For many organic vapors, the gaseous diffusion coefficient is approxi-
mated as 0.01 cm2/sec. A rule-of-thumb calculation for the distance a vapor cloud
moves through soil for many volatile compounds is estimated by Equation 5.4
(Hartman, 1997):
Distance = (2)(0.01 cm2/sec ¥ 31,536,000)1/2 = 800 cm = 25 ft (Eq. 5.4)
A more rigorous approach to this problem is via a differential equation for the
unsteady, diffusive radial flow of vapor from a source (Cohen et al., 1993):
∂2Ca/∂r2 + [1/r(∂Ca/∂r)] = (RaD*)(∂Ca/∂t) (Eq. 5.5)
where the air-filled porosity (na) is assumed to be constant (see Equation 5.7), Ra is
the soil vapor retardation coefficient, Ca is the computed concentration of the vapor
in air, and r is the source radius. The effective diffusion coefficient, D* (for TCE, 3.2
¥ 10–6 m2/sec; for PCE, 0.072 cm2/sec) (Lyman et al., 1982) is equal to:
D* = Dta (Eq. 5.6)
where ta = n a2.333/n2t, n2t is the total soil porosity which is the sum of the air-filled
porosity and the volumetric water content (Millington, 1959), and the soil vapor
retardation factor (Ra) is determined by:
Ra = 1 + nw/(naKH) + rbKd/(naKH) (Eq. 5.7)
where nw is the bulk water content, na is the air-filled soil porosity, rb is the soil bulk
density, Kd is the distribution coefficient, and KH is the dimensionless Henry’s Law
constant.
Numerous vapor transport equations are available to estimate the travel time of
vapor through pavement (Crank, 1985; McCoy and Roltson, 1992). These equations
describe specific conditions that best represent the events associated with the vapor
release. Appendix A provides a sample calculation for the vapor transport of PCE
through a concrete pavement.

5.4 CONTAMINANT TRANSPORT IN SOIL
If a liquid has penetrated the pavement, estimated transport times for the contaminant
can be calculated for the second zone (soil). Variables used to perform this calcula-
tion include:
• Saturated hydraulic conductivity and porosity of the soil
• Variability of vertical vs. lateral hydraulic conductivity
• Presence of lower permeability horizons such as clay
• Fluid properties (density, viscosity, etc.)
• Depth to groundwater
As with contaminant transport through asphalt or concrete, the hydraulic conductiv-

ity of a contaminant (if in pure form) is adjusted using the relationship for intrinsic
permeability. For diesel, the conversion is described as:
(Kdiesel – Kwater)([mwater/mdiesel][rdiesel/rwater]) (Eq. 5.8)
Assuming that diesel viscosity is 0.042 cP (water = 0.1 cP) and diesel density is 0.84
g/cm3 (water = 1.0 g/cm3), then Equation 5.8 yields an expression that describes the
saturated hydraulic conductivity of diesel through a soil as equal to about 0.20 the
velocity of water; therefore, diesel travels slower than water through this soil. If
differences in the viscosity and density of diesel are not considered, the calculated
transport time using the hydraulic conductivity for water overestimates the rate of
diesel transport.
Numerous equations exist to describe contaminant transport through soil (Ghadiri
et al., 1992; Selim et al., 1998). A common equation for the one-dimensional
transport of a single component via advection and diffusion in the unsaturated zone
is described by Equation 5.9 (Jury and Roth, 1990; Jury and Sposito, 1985; Jury et
al., 1986).
Rl∂Cl/∂t = Du ∂2Cl/∂z2 – V∂Cl/∂z – lmRlCl (Eq. 5.9)
where
Rl = liquid retardation coefficient.
Cl = pore water concentration in the vadose zone.
Du = effective diffusion coefficient.
lm = decay constant.
V = infiltration rate.
The retardation coefficient (Rl) is estimated by:
Rl = rbuKdu + qm + (fm + qm) KH (Eq. 5.10)

where
rbu = soil bulk density.

Kdu = distribution coefficient for the contaminant of interest.

qm = soil moisture content.
fm = soil porosity.
KH = Henry’s Law constant for the contaminant of interest.
The distribution coefficient (Kdu) of the contaminant of interest can be estimated via:
Kdu = 0.6 foc,u Kow (Eq. 5.11)
where
foc,u = fraction of organic carbon in the soil.

Kow = octanol-partition coefficient of the contaminant of interest.
The degradation rate constant can be estimated by Equation 5.12:
lm = ln(2)/T1/2 m (Eq. 5.12)
where T1/2 m is the degradation half-life of the contaminant of interest. The effective
diffusion coefficient is
Du = tL DLM + KH tG DGM (Eq. 5.13)
where
tL = soil tortuosity to water diffusion.

DLM = molecular diffusion coefficient in water.
tG = soil tortuosity to air diffusion.
DGM = molecular diffusion coefficient in air.
The tortuosity associated with the diffusion of a compound in water and air is
described by Equation 5.14 (Millington and Quirk, 1959):
tL = qm10/3/fm2 and tG = (fm – qm)10/3/fm2 (Eq. 5.14)
For a non-aqueous phase liquid (NAPL), the NAPL velocity (nu) for the vertical
migration via a constant rate release is approximated by Equation 5.15 (Parker,
1989):
nu = (rro kro Kn)/(hro fa S) (Eq. 5.15)
where
rro = specific gravity of the NAPL.

kro = relative permeability of the NAPL.
Kn = vertical saturated hydraulic conductivity to water.
hro = the light non-aqueous phase liquid (LNAPL)-water viscosity ratio.
fa = the initial air-filled porosity of the soil.
S = the effective NAPL saturation behind the infiltration front.

The travel time for the LNAPL to move through the unsaturated zone is therefore
equal to the distance from the source to the water table divided by the NAPL velocity
(nu).
A question that arises in environmental litigation is when did the contamination
enter the groundwater? This question is answered by using Darcy’s Law. An example
is the release of diesel from an underground storage tank. If the diesel flows through
more than one soil type, a transport rate through each soil horizon is required. Input
variables include the saturated hydraulic conductivity of the soil, soil porosity, and
the hydraulic gradient for each horizon. Assuming a knowledge of the underlying
soils (pea gravel and mixed sands) and the saturated hydraulic conductivity of these
soils between the tank bottom and the groundwater table (ª24.5 ft) and that Darcy’s
Law is valid, Table 5.3 is an example of the tabulated results. The total travel time
for the release of diesel into the soil is about 225 days. An issue regarding the results
in Table 5.3 is that it offers a unique solution. A more defensible approach is the use
of a range of input parameter values (primarily the saturated hydraulic conductivity
value) (Morrison, 1998).
A novel approach for identifying when a DNAPL has been released into a low-
permeability layer of base of an aquifer has been reported (Parker and Cherry, 1995).
Soil cores collected at discrete distances from the DNAPL provide the basis for
identifying the concentration of the dissolved contaminant. Diffusion calculations are
then employed to estimate the length of time that diffusion has occurred and therefore
the time since the DNAPL was immobilized. Assumptions include the premise that
low-permeability layers of silt and clay underlying the perched DNAPLs have
sufficient porosity to allow, without advection, migration of the dissolved constitu-
ents into the soils via molecular diffusion and that the location of the DNAPL is
precisely known.
5.4.1 CHALLENGES TO CONTAMINANT

TRANSPORT MODELS FOR SOIL
Transport mechanisms and pathways exist that are rarely included in contaminant
transport models. Artificial examples include dry wells, foundation borings, utility
trenches, sewer or stormwater backfill, cisterns, and septic lines. Natural preferential
pathways include high-permeability soils, mechanical disturbance, and cosolvent
transport. Table 5.4 lists some of these pathways and common computer model
variables along with their impact on contaminant transport.
5.4.2 COLLOIDAL TRANSPORT

Colloidal transport is a mechanism by which a hydrophobic compound preferentially
sorbs to a colloid particle in water and is transported to depth. Colloids are generally
regarded as materials up to 10 mm (10–6 m) in size. Colloids exist as suspended
organic and inorganic matter in soil or aquifers. In sandy aquifers, the predominant

TABLE 5.3
Summary of Transport Calculations for Individual Soil Layers
Kwater Thickness Kdiesela Vb Travel
Layer (cm/sec) (ft) (cm/sec) (cm/sec) Time
Pea gravel 0.1 1.0 0.02 20 1.5 sec

Sand 1.1 ¥ 10–4 7.75 2.2 ¥ 10–5 7.3 ¥ 10–5 900 hr
Sand 6.6 ¥ 10–5 10.75 1.3 ¥ 10–5 4.3 ¥ 10–5 2100 hr
Sand 2.7 ¥ 10–5 5.0 5.4 ¥ 10–6 1.8 ¥ 10–5 2400 hr
Total 225 days
a Kdiesel – Kwater (mwater/mdiesel)(rdiesel/rwater), where mwater = 0.01 cP and rwater = 1.0 g/cm3 and
mdiesel and rdiesel = 0.042 cP and 0.84 g/cm3, respectively.
b Porosity = 0.30 and dH/dL = 1.0.
colloids that are mobile range in size from about 0.1 to 10 mm. The importance of
colloidal particles on contaminant mobility diminishes as the octanol-water partition
coefficient (Kow) decreases.
The mass of contaminants associated with colloids may be significant. In a study
of PCBs and polycyclic aromatic hydrocarbons associated with different size frac-
tions of groundwater colloids underlying an abandoned landfill, over two thirds of
the total amount of contaminants were associated with colloids greater than 1.3 nm
(1 nm = 10–9 m) (Villholth, 1999). Another example is the transport of polycyclic
aromatic hydrocarbons via colloidal transport, which was examined in two creosote-
contaminated aquifers on Zealand island in Denmark. The mobile colloids were
dominated by clay, iron oxides, iron sulfides, and quartz particles. The researchers
concluded that the sorption was associated with the organic content of the colloids.
Creosote-associated contaminants were also found to be associated primarily with
colloids that were larger than 100 nm. These findings indicate that colloid-facilitated
transport of polycyclic aromatic hydrocarbons exists and may be significant. This
transport mechanism is rarely included in a soil or groundwater transport model.
5.4.3 PREFERENTIAL PATHWAYS

Preferential pathways provide a means for dissolved and precipitated phase poly-
meric species and hydrophobic compounds to be adsorbed to colloids and to be
rapidly introduced at depth. Preferential flow pathways include natural and artificial
features such as worm channels, decayed root channels (Plate 5.1*), soil fractures,
swelling and shrinking clays, insect burrows, dry wells (Plate 5.2*), open cisterns,
septic lines, macropores, and highly permeable soil layers. The significance of
preferential flow is that the actual travel time of a compound to the water table is
* Plates 5.1 and 5.2 appear at the end of the chapter.

TABLE 5.4
Variables of Contaminant Transport in Soil and their Impact on
Contaminant Velocity
Soil Variables
Impacting Transport Comments and Impacts
Soil porosity Changes in soil porosity can result in multiple velocities with depth
through the soil column. Coarse-grained materials tend to have a
higher porosity than fine-grained materials. The porosity of dense
crystalline rocks, tight shales, caliche, and unweathered limestone
may range from less than 0.01 to 0.10.
Volume of release Impacts whether saturated or unsaturated flow dominates, the time
required for residual saturation to occur, and the degree of
contaminant spreading.
Saturated vs. unsaturated flow Unsaturated flow is slower than saturated flow (see Figure 5.2).
Moisture content with depth determines the hydraulic gradient and
therefore the rate of transport in unsaturated flow conditions.
Fingering Impedes flow and introduces uncertainty regarding contaminant
velocity and the geometry of the contaminant plume.
Preferential pathways Increases the flow rate, time-dependent spreading.
Pavement composition, Impedes or accelerates flow.
thickness, presence of
cracks, presence or absence
of surface coatings
and/or expansion joints.
Surface spill volume, Determines whether sufficient liquid is available
duration, evaporation, for flow to occur into the subsurface.
surface area and thickness
of ponded liquid
Depth to groundwater at time Impacts the time required for entry into the groundwater.
of release
Cosolvation Increases the depth of penetration of otherwise low-mobility
compounds.
Chemical mixture and Impact liquid density, viscosity, and saturated or unsaturated
physical characteristics hydraulic conductivity values of the fluid.
Changes in soil redox and/or pH Increases or decreases the depth of penetration of otherwise low-
mobility contaminants, such as metals.
order of minutes or hours rather than days or months (Barcelona and Morrison,
1988).
The term “preferential flow” encompasses a range of processes with similar
consequences for contaminant transport. The term implies that infiltrating liquid
does not have sufficient time to equilibrate with the slowly moving water residing

in the soil (Jarvis, 1998). Preferential flow includes the following transport pro-
cesses: finger flow (also viscous flow) (Bisdom et al., 1993; Glass and Nicholl,
1996), funnel flow (Diment and Watson, 1985; Hill and Parlange, 1972; Kung,
1990a,b; Philip, 1975), and macropore flow (Bouma, 1981; Morrison and Lowry,
1990; White, 1985).
Finger flow (also dissolution fingering) is initiated by small- and large-scale
heterogeneities in soil such as a textural interface between a coarse-textured sand that
underlies a silt (Fishman, 1998; Miller et al., 1998). The term “finger flow” refers to
the splitting of an otherwise uniform flow pattern into fingers. These fingers are
associated with soil air compression encountered where a finer soil overlies a coarse
and dry sand layer. The contact interface between the contaminant and the water in
the capillary fringe results in an instability (see Plate 5.3*). The spacing and fre-
quency of these fingers are difficult to predict, although they are at the centimeter
scale and are sensitive to the initial water content (Imhoff et al., 1996; Ritsema and
Dekker, 1995; Wei and Ortoleva, 1990).
Numerical simulations of fingering suggest that transverse dispersion is a signifi-
cant impact on the formation and anatomy of fingers. Aspects of the fingering
phenomenon that introduce uncertainty when modeling contaminants such as NAPLs
include (Miller et al., 1998):
• The effect of dispersion

• The impact of heterogeneity on porous media properties and residual NAPL
saturation
• The validity of fingering when a NAPL solution is flushed with chemical agents
such as surfactants and alcohols
• Incorporation of the impacts of fingering on NAPL phase mass transfer models
when the model is discretized at scales larger than the centimeter scale
Funnel flow occurs in soils with lenses and admixtures of particle sizes. For a
saturated soil, the most coarse sand fraction is the preferred flow region; for unsat-
urated flow, finer textured materials are more conductive. Examination of textural
descriptions on boring logs and contaminant concentration depth profiles can provide
insight to determine if contaminant transport via funnel flow is a viable transport
mechanism.
A macropore is a continuous soil pore that is significantly larger than the inter-
granular or inter-aggregate soil pores (micropores). In general, a macropore is one
order of magnitude greater in dimension than the indigenous soil micropores. While
a macropore may constitute only 0.001 to 0.05% of the total soil volume, it may
conduct a majority of an infiltrating liquid.
Plate 5.4* illustrates the impact of liquid transport via macropores in a mature soil
in the United Kingdom. Hydrated gypsum was ponded on the ground surface and
drained into the underlying soil via macropores. The gypsum then dehydrated,
leaving the macropore channels clearly visible.

5.4.4 COSOLVENT TRANSPORT
Hydrophobic compounds are generally considered to be immobile in the soil profile,
due primarily to their low water solubility and their tendency to be adsorbed by clay,
organic matter, and mineral surfaces (Odermatt et al., 1993). Soil contaminant
transport models tend to predict low velocities for these compounds. Cosolvation of
these compounds with a fluid can introduce these contaminants at depth, but this
phenomenon is rarely included in contaminant transport models. Contaminants such
as polychlorinated biphenyls (PCBs) or DDT can be re-mobilized by the preferential
dissolution of the PCBs into a solvent released into the same soil column (Morrison
and Newell, 1999). A variation of this scenario is the preferential dissolution of an
immobile chemical into a solvent prior to its release (e.g., PCBs dissolved in a
dielectric fluid).
A similar transport mechanism occurs when a contaminant sorbed by a soil is
washed with a liquid that re-mobilizes the compound. An example is the presence of
copper bound in soil under a leaking neutralization pit. Low pH wastewaters leaking
through an expansion joint and contacting the precipitated copper will remobilize and
transport the copper with the low pH wastewaters to depth until the acidic wastewater
and copper solution is buffered and the copper re-precipitates at a lower depth.
5.5 CONTAMINANT TRANSPORT

IN GROUNDWATER
In environmental litigation, groundwater models are usually used in a predictive,

interpretative, or generic application. Predictive models forecast the future of some
action and require calibration. Interpretative models are used to study aquifer and
contaminant dynamics. Generic models are used to analyze flow in hypothetical
systems, such as for regulatory purposes.
The transport of a contaminant in groundwater is controlled by the aquifer
parameters (advective model) and by physical and chemical processes that are
simulated in the contaminant transport portion of the model. The advective portion
of a contaminant transport model requires measured groundwater elevations. The
primary hydraulic forces in an advective model are the main driving forces, natural
transient forces, and manmade transient forces. An example of an advective model
is MODFLOW. Since its release by the U.S. Geological Survey in the early 1980s,
MODFLOW has become the international standard code for three-dimensional,
finite-difference groundwater flow modeling (McDonald and Harbaugh, 1988).
Mass transport models such as MT3D (Modular Transport Three-Dimensional)
are coupled to an advective model such as MODFLOW to simulate the three-
dimensional advection, dispersion, and chemical transformations of contaminants
(Zeng, 1993, 1994). MT3D is available commercially and in the public domain (the
U.S. Environmental Protection Agency provided partial support for the development
of MT3D).

FIGURE 5.3 Effects of aquifer physical parameters on contaminant transport.
The selection of a model is made in large part by identifying the primary

processes controlling contaminant transport that the user intends to simulate. These
processes include aquifer physical parameters, the initial contaminant concentra-
tions, physical processes, chemical attenuation, and biological attenuation. Figures
5.3 and 5.4 summarize the impact of these hydraulic, physical, chemical, and biologi-
cal processes on contaminant transport in groundwater (Szecsody, 1992). If the
model intends to simulate any or all of these processes, the value assigned and the
accuracy of the number should be fully evaluated.
The developmental progression of a model used for contaminant transport in-
cludes the following steps:
• Identification of the goal of the modeling

• Creation of a conceptual model
• Selection of the governing equations and computer code
• Adjustment of the conceptual model for modeling
• Model calibration with field measurements
• Sensitivity analysis to establish the effect of input parameters variations on model
output
• Model verification via calibrated of parameter values and stresses
• Performance of computer simulations or runs to predict future events

FIGURE 5.4 Effects of physical, chemical, and biological processes on contaminant transport.
• Post-auditing to test the reliability of the simulations by comparing simulated

results with new acquired field measurements
• Model calibrations to reflect changes in the post-audit step
5.5.1 TYPES OF GROUNDWATER MODELS

Three types of groundwater models are physical or scale models, analog, and
mathematical models. Physical or scale models include physical experiments using
boxes filled with a representative media into which fluids are introduced. Analog
models use materials such as electrical circuits to represent a groundwater system.
While popular prior to the advent of personal computing, they are seldom used.
Mathematical models are divided into three types: analytical, numerical, and analytic
element and contain the following components:
• Definition of the site boundary conditions

• Equation(s) describing the contaminant mass balance within the modeled boundary

• Equations that relate contaminant flux to relevant variables
• Equation(s) that describe the contaminant and hydrogeological conditions at an
initial time
• Equation(s) that describe the interaction of the contaminant within the prescribed
boundary conditions
Analytic element models are adaptations of established analytical techniques

whereby several analytic functions are solved simultaneously. Analytical models use
closed-form equations or solutions to the partial differential equations governing
groundwater flow (Bear 1979; Van Genuchten and Alves, 1982). An analytical
model is easily solved. This simplification is a limitation, as aquifer homogeneity,
isotropy, and an infinite horizontal extent are assumed. For complex hydrogeological
settings, they are usually inadequate.
A numerical flow model solves partial differential equations governing flow at
discrete points or nodes within a groundwater system. Numerical models require
elaborate computational methods to solve flow equations at a discrete set of points
within an aquifer(s). Examples include:
• Finite-difference
• Finite-element
• Boundary-element
• Particle tracking: method of characteristics (MOC), modified method of character-
istics (MMOC), and random walk
• Integrated finite-difference models
Numerical models can be converted to a format amenable to visualization. Because

the physical properties at each point in the model can be varied, numerical methods
can solve flow problems in complex hydrogeological systems. Features such as
biodegradation, radioactive decay, sources, and sinks can be included in the
model.
Analytic element models combine aspects of analytical and numerical models. A
set of simultaneous equations with an equal number of unknowns are solved using
numerical techniques, while analytic functions are superimposed onto a particular
site feature, such as a river or pumping groundwater well. An advantage of an
analytic element model is that a small portion of the site can be intensively modeled
or multiple aquifer systems can be examined. Most analytic element models are
proprietary.
Groundwater models can provide greater understanding of a flow system and
contaminant transport. Groundwater models are commonly encountered in insurance
coverage cases, in litigation to demonstrate that a potentially responsible party has
contributed to the contamination of a Superfund site, and to illustrate long-term
impacts of an unremediated contaminant plume over time. The following is a brief
outline of the use of groundwater modeling and its application in environmental
litigation. For a further understanding, numerous texts on groundwater modeling are
available (Freeze and Cherry, 1979; Zeng and Bennett, 1995).

The foundation of groundwater modeling is the advection-dispersion equation.
Governing assumptions are that the porous medium is homogeneous and isotropic,
the medium is saturated with a fluid, and Darcy’s Law is valid. If these assumptions
are violated, the applicability or precision of the model in predicting contaminant
flow is compromised to some degree.
The selection of the contaminant transport model that is appropriate for the
particular site is important and should be carefully considered when evaluating a
contaminant groundwater model. If the conceptual model does not represent the
relevant flow and contaminant transport phenomena, the subsequent modeling effort
is wasted. This is not to say that misuses may not occur during any phase of the
modeling process. Common misuses and mistakes associated with modeling include
(Bear et al., 1992; Mercer, 1991):
1. Improper conceptualization of a groundwater model relative to the site — for

example, selection of a three-dimensional model when a two-dimensional model is
sufficient can lead to complications in the modeling effort. Incorrect assumptions
concerning the significant contaminant processes, such as contaminant transport,
which are then incorporated into the model can magnify the inaccuracy of the
model. Disregarding the importance of retardation of a chemical or discounting the
impact of biological transformations are other examples.
2. Selection of an inappropriate computer code for solving the problem — it is not
uncommon for a consultant to select a computer code that is too versatile or
powerful for the site and the availability of input parameters.
3. Improper model applications usually results in the selection of improper values for
modeling. Examples include the misrepresentation of aquitards in a multi-level
system or identifying and modeling contaminant transport in a series of aquifers
which are actually one hydraulically connected aquifer.
4. Misinterpretation of modeling results occurs if mass balance is not achieved or if
calibration of the modeling results with field data is not performed. The end result
of the model is the ability to simulate contaminant transport based on actual field
measurements.
5. Uncertainty is posed by the inability to accurately model various sinks (irrigation
wells, spring discharge, etc.) and sources (rivers, lakes, temporal irrigation, or
watering, etc.) over time that impact model precision.
Inappropriate model selection is one of the most common shortcomings. It is

useful to direct the expert witness to prepare a table describing the model and then
compare it to the site. Differences in the capabilities of two computer models are
summarized in Table 5.5.
The SWIFT model permits a great deal more model complexity and flexibility
than does the QUICKFLOW model. This is because the two models address the
groundwater flow systems in different ways. The analytical element model
QUICKFLOW uses hand-derived analytical solutions which are then incorporated
into the program. These analytical solutions are derived for simplified flow situa-
tions; otherwise, the mathematics become too difficult to solve. The numerical model
SWIFT permits greater complexity because the flow and transport equations are
solved by computer code.

TABLE 5.5
Comparison of SWIFT III and QUICKFLOW Computer Models
SWIFT III QUICKFLOW
Solves for both groundwater flow and transport Solves for groundwater flow only
of contaminants
Three-dimensional Two-dimensional
Allows vertical groundwater flow Does not allow for vertical groundwater flow
Numerical model (finite difference grid) Analytical model (continuous analytical
elements)
Allows multiple layers Single layer only
Allows partially penetrating wells Assumes fully penetrating wells
Pumping rates from wells can vary over time Pumping rates in all wells are constant over
time
Complex starting head distribution allowed Assumes uniform regional flow
Complex hydraulic conductivity, porosity, and Aquifer must have a uniform hydraulic
storativity distributions allowed conductivity, porosity, and storativity
Boundary conditions are required Reference head is required
5.5.2 SELECTION OF BOUNDARY CONDITIONS,

GRIDS, AND MASS LOADING RATES
Boundary conditions are required whenever a computer model is created. For a
program such as MODFLOW, general head boundaries are used to define the lateral
boundary conditions that define the flux of water recharge or discharge along these
boundaries. The boundary conditions are a function of the hydraulic conductivity,
groundwater flow gradient, and the absolute difference in water level elevations
between the block elements located on the lateral boundaries with locations located
outside of the model grid.
Common specified boundary conditions include no-flow, specified flux, and
fixed head boundaries. While model boundary conditions are fixed and cannot be
changed during a single simulation, they can be adjusted between simulations. It is
conceptually undesirable to alter the boundary flux conditions to assist in calibration
of each stress period vs. accounting for these differences by adjustments in dynamic
features such as pumping wells or recharge of surface water bodies located within the
grid. The impact of a model boundary can be examined if all model input files and
software are available to reproduce the modeling result using different boundary
conditions.
Grid selection is important. For numerical models, finite difference and finite
element grids are used, while block-centered and mesh-centered grids are used for
finite element grids. Finite element grids are generally more versatile than finite
difference grids. For a finite difference model, examine the grid density to ascertain
whether the data support finer mesh nodes or whether higher grid densities are
selected in areas of interest but which contain insufficient data to warrant a higher
grid density.

In finite-difference modeling, numerical dispersion is inherent due to errors
associated with model design, especially in areas of varying grid size. The three-
dimensional block size selected must be examined to determine the relative horizon-
tal and vertical element aspect ratio. Aspect ratios less than four are generally
acceptable; horizontal and vertical aspect ratios that are greater than four become
more susceptible to numerical dispersion. Minimization of numerical dispersion in
the model grid used for solute transport is accomplished by selecting a Peclet
number (Pe = DL/a) where DL is the length of the elemental box and a is the
dispersion coefficient (£1). Grids designed with a DL less than 4a are recom-
mended; if the model violates this value, the model is susceptible to considerable
numerical errors.
For multiple-layered models, determine whether the vertical gradients between
the layers are measured or estimated. To confirm measured vertical gradients, divide
the head difference between a shallow and deep well by the vertical distance between
the bottom of both well screens. A negative value indicates a downward flow
component. If the vertical gradients are estimated, attempt to determine the level of
uncertainty associated with these values and their overall impact on solute transport
between layers.
For contaminant transport models, contaminant loading rates at sources located
within a grid are arbitrary. Issues regarding the validity of a particular loading rate
and its location include determining whether:
• The soil and groundwater chemistry justify the selected location and input rate
• The mass loading rate is continuous or is transient in response to groundwater
fluctuations or remediation activities
• The start date for the mass loading is consistent with the operational history of the
contributing surface sources
Most contaminant transport models automatically perform a mass balance, and this
output should be obtained. A significant error in the mass balance calculation
indicates that the solution is numerically imprecise to some degree.
5.5.3 SOFTWARE APPLICABILITY

An individual familiar with contaminant transport models is needed to ascertain if the
appropriate computer software was selected and if it was adequate and/or capable of
modeling the physical system of interest. In 1984, for example, there were in excess
of 400 groundwater flow and transport models around the world (van der Heijde,
1984). A contaminant transport model used to create a trial exhibit should be
sufficiently complex to account for all relevant physical processes. Model complex-
ity is determined by the quality of the data available for its design and verification.
An example of inappropriate model selection is using a simple two-dimensional
model for a complex three-dimensional system. Conversely, a complex three-dimen-
sional model may be selected that is overpowered relative to the available data.
Model selection considerations include the following issues (Cleary, 1995):

• Select a model with the prestige of a state or governmental agency which has a
substantial published history in peer-reviewed journals and has already been tested
in court. If the model code is obscure, thoroughly scrutinize the code.
• The model should include a user’s manual listing its governing assumptions,
advantages, and capabilities.
• The model can be validated against analytical solutions for comparison. The
analytical solution should have the same number of space dimensions as the
numerical model.
• The model should be benchmarked against a numerical code.
• The model should have an available source code.
• The selection of a three-dimensional model always has an advantage of better
representing reality than a two-dimensional approximation.
The model simulation ultimately selected to create a trial still or animation should
be evaluated in the context of all the simulations. It is not unusual for hundreds of
simulations to be performed until a simulation is obtained for use as evidence for
a particular allegation. Discarded simulations should be obtained and compared
with the selected simulation so that the legitimacy of the selected simulation can be
evaluated.
5.6 APPLICATION OF GROUNDWATER

MODELING IN ENVIRONMENTAL
LITIGATION
The rate of contaminant transport in groundwater is often alleged to provide a basis

for determining the source and the length of time required for the contaminant plume
to reach its observed dimensions. Groundwater models used in this context are
known as confirmation or reverse models (Morrison et al., 1999a,b).
5.6.1 CONFIRMATION MODELS

Confirmation models are used with other corroborative evidence to (1) confirm the
time when a reported release occurred, and/or (2) examine the consistency of an
observed contaminant plume with contaminant release information (i.e., rate of
release, location, and duration) (Morrison, 1999a). Model parameters are adjusted so
that model predictions agree with measured hydraulic head and contaminant concen-
trations at specific monitoring well locations. If the distance between the leading
edge of a contaminant plume and the source is known, this distance provides insight
into the long-term average groundwater flow rate and direction. A common legal
application of a confirmation model is to verify deposition testimony or testing
concerning the volume and/or direction of a release (Hughes v. Beagley, 1995;
Hughes v. Hartford, 1994).
A confirmation model assumes that a release occurred at a specific point in time.
Model parameters are adjusted so that model predictions agree with measured water

and contaminant levels. Plate 5.5* is an example of a confirmation model where the
presence of TCE in groundwater is correlated to an estimated release approximately
25 years prior to the TCE plume observed in 1985. In this figure, hydraulic and
groundwater chemical data were only available from 1980 to 1985; therefore, ground-
water and chemical distributions from 1970 to 1980 are inferred. A variation to this
figure would be hydraulic and chemical data available from 1970 to 1985. The
observed contaminant distribution from 1970 would then be simulated forward to
1985 to verify the consistency of the testimony concerning the timing of a release
with the contaminant plume geometry.
5.6.2 REVERSE MODELS

Reverse (also called backward extrapolation and backcasting) models are used to
predict, in reverse, when and where a contaminant entered the groundwater (Bois and
Luther, 1996; Kezsbom and Goldman, 1991; Kornfeld, 1992; Morrison and Erickson,
1995). Reverse modeling is distinguished from confirmation models in that detailed
information about the contaminant release are unknown. In its simplest application,
reverse modeling relies upon the observed length of a contaminant plume and a
representative groundwater velocity to estimate the timing of a release. As with
confirmation modeling, this approach is predominantly used in insurance litigation
to identify the timing of an alleged release of a contaminant or to associate a
particular release with detection of the released contaminant in groundwater (Carrier
Corp. v. Detrex, 1996; Sterling v. Velsicol Chemical Corp.; 1988).
5.6.3 HYDROGEOLOGIC VARIABLES

Confirmation and reverse models rely on hydrogeologic and contaminant character-
istics to estimate the origin and timing of a release. Hydrogeologic variables include
the following:
• Saturated hydraulic conductivity

• Groundwater gradient
• Soil porosity
• Horizontal and transverse dispersivity
The reliability of these values depends on whether they are measured in the field or
laboratory or are from published values.
Of the hydrogeologic parameters, the saturated hydraulic conductivity value
introduces significant variability in the computer simulations (Rong et al., 1998). It
is generally recognized that the most representative measurements for determining the
hydraulic conductivity of a formation are obtained with a pump test. Hydraulic con-
ductivity values that rely upon slug tests, sieve analyses, and laboratory measurements

of soil cores are considered less reliable. The values obtained from a slug test are
generally reliable to about one or more orders of magnitude, with its accuracy
increasing for less-permeable aquifers. Because the slope of the groundwater table
and changes in soil porosity differ significantly with soil texture, a scientifically
defensible approach is to use a range of values for the saturated hydraulic conduc-
tivity, hydraulic gradient, and soil porosity.
The selected hydraulic gradient value can vary in time and distance. The ground-
water gradient can vary considerably in both direction and gradient with distance. If
regional or vicinity-wide data are relied upon to define the hydraulic gradient vs. site
measurements, considerable differences can occur. Sources of localized variations in
the gradient include pumping wells, rivers, streams, and groundwater recharge, or
spreading basins. If pumping wells in the immediate vicinity of the site are present,
collecting the extraction rates and representative transmissivity values for the aquifer
and calculating the radius of pumping influence are useful to demonstrate the
potential impact of pumping wells on the local gradient. Historical variations in the
hydraulic gradient introduce uncertainty regarding the historical direction of ground-
water flow and hence the time required for the contaminant plume to attain its
measured leading-edge geometry. Typical values range from 0.1 to 0.001.
The soil porosity within an aquifer and with distance can change dramatically.
A representative porosity value, especially on a field scale, is usually a fitted
parameter within a published range of values for the predominant soil type encoun-
tered; as a result, considerable differences in the modeling results can be adjusted by
slight variations in the selected porosity value. Typical porosity values range from
0.25 to 0.50 for unconsolidated soils.
Dispersivity describes the three-dimensional spreading of a contaminant plume
in groundwater with distance. Most contaminant transport models require a horizon-
tal (longitudinal), vertical, and transverse dispersivity value. Longitudinal dispersivity
is caused primarily by differences in groundwater flow through aquifer pores at a
scale less than that used to characterize values of saturated hydraulic conductivity.
Longitudinal dispersivity increases with distance from the source (also known as
macrodispersivity). If a model assumes that the contaminant plume length is only due
to advective flow, the estimated date of the release will be longer than if dispersivity
and advective flows are considered. An expression of longitudinal dispersivity (DL)
is given by Equation 5.16 (Gelhar et al., 1992).
DL = exp [1.6t – 3.795 + 1.774 ln(x) – 0.093 (ln(x)2] (Eq. 5.16)
where
x = travel distance of the compound in groundwater.
t = normalized deviation from the median such that t = 0 is the median; t = ±1 is the
lower and upper 67% confidence limits; t = ±2 is the 95% confidence level, etc.
Another expression for longitudinal dispersivity (ax) is ax = 0.32L0.83 where L

is the scale of the plume length or a characteristic length assumed to be equal to 0.10
of the plume length (20 or 15 m, respectively) (Neumann and Zhang, 1990).

Vertical dispersivity is defined as av = ax/160 (Gelhar et al., 1985). Vertical
dispersivity values are commonly encountered in mathematical expressions used to
describe the vertical extent that a chemical plume will extend in the saturated zone
below the water table from a source in the unsaturated zone. An expression illustrat-
ing this technique is described as (Tetra Tech, Inc., 1993):
Dp = (2avXa)1/2 + H[1 – exp(–XaI/HVsq)] (Eq. 5.17)
where
Dp = penetration depth.
av = vertical dispersivity.
Xa = length of the waste disposal site in the primary groundwater flow direction.
H = aquifer thickness.
I = infiltration rate.
Vs = horizontal seepage velocity.
q = porosity.
Transverse dispersivity controls the dispersion of the contaminant plume in

groundwater in the horizontal direction perpendicular to the direction of flow.
Transverse dispersivity (DT) is primarily controlled by the degree of aquifer hetero-
geneity and can be described as DT = aDL, where values for a range from about 0.05
to 0.5.
In confirmation and reverse modeling, dispersivity is used as one variable to
match the shape of the simulated contaminant plume to the observed plume at
one point in time. Longitudinal dispersivity values used with solute transport
models are commonly in the range of 90 to 300 ft, while horizontal dispersivity
values can be as much as 150 ft. There is little physical evidence for using such large
numbers except to simulate contaminant concentrations that compare favorably
with observed values. In cases where no data exist to estimate dispersivities, the
EPA recommends multiplying the length of the plume by 0.1 to estimate the
horizontal dispersivity (Lallemand-Barres and Peaudecerf, 1978; Wilson, et al.,
1981). Other authors have used probabilistic theory to estimate transverse and
vertical dispersivity as 0.33 and 0.056 times the plume length, respectively (Gelhar
and Axness, 1981, 1983; Gelhar et al., 1992; Salhotra et al., 1993; U.S. EPA,
1985). Dispersivity is also considered to be hysteretic with distance from the
contaminant source. As a result, a simple linear expression for dispersivity intro-
duces some degree of bias.
5.6.4 CONTAMINANT PROPERTIES

Contaminant characteristics that impact the modeled transport of a contaminant
include contaminant density, viscosity, retardation, and biodegradation. Of these
variables, retardation has the greatest impact on contaminant velocity (see Table 1.20
in Chapter 1).

Retardation values generally increase with increasing fractions of organic car-
bon, which increases with the clay content of the soil. If groundwater flow is 6 ft/day
and a selected retardation coefficient for perchloroethylene (PCE) is 2, PCE is
therefore transported at a rate of 3 ft/day. Published values for the retardation of PCE
in sand and gravel aquifers are between 1 (no retardation) and 5 (Barber et al., 1988;
Schwarzenbach et al., 1983). The retardation value for trichloroethylene (TCE) is
reported as being less than 10 and usually between 1 and 2.5. Given the range in
retardation values, these values can be adjusted to correspond to a prescribed time of
release of TCE. In general, predicted retardation coefficients are generally two to five
times lower than measured values (Ball and Roberts, 1991; Curtis, et al., 1986;
MacKay, 1990; MacKay et al., 1986; Mehran et al., 1987). The retardation value of
a selected chemical in groundwater is usually a fitted parameter.
The selected retardation value can also be an artifact of well design and the
purging and sampling processes employed (see Section 3.5 in Chapter 3). Apparent
retardation rates in one study were found to be inconsistent between monitoring
wells, depending upon the saturated screen length, the degree of screen desaturation
during purging, and the distance from the contaminant source (Martin-Hayden and
Robbins, 1997; Robbins 1989). The selection of one retardation factor for a com-
pound for an entire well field may therefore be inappropriate in cases where
concentration averaging is used (see Section 6.3, Chapter 6). These variables may
result in a contaminant plume that appears to be attenuated to some degree being
used for the modeling but which grossly under-represents the extent of the contami-
nant plume due to these monitoring well construction and sampling practices. An
example is the apparent retardation factor that was modeled with variables including
the distance from the contaminant source, screen length, and screen desaturation
during purging. The results indicated that the apparent retardation factor increased
with increasing screen length and degree of purging desaturation and decreased with
the longitudinal distance from the contaminant source (Martin-Hayden and Robbins,
1997).
5.6.5 CHALLENGES TO REVERSE MODELS

The successful review of a reverse model includes an analysis of model parameters
and computer code. Examples of model parameters to be examined include:
• Representativeness of the effective porosity value(s) selected

• Consistency of the groundwater flow direction over time
• Validity of the hydraulic conductivity and/or transmissivity values selected
• Validity of the selected hydraulic gradient values over time and distance from the
release
• Value selected for aquifer thickness
• Assumptions used to determine when and where the contaminant entered the
groundwater
• Horizontal and transverse dispersivity values
• Contaminant retardation and/or degradation rates

FIGURE 5.5 MTBE release scenarios for its use as a tracer to determine the age of a release
and for reverse model calibration. (Adapted from Davidson and Parsons, 1996.)
• Identification of the leading edge of the contaminant plume

• Effect of recharge/discharge rates (if applicable) of water into the system and its
impact on plume geometry and contaminant velocity
Since a reverse model requires an accurate value for the length of the contami-
nant plume, locating the origin of the release and leading edge of the contaminant
plume is required. If the location of the contaminant release into the groundwater
and/or the leading edge of the contaminant plume is unknown or approximated (e.g.,
within ±100 ft relative to a groundwater velocity of 25 ft/yr), significant variations
in the estimated age of the release occurs. Uncertainty can also exist relative to where
the contaminant entered the groundwater, especially if multiple or overlapping
releases occur or if a chemical unique to a release is used as a tracer to date the
release. An example is the case of a gasoline plume that is sampled between 4 and
10 years after a release occurred. MTBE is used as a tracer to date the plume for
purposes of determining a representative groundwater velocity for use in the reverse
model (see Figure 5.5). In the lower panel of Figure 5.5, MTBE is contained in a
second release that overlies a pre-existing release of gasoline without MTBE. While
MTBE provides a tracer for the second release, it does not provide information for
identifying the date of the earlier, non-MTBE-containing gasoline release.
An example of the impact of overlapping surface releases on reverse modeling
is shown in Figure 5.6. If assumptions include a plume length of 600 ft, a ground-
water velocity of 30 ft/yr, and a point source release, then 300 ft divided by 30 ft/yr
yields a release date of 20 years ago. If the contaminant plume is the result of
overlapping point source releases in 1970 and 1980, then the dividing the plume by
contaminant velocity is invalid as illustrated in Figure 5.6.
The measured distance to the leading edge of the contaminant plume is important
in reverse modeling and often requires considerable judgment. Figure 5.7 illustrates
several interpretations of the distance to the leading edge of a contaminant plume. In
plume A, the concentration of 5.5 ppb in the downgradient monitoring well was
selected as the leading edge. In plume B, the laboratory reported the presence of the

FIGURE 5.6 Impact of multiple releases on reverse modeling.
contaminant (J flag) but was unable to report the concentration. An estimated value
of 3 ppb was included on the laboratory sheet as a footnote. In plume C, the <5 ppb
was selected as the leading edge of the plume. Whether A, B, or C is selected
represents significant differences in plume length and therefore the maximum esti-
mate for which contaminants have been in the groundwater.
FIGURE 5.7 TCE in monitoring wells down-gradient of a release. Three interpretations for
defining the leading edge of a contaminant plume in groundwater.

FIGURE 5.8 Potential impacts of monitoring well locations and screen intervals on determin-
ing the leading edge of a contaminant plume.
In addition, more subtle issues such as the spatial locations of the monitoring
wells and the screen interval can introduce considerable variability in defining the
leading edge of the contaminant plume (Figure 5.8). Numerous examples can be
developed to illustrate these limitations, such as:
• Adjust model-input parameters within a reasonable range for those parameters to

produce a result consistent with measured values but inconsistent with the alleged
released date. For example, the distribution of simulated head measurements de-
pends to some degree on the ratio of the recharge rates to saturated hydraulic
conductivity values, not on magnitude. Many recharge and hydraulic conductivity
values are therefore possible to produce a ratio resulting in similar distributions of
modeled heads.
• Identify model uncertainties, such as groundwater direction and velocity, during
time periods when these data are absent and query the author as to the level of
confidence that these parameters are known during this time period.
• Collect water level measurements coincident with an activity, such as a pumping
well, that stresses the aquifer. Use the model to simulate this activity and compare
the actual measurements with those predicted by the model.

FIGURE 5.9 Groundwater models with different retardation values.
• Identify whether the water mass balance is conserved. A well-calibrated model will
exhibit a small difference in the water balance and is often included as output to the
model.
• Evaluate model calibration via the preparation of scattergrams comparing values
for measured heads with simulated heads for each well. If the calibration is perfect,
both data sets will fall along a 45-degree line. the further that the data points are
from this line, the greater the model deviation from actual flow conditions (Sklash
et al., 1999). Plotting the residuals (the difference between the simulated and
observed heads) can also provide insight into model calibration.
• Compare the input parameters of the reverse model with other site models for
consistency (e.g., remediation models, risk assessment models). It is not uncom-
mon that hydraulic and chemical properties selected for a Risk-Based Corrective
Action (RBCA) study or a model used to obtain site closure are different than those
for the reverse modeling.
Groundwater velocity, for example, can be adjusted by varying the porosity value
used for the sediments through which groundwater is flowing. A change in porosity
from 30 to 20% results in an increase of groundwater velocity by one third. Another
example is the effect of retardation on plume geometry. In Figure 5.9, the only
parameter adjusted in the model is the retardation value (2.5 vs. 1.0). Selection of a
retardation factor of 2.5 produces a plume that originated in 1950 while a value of
1.0 produces a contaminant plume originating in 1975. Both shapes are consistent
with the contaminant plume geometry measured in 1996.

In most cases, reverse modeling results provide the alleged time at which a
contaminant entered the groundwater at a given location. In cases where groundwater
is shallow or the contaminant is introduced into the groundwater via a dry well or cistern,
this may be a reasonable assumption. In cases where the release occurred at the surface,
the cumulative time required for the contaminant to flow through the surface pave-
ment (if present) and soil prior to entering the groundwater must be considered.
5.6.6 CHALLENGES TO PHASE-SEPARATE REVERSE MODELS

If a reverse or confirmation model is used to predict phase-separate migration, a
different set of governing equations and additional parameters are needed than for a
dissolved species in groundwater. For a light, non-aqueous phase liquid (LNAPL)
transport along the water table, its movement can be described by the following
(Parker and Lenhard, 1990):
Qo = –To—Zao (Eq. 5.18)
where Qo is the vertically integrated Darcian velocity, To is the light, non-aqueous

phase liquid, and Zao is the height at which the water and LNAPL capillary pressures
are equal, which corresponds to the LNAPL/air interface. The transmissivity of the
LNAPL is then described by:
Zu
To = Ú r ro k ro K h / hro dZ (Eq. 5.19)
y
Zo
where Zu is the uppermost elevation at which mobile LNAPL occurs, Z yo is the

elevation where the water and LNAPL pressures are equal, rro is the specific gravity
of the LNAPL, kro is the relative permeability of the NAPL, Kh is the horizontal
saturated hydraulic conductivity relative to water, and hro is the LNAPL-to-water
viscosity ratio. The pore velocity of the leading edge of the LNAPL at the water table
(vn) is then defined as:
vn = Qo / VLNAPL (Eq. 5.20)
where VLNAPL is the mobile LNAPL volume per unit area.

A key variable for a reverse or confirmation model for a light, non-aqueous phase
liquid is the representativeness of the three-phase (air, water, NAPL) expression that
describes the pressure distributions between these fluids for a particular soil texture
(Gardner, 1960; Parker and Lenhard, 1990). If this expression is reduced to a
monotonic nonlinear relationship, the legitimacy of this non-hysteretic expression
requires scrutiny.
Challenges to phase-separate confirmation and reverse models include the rep-
resentativeness of values selected for fluid viscosity, interfacial tension, and soil
texture used to describe the interaction between the three liquid phases. Fluid

viscosity and density measurements are rarely measured and more commonly are
published values. As a result, published values used in the model can deviate from
field density measurements due to weathering and/or co-mingling of the LNAPL
with other compounds.
REFERENCES
Ball, W. and P. Roberts, 1991. Long-term sorption of halogenated organic chemicals by

aquifer material. 1. Equilibrium, Environmental Science and Technology, 24:1223–
1236.
Barcelona, M. and R. Morrison, 1988. Sample collection, handling and storage: water, soils
and aquifer solids, in Proc. of a 1988 National Workshop on Methods for Ground Water
Quality Studies, Agricultural Research Division, University of Nebraska at Lincoln, pp.
49–62.
Barber, L., Thurman, M., Schroder, M., and D. LeBlanc, 1988. Long-term fate of organic
micropollutants in sewage contaminated groundwater, Environmental Science and Tech-
nology, 22:205–211
Bear, J., 1979. Hydraulics of Groundwater, McGraw-Hill, New York, p. 210.
Bear, J., Beljin, M., and R. Ross, 1992. Fundamentals of Ground-Water Modeling: EPA
Ground Water Issue, EPA/540/S-92/005, Office of Research and Development, Office
of Solid Waste and Emergency Response, U.S. Environmental Protection Agency,
Bisdom, E., Dekker, L., and J. Schoute, 1993. Water repellency of sieve fractions from sandy
soils and relationships with organic materials and soil structure, Geoderma, 56:105–
118.
Bois, T. and B. Luther, 1996. Groundwater and Soil Contamination: Technical Preparation
and Litigation Management, John Wiley & Sons, Somerset, NJ, pp. 135–144.
Bouma, J., 1981. Soil morphology and preferential flow along macropores, Agricultural
Water Management, 3:235–250.
Carrier Corp. v. Detrex Corp., 1996. Superior Court of the State of California, County of
Los Angeles, No. C703625.
Cleary, R., 1995. Introduction to applied mathematical modeling in groundwater pollution
and hydrology with IBM-PC applications, in Proc. of the NGWA IBM-PC Applications
in Groundwater Pollution and Hydrology Conference, August 13–18, San Francisco,
CA, p. 164.
Cohen, R., Mercer, J., and J. Matthews, 1993. DNAPL Site Evaluation, CRC Press, Boca
Raton, FL, p. 48.
Crank, J., 1985. The Mathematics of Diffusion, 2nd ed., Oxford University Press, London,
p. 21–67.
Curtis, G., Roberts, P., and M. Reinhard, 1986. A natural gradient experiment on solute
transport in a sand aquifer. 4. Sorption of organic solutes and its influence on mobility,
Water Resources Research, 22, 2059–2067.
Davidson, J. and R. Parsons, 1996. Remediating MTBE with current and emerging technolo-
gies, in Proc. of the 1996 Petroleum Hydrocarbons and Organic Chemicals in Ground
Water: Prevention, Detection, and Remediation Conference, National Ground Water
Association, November 13–15, Houston, TX, pp. 15–29.

Diment, G. and K. Watson, 1985. Stability analysis of water movement in unsaturated
porous materials: experimental studies, Water Resources Research, 21:979–984.
Fishman, M., 1998. DNAPL infiltration and distribution in subsurface: 2D experiment and
modeling approach, in Wickramanayake, G. and R. Hinchee (Eds.), Nonaqueous Phase
Liquids: Remediation of Chlorinated and Recalcitrant Compounds, Battelle Press, Co-
lumbus, OH, p. 37–42.
Freeze, R., and J. Cherry, 1979. Groundwater, Prentice-Hall, Englewood Cliffs, NJ, p. 604.
Gardner, W., 1962. Approximate solution of a non-steady state drainage problems, Soil
Science Society Proceedings of America, 25:129–132.
Gelhar, L., and C. Axness, 1983. Three-dimensional stochastic analysis of macrodispersion in
aquifers, Water Resources Research, 19(1):161–180.
Gelhar, L. and C. Axness, 1981. Stochastic Analysis of Macro-Dispersion in Three Dimension-
ally Heterogeneous Aquifers, Report No. H-8, Hydraulic Research Program, New Mexico
Institute of Mining and Technology, Soccorro, p. 140.
Gelhar, L., Welty, C., and K. Rehfeldt, 1992. A critical review of data on field-scale dispersion
in aquifers, Water Resources Research, 28(7):1955–1974.
Ghadiri, H. and C. Rose, 1992. Modeling Chemical Transport in Soils Natural and Applied
Contaminants, Lewis Publishers, Chelsea, MI, p. 217.
Glass, R. and M. Nicholl, 1996. Physics of gravity fingering of immiscible fluids within porous
media: an overview of current understanding and selected complicating factors, Geoderma,
70:133–163.
Hartman, B., 1999. Which Compound Requires More Attorneys: MTBE or Benzene?, LUSTline
Bull. No. 31, New England Interstate Water Pollution Control Commission, Wilmington,
MA, pp. 15–17.
Hartman, B., 1997. Applications and interpretation of soil vapor data to chlorinated solvent
contamination, in Legal and Technical Considerations of Chlorinated Solvent Contami-
nation, Argent Communications, Foresthill, CA, pp. 81–110.
Hill, D. and J. Parlange, 1972. Wetting front instability in layered soils, Soil Science Society
of America Proc., 36:697–702.
Hughes Aircraft Company v. Brian Eustace Beagley et al., 1995. Superior Court of the State
of California, Los Angeles County, Case No. BC062120.
Hughes Aircraft Company v. Hartford Accident & Indemnity Company, 1994. Superior Court
of the State of California, Los Angeles County, Case No. 92-6031-LGB (JRx).
Imhoff, P., Thyrum, G., and C. Miller, 1996. Dissolution fingering during the solubilization
of nonaqueous phase liquids in saturated porous media. 2. Experimental observations,
Water Resources Research, 32(7):1929–1942.
Jarvis, N., 1998. Modeling the impact of preferential flow on nonpoint source pollution, in
Selim, H. and L. Ma (Eds.), Physical Nonequilibrium in Soils: Modeling and Application,
Ann Arbor Press, Chelsea, MI, p. 492.
Kung, J., 1990a. Preferential flow in a sandy vadose zone. 1. Field observation, Geoderma,
45:51–58.
Kung, J., 1990b. Preferential flow in a sandy vadose zone. 2. Mechanism and implications,
Geoderma, 46:59–71.
Jury, W. and K. Roth, 1990. Transfer Functions and Solute Movement through Soil: Theory
and Applications, Birkhauser-Verlag, Basel, p. 226.
Jury, W. and G. Sposito, 1985. Field calibration and validation of solute transport models for
the unsaturated zone, Soil Science Society of America Journal, 49:1331–1341.
Jury, W., Sposito, G., and R. White, 1986. A transfer function model of solute transport
through soil. 1. Fundamental concepts, Water Resources Research, 22:243–247.

Kezsbom, A. and A. Goldman, 1991. The boundaries of groundwater modeling under the law:
standards for excluding speculative expert testimony, Environmental Claims Journal,
4(1):5–30.
Kornfeld, I., 1992. Comment to the boundaries of groundwater modeling under the law:
standards for excluding speculative expert testimony, Tort and Insurance Law Journal,
28(1):59–67.
Kosmatka, S. and W. Panarese, 1988. Design and Control of Concrete Mixtures, 13th ed.,
Portland Cement Association, Skokie, IL, p. 10.
Lallemand-Barres, A. and P. Peaudecerf, 1978. Recherche de reltions entre les valeurs mesurees
de la dispersivite macroscopique d’un milieu aquifere, ses autres caracteristiques et les
conditions de mesure, etude bibliographique, Bull. Bur Rech. Geol. Min. (BRGM), Ser.
2, Sec. III, No. 4, pp. 277–284.
Lohman, S., Bennett, R., Brown, R., Cooper, H., Drescher, W., Ferris, J., Johnson, A.,
McGuinness, C., Piper, A., Rorabaugh, M., Stallman, R., and C. Theis, 1972. Definitions
of Selected Ground Water Terms: Revisions and Conceptual Refinements, U.S. Geology
Survey, U.S. Government Printing Office, Washington, D.C., p. 14.
Lyman, W., Reehl, W., and D. Rosenblatt, 1982. Handbook of Chemical Estimation Methods,
McGraw-Hill, New York, p. 960.
MacKay, D., 1990. Characterization of the distribution and behavior of contaminants in the
subsurface, in Ground Water and Soil Contamination Remediation: Toward Compatible
Science, Policy and Public Perception, report on a colloquium sponsored by the Water
Science and Technology Board, National Academy Press, Washington, D.C., pp. 70–90.
MacKay, D., Freyberg, D., Roberts, P., and J. Cherry, 1986. A natural gradient experiment on
solute transport in a sand aquifer. 1. Approach and overview of plume movement, Water
Resources Research, 22:2017–2029.
McCoy, B. and D. Rolston, 1992. Convective transport of gases in moist porous media: effect
of absorption, adsorption, and diffusion in soil aggregates, Environmental Science and
Technology, 26(12):2468–2476.
McDonald, M. and A. Harbaugh, 1988. A modular three-dimensional finite-difference ground-
water flow model, in Techniques of Water Resources Investigations. 6. Modeling Tech-
niques, U.S. Geological Survey, U.S. Government Printing Office, Washington, D.C., pp.
1.1–14.39.
Mehran, M., Olsen, R., and B. Rector, 1987. Distribution coefficient of trichloroethylene in
soil-water systems, Ground Water, 25:275–282.
Mercer, J., 1991. Common mistakes in model applications, in Proc. of the American Society
of Civil Engineers (ASCE) Symposium on Ground Water, July 29–August 1, Nashville,
TN, p. 7.
Miller, C., Gleyzer, S. and P. Imhoff, 1998. Numerical modeling of NAPL dissolution
fingering in porous media, in Selim, H. and L. Ma (Eds.), Physical Nonequilibrium in
Soils Modeling and Application, Ann Arbor Press, Chelsea, MI, p. 492.
Millington, R., 1959. Gas diffusion in porous media, Science, 130:100–102.
Millington, R. and J. Quirk, 1959. Permeability of porous media, Nature (London), 183:387–
388.
p. 271.
Morrison, R., 1999a. Critical review of reverse and confirmation models used to date a
contaminant release, Environmental Claims Journal, in press.

Morrison, R., 1999b. Reverse and confirmation models: applications and challenges, Interna-
tional Journal of Environmental Forensics, in press.
Morrison, R., 1998. Estimating the timing of a contaminant release via transport modeling,
Environmental Claims Journal, 10(2):75–90.
Morrison, R. and R. Erickson, 1995. Groundwater investigations, in Morrison, R. and R.
Erickson (Eds.), Environmental Reports and Remediation Plans: Forensic and Legal
Review, John Wiley & Sons, Somerset, NJ, p. 155.
Morrison, R. and B. Lowry, 1990. Sampling radius of a porous cup sampler: experimental
results, Ground Water, 28(2):262–267.
Morrison, R. and E. Newell, 1999. The cosolvation transport of DDT and xylene at a pesticide
formulation facility, Journal of Soil Contamination, 8(1):63–80.
Neumann, S. and Y. Zang, 1990. A quasi-linear theory of non-Fickian and Fickian subsurface
dispersion. 1. Theoretical analysis with application to isotropic media, Water Resources
Research, 26(5):887–902.
Norton, P. and D. Pletta, 1931. The permeability of gravel concrete, Journal of the American
Concrete Institute, 27:1093–1132.
Odermatt, S., Johnson, T., and R. Hummeldorf, 1993. Distribution of DDT residues (DDT,
DDD, and DDE) in California sediments, Journal of Soil Contamination, 2(4):315–329.
Pankow, J. and J. Cherry, 1996. Dense Chlorinated Solvents and Other DNAPLs in Groundwater,
Waterloo Press, Portland OR, p. 522.
Parker, B. and J. Cherry, 1995. Age-dating DNAPL source zones from diffusion profiles in low-
permeability layers, in Innovative Characterization of DNAPL Impacted Aquifers, Geologi-
cal Society of America Annual Meeting, November 6–9, New Orleans, LA, p. A-403.
Parker, J., 1989. Multiphase flow and transport in porous media, Water Resources Research,
2:2187–2196.
Parker, J. and R. Lenhard, 1990. Vertical integration of three phase flow equations for analysis
of light hydrocarbon plume movement, Transport in Porous Media, 5:618–624.
Philip, J., 1975. The growth of disturbances in unstable infiltration flows, Soil Science Society
of America Proc., 39:1049–1053.
Richards, L., 1931. Capillary conduction of liquids in porous media, Physics, 1:318–333.
Ritsema, C. and L. Dekker, 1995. Distribution flow, a general process in the top layer of water
repellent soils, Water Resources Research, 31:1187–1200.
Robbins, G., 1989. Influence of using purged and partially penetrating monitoring wells on
contaminant detection, mapping and modeling, Ground Water, 27(1):155–162.
Rong, Y., Want, R., and R. Chou, 1988. Monte Carlo simulation for a groundwater mixing
model in soil remediation of tetrachloroethylene, Journal of Soil Contamination, 7(1):87-
102.
sure Assessment Model for Evaluating the Land Disposal of Wastes: Model Theory, EPA
600/R-93/081, U.S. Environmental Protection Agency, Washington, D.C., p. 122.
Schwarzenbach, R., Giger, P., Hoehn, W., and J. Schneider, 1983. Behavior of organic
compounds during infiltration of river water to groundwater: field studies, Environmental
Science and Technology, 17:472–479.
Selima, H. and L. Ma, 1998. Physical Nonequilibrium in Soils Modeling and Application, Ann
Arbor Press, Chelsea, MI, p. 492.
Sterling v. Velsicol Chemical Corp., 1988. 855 F.2d 1188, 1199 (6th Circuit).
Streile, G., 1984. The Effect of Temperature on Pesticide Phase Partitioning, Transport and
Volatilization from soil, Ph.D. dissertation, Department of Soil Science, University of
California, Riverside, pp. 15–100.

Szecsody, J., 1992. Solute transport processes in groundwater systems, in Subsurface Inves-
tigation and Remediation for Sites Contaminated with Hazardous Wastes, Department of
Engineering and Engineering Professional Development, University of Wisconsin, Madi-
son, p. 44.
Tetra Tech, Inc., 1993. ROAM Version 1.0 Remedial Options Assessment Model, TR-103202,
Electric Power Research Institute, Land and Water Quality Studies Program, Environ-
ment Division, Research Project 2485-02.
U.S. EPA, 1985. Water Quality Assessment: A Screening Procedure for Toxic and Conven-
tional Pollutants in Surface and Ground Water, Parts I and II, rev. ed., EPA/600/6-85-
002a (Part I, 609 pp.), EPA/600/6-85/002b (Part II, 444 pp.), U.S. Environmental Protec-
tion Agency, Environmental Research Laboratory, Athens, GA.
Van der Heijde, P., 1984. Availability and applicability of numerical models for ground water
resources management, in Proc. of the National Water Well Association Conference on
Practical Applications of Ground Water Models, Battelle Press, Columbus, OH, pp. 3–
18.
Van Genuchten, M. and W. Alves, 1982. Analytical Solutions of the One-Dimensional Con-
vective-Dispersive Solute Transport Equation, Tech. Bull. No. 1661, U.S. Department
of Agriculture, Washington, D.C., p. 151.
Villholth, K., 1999. Colloid characterization and colloidal phase partitioning of polycyclic
aromatic hydrocarbons in two creosote-contaminated aquifers in Denmark, Environmen-
tal Science and Technology, 33(5):691–699.
Wei, C. and P. Ortoleva, 1990. Reaction front fingering in carbonate-cemented sandstones,
Earth Sciences Review, 29:183–198.
White, R., 1985. The influence of macropores on the transport of dissolved and suspended
matter through soil, Advances in Soil Science, 3:95–113.
Whiting, D. and A. Walitt, 1988. Permeability of Concrete, ACI SP-108, American Concrete
Institute, Chicago, IL.
10:501–506.
Zeng, C., 1994. Analysis of particle tracking errors associated with spatial discretization,
Ground Water, 32(5):821–828.
Zeng, C., 1993. Extension of the method of characteristics for simulation of solute transport
in three dimensions, Ground Water, 31(3):456–465.
Zeng, C. and G. Bennett, 1995. Applied Contaminant Transport Modeling: Theory and
Practice, Van Nostrand-Reinhold, New York, p. 440.

Plate 5.1 Thin section of soil impregnated with resin showing a decayed root
channel with the remains of the root in the middle of the root channel. The lighter
colored soil around the root channel is due to the osmotic stripping of nutrients
from the surrounding soil.

Plate 5.2 A rubble-filled dry well providing a preferential transport pathway
for contaminants.

Plate 5.3 Examples of finger and macropore flow.
Plate 5.4 The impact of liquid transport via macropores in a mature soil in
the U.K. Hydrated gypsum was ponded on the ground surface and drained into the
underlying soil via macropores. The gypsum then dehydrated, leaving the
macropore channels clearly visible.

Plate 5.5 Example of confirmation modeling exhibit to estimate the date of a
contaminant release.

6 Forensic Review
of Environmental
Trial Exhibits
An accurate picture is worth a thousand words.
6.1 INTRODUCTION
Environmental exhibits that are clear, accurate, and simple are a prerequisite for
explaining the technical elements of an environmental case. Exhibits must also be
factually and scientifically correct. Exhibit errors are unintentional due to transcrip-
tion or preparation errors or intentional, as identified by a pattern of bias (Tufte, 1983,
1990, 1997). Intentional errors include:
• Exaggerated vertical or horizontal scales

• Selective data presentation
• Data contouring (manually and computer-generated)
• Color-coded data that obscure source areas
• Contaminant transport models based on biased data
When trial exhibits are exchanged, a concerted effort is required to validate their
accuracy. Obtain the underlying information such as chemical results, especially in
an electronic format, early in the discovery stage so that your expert witness and/or
confidential consultant can quickly review the underlying data used to produce the
trial exhibits. Determining that a trial exhibit is scientifically accurate benefits all
parties.
6.2 EXAGGERATED VERTICAL

AND HORIZONTAL SCALES
Exhibit scales are often exaggerated, especially for geologic cross-sections and fence
diagrams. When portraying a relatively small vertical scale, such as shallow soil

contamination (<100 ft.), relative to a substantially larger horizontal scale (>1000 ft),
exaggeration is a reasonable way to present the data. Conversely, the depiction of
subsurface contamination is skewed by excessively increasing the vertical scale
relative to the horizontal scale. When vertical or horizontal scale exaggeration
occurs, it should be posted on the exhibit and described in the testimony so that the
viewer is informed. Plate 6.1* depicts the concentration of trichloroethylene (TCE)
in soil with a 1:1 and 1:10 vertical-to-horizontal scale (Morrison, 1998). The TCE
distribution is represented as an iso-surface for the purpose of depicting the volume
of contaminated soil. While the respective horizontal-to-vertical ratios are accurate
in both versions, the perception regarding the extent of contamination is different.
Exhibits relying on this technique are routinely employed in cases that address the
reasonableness of remediation costs. When an exhibit prejudices the observers’
perspective, prepare a rebuttal exhibit with a 1:1 vertical-to-horizontal scale with the
same data or decrease the three-dimensional area so that the exaggeration bias is
reduced.
6.3 SELECTIVE DATA PRESENTATION
It is the author’s experience that omission of selective data is common in environ-

mental exhibits. Observed practices include:
1. Data omission
2. Use of averages or mean data (i.e., obtaining the average of quarterly data, moving
averages, geometric means, time series presentations; using averaged values, aver-
aged value with standard variation, mean plus confidence interval, measured value
plus the percentage of relative standard deviation or coefficient of variation, etc.)
which results in an underestimation of contaminant concentrations and plume
geometry
3. Selection and presentation of the higher or lower value from split samples
4. Creation of multi-chemical composite contour maps (i.e., combining all solvent
measurements and reporting them as total volatile organic compounds [VOCs]
rather than for each compounds) to mask source identification
5. Arbitrary elimination of anomalous data
6. Data presentation generated from imprecise or non-specific analytical methods
7. Data filtering to reduce or eliminate reported measurements
8. Aerial photo cropping
9. Arbitrary revisions to the original data
There is usually client reluctance to spend the money required for exhibit
validation, especially when large data sets are used. For large invalidated data sets
(>1000 data entries), a 5 to 15% transcription error between laboratory data and the
computer spreadsheets is common. If the data entered onto the spreadsheet are double
entered or cross-checked, this error is significantly reduced.

Validating a large data set (e.g., ≥100,000 entries) when the exhibit is based on
500 data points is unproductive. Identification of transcription errors is cost effec-
tively performed by validating only those locations and compounds used in key
exhibits. This strategy requires that the underlying chemical data sheets are quickly
accessible once the exhibits are exchanged. Once the data used to create an exhibit
is validated, it is used with the identical modeling and/or visualization software to
determine if the trial exhibit is reproducible. If the animation software is proprietary,
additional cost and time can result in purchasing or licensing the software from the
company. In addition, the software may require unique hardware as well as a person
fluent with the software. These hardware, software, and personnel issues should be
resolved in advance of receiving the exhibits.
Confirmation of the validity of data used to generate an exhibit may not be
straightforward. Consider 100 split soil samples collected and tested for trichloro-
ethylene. Is it more appropriate to use the lowest, highest, or average of the two
values in the exhibit or to plot all three? If a trial exhibit relies on averaged values
in some instances and alternates between high and low values for others, determine
if a pattern of intentional data bias exists. A consistent method should be used and
the rationale for the selection clearly stated on the exhibit and/or testimony.
Exhibits that rely upon the geometric mean of a data set are often encountered,
as water quality results are generally distributed geometrically in time and space. The
geometric mean is obtained by taking the log of multiple values, adding the log, and
then taking the anti-log of the averaged log values. This technique tends to dampen
the impact of data outliers or individual anomalous values that may be important in
identifying contaminant sources. Similarly, other statistical averaging techniques that
assume a normal distribution should be confirmed. Minimization of biases due to
concentration averaging, geometric means, and mean values is accomplished by
using the actual values for a point in time. This latter approach improves the validity
of the data interpretation, transport modeling, and ultimately the effectiveness of the
remediation design (Martin-Hayden and Robbins, 1997).
The interpretation of non-detect (ND) results can skew the results of the data set
used to create an exhibit. A sample reported as ND can be interpreted as 0, as the
value of the method detection limit, or as a value of one half the detection limit or
omitted in the data set. If the geometric mean of a data set is used, the central
tendency of the geometric mean will be significantly different if non-detects are
excluded vs. if values equal to one half the method detection limit are used.
For time-series data using single or averaged data (e.g., 10 years of quarterly
groundwater sampling data), graphing data from a single quarter or averaging values
for several quarters can skew the viewer’s perception if the chosen quarter(s) are
anomalous relative to historical trends. Combining 6 or 12 months of non-sequential
groundwater data (e.g., annual, quarterly, and biannual sampling) for an aquifer with
a high velocity (e.g., >1000 ft per year) onto one exhibit when monitoring wells are
spaced less than 1000 ft apart results in an unrepresentative portrayal of contaminant
distribution. Creating a rebuttal exhibit depicting seasonal or more consistent histori-
cal trends including anomalous sampling quarter data places the trial exhibit in a
more balanced historical perspective.

FIGURE 6.1 TCE concentrations from five groundwater monitoring wells collected by three
consultants between 1991 and 1994.
If sample integrity is suspected due to sampling bias, especially for volatile

compounds collected by multiple consultants, plotting the chemical results vs. time
and labeling the tenure of the various consultants may identify whether this potential
exists. Figure 6.1 illustrates trichloroethylene (TCE) concentrations in groundwater
samples collected from multiple wells by three consultants between 1991 and 1994.
In Figure 6.1, the TCE values for samples collected by Consultants A and B between
1991 and 1993 are smaller than the TCE concentrations from samples collected by
Consultant C. The higher TCE concentration collected by Consultant C may indicate
the use of different sampling equipment or procedures.
Valid reasons exist for eliminating anomalous (e.g., outlier) values from a data
set used to create an exhibit; however, the presence of anomalous data may be the
only indication that the data are skewed and hence may be one of the most important
data points in the population. If data are omitted, the rationale should be prominently
posted on the exhibit. An example of omitted data is the presentation of changes in
groundwater flow direction via rose diagrams. Figure 6.2 depicts the frequency of the
groundwater flow direction from quarterly monitoring reports. The purpose of Figure
6.2 is to demonstrate that a contaminant plume in groundwater is captured with a
groundwater extraction system located downgradient of the source. The groundwater
extraction system was designed to capture the contaminant plume when the ground-
water flow direction is west to southwest (Figure 6.2A). Groundwater flow to the
north results in the transport of contaminated groundwater beyond the capture zone
of the extraction system. Figure 6.2A shows nine quarters of groundwater flow that
is predominately to the west to southwest. Figure 6.2B is a rebuttal exhibit depicting
all 13 quarters with the direction of flow alternating between the southwest and
northeast. Figure 6.2A does not contain reference to the omitted data.

FIGURE 6.2 Rose diagrams showing historical groundwater flow directions. (From Morrison,
R., in Environmental Claims Journal, 11(1), 93–107, 1998. With permission.)
While omission of anomalous data adverse to one’s position is usually obvious,

subtle permutations are also encountered. An example is a chemical or geologic
cross-section. A cross-section is a slice through the subsurface with information
intersected by the slice displayed two or three dimensionally. A common cross-
section manipulation is the inclusion or omission of data points not intersected on the
cross-section. Figure 6.3(3a) depicts a plan view of a cross-section (A-A¢) that
intersects total petroleum hydrocarbon (TPH)-impacted soil. Figure 6.3(3b), how-
ever, is the actual transect line reflecting the sampling points from which soil
chemistry was used in the cross-section. In the case of the transect A-A¢ in Figure
6.3(3b), data along the transect that were not used included locations S-EX7 and S4-
3-PL. Sampling locations within 5 ft of the A-A¢ transect from locations S1-EX3 and
S9-EX5 (see 3a) were also omitted. Sample locations located 30 ft to the east (S5-
5-PL, S9-7-PL), however, were projected onto the A-A¢ transect in 3a and incorpo-
rated into the accompanying cross-section.
Another example of data omission is the exclusion of non-CLP (Contract Labo-
ratory Program) data. Contract Laboratory Program data are the documentation
required for sample testing associated with the Comprehensive Emergency Cost
Recovery Act (CERCLA) or Superfund and Resource Conservation and Recovery
Act (RCRA) investigations. The primary components of this program include field
and/or trip blanks, field duplicate sample results, and internal laboratory quality
control results (e.g., matrix spikes, matrix spike duplicates, and laboratory method
blanks). Historical CLP and non-CLP (e.g., Phase I or II investigations) may not be
available. If non-CLP data are excluded in an exhibit, plot the CLP and non-CLP data
and compare the results. If one component of the CLP documentation is unavailable
or has been violated (e.g., broken travel or field blank bottles) and is included in the
exhibit, create the same graph or figure with and without the suspected data.

FIGURE 6.3 Plan view of cross-section transects A-A¢. (From Morrison, R., in Environmen-
tal Claims Journal, 11(1), 93–107, 1998. With permission.)
Another data omission example is the case of split samples from one laboratory
using CLP procedures and a second data set with non-CLP documentation. Plot the
split CLP and non-CLP sample data collectively and individually to determine if
significant differences in interpretation occur. If the non-CLP data are significantly
dissimilar, the non-CLP data can be used for a different purpose (e.g., qualitatively
vs. quantitative) or weighed differently. For example, the CLP data may be used for
risk assessment purposes or to provide a quantitative measure of the volume of soil
exceeding a clean-up concentration. The combined CLP and non-CLP data can be
used to establish the boundaries of the contamination.
Determining the reasonableness of an analytical method relied upon to create an
exhibit may be required. In Plate 6.2,* 24 soil samples from a soil excavation are split
into three discrete samples, with each sample forwarded to an analytical laboratory
and tested for total petroleum hydrocarbons as gasoline. When each data set is
contoured, different contaminant source areas as well as volumes above a remediation
concentration of 100 mg/kg occur. A plan view of the contours from the Method 3
data depicts three source areas, while Method 1 and 2 data indicate two source areas.
The exhibit relying on the Method 3 data or an average of the three data sets will
result in significantly different interpretations of the distribution of the TPH in the
soil. The data set selected for the exhibit influences the interpretation regarding the
location of TPH contamination. The solution is to perform an analysis of the repre-
sentativeness or accuracy of each analytical method to determine which data set is
most representative. In Plate 6.2, Method 1 introduced false positive readings, while
the methanol extract used in Method 2 was less effective in contaminant removal than

FIGURE 6.4 Excavation cross-section using EPA Methods 418.1 and 8015.
Method 3. For this soil type and contaminant, Method 3 is the most representative
data set.
A variation of the Plate 6.2 example is reliance on a testing technique such as
EPA Standard Method 418.1 to detect total petroleum hydrocarbons (TPHs) in soil
samples used to guide the excavation of hydrocarbon-impacted soil. EPA Method
418.1 is a non-chromatographic technique and detects the presence of biogenic
compounds in the soil (i.e., peat, pine needles, organic matter) resulting in false-
positive measurements (George, 1992; Zemo et al., 1995). The author has observed
cases when EPA Method 418.1 is used to define where to excavate, until the
excavation is inhibited by the presence of a building or road. The consultant then
changes to an analytical method that does not introduce a false bias (i.e., EPA Method
8015). Testing using EPA Method 8015 results in non-detect sample measurements
and becomes the basis for halting the excavation. Whether the original excavation
using EPA Method 418.1 was warranted becomes not only a source of contention but
also affects the reliability of an exhibit combining test results using EPA Methods
418.1 and 8015.
Figure 6.4 is a cross-section of a soil excavation where soil samples were tested
for TPHs using EPA Standard Methods 418.1 and 8015. Soil samples collected
within the interior of the excavation were tested via EPA Method 418.1, while EPA
Method 8015 was selected for confirmation soil sampling along the excavation
perimeter. The potential implications of this observation are that over-excavation
probably occurred and that the consultant may have intentionally relied upon the
false-positive bias results inherent with EPA Method 418.1 to excavate non-petro-
leum-contaminated soil as a means to generate income. EPA Method 8015 was then
used to halt the excavation, in this case when its proximity to subsurface piping
presented significant complications to continued excavation. Once the excavated soil

FIGURE 6.5 Plan view of soil excavation and selective use of EPA Standard Methods 418.1
and 8015.
is remediated or co-mingled with other petroleum-impacted soil, it becomes prob-

lematic whether subsequent test results of these excavated soils can determine if the
original EPA Method 418.1 results were valid.
Figure 6.5 depicts a plan view of excavated gasoline-contaminated soil. The
organic-rich subsurface soils provided consistent false-positive measurements when
using EPA Standard Method 418.1. Once the excavation proceeded close to a cooling
tower and manufacturing building, the consultant switched to soil analysis using EPA
Standard Method 8015 which resulted in non-detect sample results. Excavation near
the surface structures then ceased. The distribution of analytical methods used for soil
analysis relative to the above-ground structures in Figure 6.6 suggests an intent to
create non-detect boundaries in areas in which extensive shoring was required.
It may be warranted to retain an analytical chemist to reconstruct the validity of
the test method(s) used to direct a soil excavation. The chemist can identify data
believed to be unreliable which should be omitted from an exhibit. Conversely, if no
quality assurance analysis is performed, both parties may erroneously assume that the
detection of a particular compound is correctly identified. It is the author’s experi-
ence that in the case of gas chromatography/mass spectrophotometry (GC/MS), it is
not unusual to find that 5 to 10% of the compounds are misidentified, especially if
the interpretations are not manually examined.

Data filtering is the revision or omission of data based on identification of the
removed data as anomalous and/or non-representative. An example is the detection
of 20 parts per billion (ppb) of TCE in a rinsate sample collected from a groundwater
bailer. The bailer is subsequently used to collect a groundwater sample that results
in a reading of 24 ppb. The data (24 ppb) are omitted from the data set based on a
concentration of 4 ppb (lower than the maximum contaminant level of 5 ppb) via
subtracting the equipment blank value from the measured groundwater sample.
Another example of data filtering is assigning a new detection limit at five times
the contamination level detected in the rinsate sample. The new detection limit is
therefore 5 ¥ 20 = 100 ppb. The detection of 24 ppb in the groundwater sample is now
regarded as non-detect, as are trichloroethylene concentrations up to 100 ppb. This
method results in significant data omissions.
Data filtering may be represented as justified through re-sampling. For example,
monitoring wells may be re-sampled immediately after contamination is detected or
re-sampled several times until contamination is not detected. The non-detect sample
is then reported in the quarterly groundwater monitoring report and relied upon for
the trial exhibit. Another technique is repeated groundwater sampling at the same
location using a cone penetrometer test (CPT) rig or less quantitative technology (soil
gas), with the re-sampling occurring days, months, or years after the original results
to confirm the use of the non-detection measurements shown on a trial exhibit.
For data sets where measurements are omitted, the major difficulty often lies in
identifying the omissions. For large data sets (>1000 entries), omissions may not be
apparent without a thorough review. Another difficulty is the testing of split samples
by multiple samples, with only those sample results supportive of a particular
position being reported. One technique for identifying data omissions is to aggres-
sively pursue any electronic databases kept by the consulting firm or facility operator.
Another option is to subpoena the original laboratory sheets and create a separate
database.
Aerial photo cropping is a technique that can remove undesirable information.
Figure 6.6 shows two versions of an aerial photo of a tank farm in 1925 — uncropped
and cropped; the cropped version deletes a tank under construction in the upper left
corner. Be aware that when a person selects an aerial photo from a repository or
dealer, the portion that is selected for the hard copy is usually a subset of the original,
usually due to the scale of the parent aerial photograph. When ordering aerial
photography, a number of scales and coverage dates are available. It is the author’s
experience that all of the coverage dates are rarely ordered. This can result in the
omission of aerial photo information if the opposing side obtains copies during
discovery and relies on these rather than independently obtaining their own aerial
photographs.
When forensically evaluating a trial exhibit, examine all the underlying founda-
tional information, especially field and laboratory notes. Figure 6.7 depicts a field
and final soil-boring log contained in an environmental report. The field log depicts
a 3-ft zone of contamination, while the final log contained in the environmental
report shows a contaminant zone that is 7 ft thick. The final boring log was used with
other boring logs to estimate the volume of contamination and associated remediation

FIGURE 6.6 Uncropped (top) and cropped (bottom) aerial photograph.
costs. While the difference between the field and final boring log is small (ª4 feet),
this difference extrapolated over a large area results in substantial differences in
contaminant distribution and associated remediation costs.
6.4 DATA CONTOURING

Data contouring (manual or computer-generated) is the interpolation of numbers of
equal value in space (i.e., connecting the dots). Contouring provides useful visual

FIGURE 6.7 Field and final soil boring logs. (From Morrison, R., in Environmental Claims
Journal, 11(1), 93–107, 1998. With permission.)
displays showing regions of elevated concentrations. Contouring can identify con-

taminant source areas and is useful for designing remedial programs. Whether two
or three dimensional, contouring forms the foundation for most environmental exhib-
its depicting chemical/spatial information (Joseph, 1996). Contour reliability is a
function of the following items:
• Data density
• Mathematical contouring method
• Nature of the contaminant (a pure phase liquid vs. a dissolved phase contaminant)
• Site-specific geologic environment that controls contaminant movement (move-
ment in fractured bedrock vs. in a uniform fine sand)
The last item is important, as geologic environments may be encountered (e.g., a

highly heterogeneous aquifer) for which contouring of a dissolved contaminant may
be misrepresented by concentration contouring. In cases such as groundwater eleva-
tions and LNAPL thickness on groundwater, however, contouring may be more
appropriate in the same setting.

6.4.1 MANUAL CONTOURING
Manual contouring relies upon the judgment of the author to connect the dots.
Whenever a manually generated contour map is offered into evidence, plot the data
to confirm that the contouring has honored the data. Plate 6.3* is an example showing
the distribution of trichloroethylene in soil gas. The manually generated contour map
and shading in Plate 6.3a suggest a single trichloroethylene source bounded within
the 1000-ppb contour line. Plate 6.3b is a computer-generated contour map of the
same data. By comparing the two maps, differences in the interpretation of the same
data arise as to potential contaminant source areas. Plate 6.3a suggests a single
contaminant source, while Plate 6.3b indicates multiple sources.
Another mapping technique is shown in Plate 6.3c, where the size and color of the
symbol are log scaled as a function of trichloroethylene concentration. Plate 6.3c is
a useful presentation technique to examine data for source identification and elimi-
nates biases associated with contouring. When these data are overlain with other features
such as a sewer piping map (Plate 6.3d), a causal relationship between the presence of
the TCE in soil gas and possible releases from the sewer piping becomes apparent.
When examining an exhibit using color and size-ramped dots as a function of
concentration, determine whether the method used to size ramp the concentrations is
consistent or whether it is manually adjusted to bias the viewer’s perception. Plate
6.4* depicts average benzene concentrations in soil. No information is available to
ascertain how the size ramping of the benzene concentrations was selected (e.g.,
linear or logarithmic methods).
6.4.2 COMPUTER CONTOURING

Computer-generated contour maps are generated by connecting data points using
mathematical equations known as algorithms. The proper algorithm selection and
data density exert a profound impact on the contouring. Abrupt shapes or anomalous
features are often symptomatic of improper algorithm selection. Peculiar contouring
shapes occur in areas with little data. A tendency to draw closed contours or “bull’s
eyes” around individual data points rather than enclosing a series of high values
within a single contour can occur in areas with few data points. In general, the smaller
the data density and smaller the contour interval, the greater the probability of
computer artifacts. Figure 6.8 contains examples where a computer program has
generated erratic contours in areas where the data are absent or scarce. Areas framed
in A, C, and D are patterns where no data are available, while B is a contour which
is extended in a direction which is similarly lacking data. Contours in the upper
middle of Figure 6.8 reflect a sufficient data density so that the biases observed in
frames A through D are not generated.
Examine the contours relative to individual data points. If closed contours are
offset from discrete data points, the contour and site map may be improperly scaled.
The framed contours in Figure 6.9 illustrate these types of features. The closed

FIGURE 6.8 Examples of computer-generated contour biases.
contours in the upper and lower right-hand quadrant are similar to the framed regions
in A through D on Figure 6.8.
A means to emphasize or minimize environmental data in a computer-generated
contour map is to adjust the contour intervals. The selection of a large contour
interval can mask a source of contamination, while a smaller contour interval tends
to emphasize potential source areas (Erickson and Morrison, 1995).
FIGURE 6.9 Example of contouring errors and scales between data point coordinates and a
base map.

FIGURE 6.10 Adjustment of data contour interval for source identification.
Figure 6.10 depicts two-dimensional contour maps for trichloroethylene concen-

trations in groundwater where identical data sets were used. For the map with a
trichloroethylene contour interval of 500 ppb, the data are not posted, which does not
allow for confirmation that all of the data were used to generate the contours. The
100-ppb contour map depicts multiple potential sources obscured on the 500-ppb
map due to the contour interval selection. The 100-ppb contour map also contains
posted data, thereby allowing confirmation of the contouring.
Common contouring methods used in constructing two- and three-dimensional
contour maps and animations include inverse distance, kriging, minimum curvature,
Sheppard’s method, and polynomial regression. Characteristics of each method are
summarized below.
6.4.2.1 Inverse Distance Method

The inverse distance method weights the influence of a single data point over all
others. This influence declines as one proceeds farther from the value; the greater the
weighting power, the faster the decrease in influence on the interpolation. One of the
characteristics of inverse distance gridding is the generation of bull’s eyes surround-
ing data within a gridded area.
6.4.2.2 Kriging
Kriging, or a form of kriging (i.e., indicator kriging), is a geostatistical method that
assumes an underlying linear variogram and attempts to express trends suggested by
a data set (Cressie, 1990; Delhomme, 1979; Journel et al., 1984; Olea, 1974). Kriging

obtains estimates by assigning larger weights to nearby sample location measure-
ments and smaller weights to those more distant. Kriging is considered more accurate
than the inverse distance method except in areas that have fewer data points relative
to other portions of the area being kriged. Because contouring data is usually limited,
the results of kriging can be misleading; depending on the parameters used to define
the semi-variogram, the same data can yield different results.
Kriging honors data, although the estimated values at locations between sample
sites is nonunique (Wingle and Poeter, 1993). While kriging can be a good procedure
for interpolating between data points, it is usually an inappropriate procedure for
extrapolation of data that are beyond the range of the sample locations. Comparisons
between conventional least-squares methods and kriging estimators indicate that for
samples of size less than about 50, kriging offers no clear advantages over a least-
squares method. Kriging may therefore be more useful for designing a network for
collecting data points than for data analysis (Hughes et al., 1981).
A variation of kriging is indicator kriging, which combines kriging with stochas-
tic simulation. (Journel et al., 1994). Indicator kriging differs from simple or ordinary
kriging in that a range of values is reduced to discrete values by defining threshold
values. This arrangement allows the rapid examination of multiple interpretations
that are distinctly different but which honor all of the original data and the nature of
the model semi-variogram. The consultant can then evaluate the effects of different
variations of the parameter being modeled; however, there is a difference between a
mathematical solution that while probable is not realistic for the parameter values
contoured using kriging.
6.4.2.3 Minimum Curvature Method

This method calculates the initial value of the grid based on the data, then repeatedly
smooths the gridded surface. For an identical data set, the minimum curvature
method projects trends in areas of missing data, which results in a greater degree of
variation than in the inverse distance method. Contouring software programs usually
allow the degree of projection to be adjusted.
6.4.2.4 Sheppard’s Method

Sheppard’s method is similar to the inverse distance method except that the least-
squares method has a tendency to eliminate the bull’s-eye contours frequently
created with the inverse distance method (Franke and Nielson, 1980).
6.4.2.5 Polynomial Regression

Polynomial regression is used to identify large-scale trends and data patterns. Many
variations exist in the degrees of polynomial regression to examine data trends.
In addition to selecting a contouring algorithm, an expert or confidential consult-
ant can adjust the data prior to contouring. Such techniques include smoothing or log-
normalizing the data. If the underlying data are manipulated prior to contouring, the
scientific validity and impact of these changes on the contouring should be examined.

FIGURE 6.11 Inverse distance, kriging, and minimum distance contours for identical data sets.
Different contouring algorithms can produce different contours for identical data
sets, as shown in Figure 6.11. Contours on maps A through C are from the identical
data set and contour interval. The contour on map D is an overlay of contours created
by inverse distance and kriging. The differences between these two methods may
visually appear minor; however, for large areas with limited data, contaminated
volume calculations and hence cost and time required for in situ remediation can be
dramatically impacted. While Figure 6.11 presents a two-dimensional example,
identical issues exist with three-dimensional representations.
6.4.3 COLOR-CODED DATA

Two and three-dimensional exhibits can be created that, while scientifically correct
and based on a complete and validated data set, obscure key information. An
example is selection of the contour interval. The contour maps in Plate 6.5* were
prepared using identical data. In the color-shaded contour map in Plate 6.5, the

contour interval selection is not constant. No information is provided regarding the
concentration range greater than 1500 parts per billion (ppb); therefore, the viewer
is unable to determine if the data in the shaded areas are closer to 1501 or 50,000
ppb. A means to re-examine these data forensically is to reproduce the contour map
using a constant contour density (Plate 6.5). The source area absent in the color-
shaded contour map becomes apparent when a consistent contour interval density
(100 ppb) is selected. An identical forensic methodology can be employed when
displaying hundreds or thousands of data points in a three-dimensional, computer-
generated animation. Plate 6.6* is an example of two stills from an animation that
relies upon a similar principle as Plate 6.5. A similar example is shown in the four
colored panels in Plate 6.7*, where differences in the color range are used to mask
potential contaminant source areas.
When examining three-dimensional stills or animations using iso-surfaces, real-
ize that the contouring programs employed to construct these surfaces default to a
confidence and/or probability level used to create these surfaces. Plate 6.8* illustrates
contaminant iso-surfaces with two different contouring confidence levels for an
identical data set. The iso-surface in both panels is set to include all of the soil
concentration data between non-detect and 150 ppb. The upper panel illustrates an
iso-surface with a 95% confidence level, while the lower panel is set at a 50%
confidence level. Tremendous latitude, therefore, exists for visually manipulating the
perceived extent of the subsurface contamination via the selection of lower iso-
surface confidence levels, especially for small data sets and/or for instances where
there are large distances between the data points.
Contaminant transport simulations are frequently used as demonstrative evi-
dence associated with contaminant fate and transport analysis. As such, the input
data used in the model permit the author to fit the data to produce a prescribed result
(see Chapter 5). The forensic evaluation of graphics depicting the results of con-
taminant transport modeling (stills or animations) includes examination of the
following:
• The accuracy and representativeness of the input data

• Applicability of the visualization software
• Selection of the simulation used for presentation (assuming multiple simulations
were performed)
• Exhibit scaling
• Angle of inclination and rotation selected
• For iso-surfaces, the statistical confidence level assigned to the iso-surface depicted
in the exhibit
• Whether the contaminant depicted is representative of other compounds of concern
Several of the tasks are identical to the technique used to evaluate other types of
environmental exhibits. The selection of model boundary conditions, the applicabil-
ity of the computer software relative to the site, data density, and the selection of a
particular simulation, however, are unique to contaminant transport models.
* Plates 6.6 through 6.8 appear at the end of the chapter.

REFERENCES
Cressie, N., 1990. The origin of kriging, Mathematical Geology, 22:239–252.

Delhomme, J., 1979. Spatial variability and uncertainty in groundwater flow parameters: a
geostatistical approach, Water Resources Research, 15(2):269–280.
Franke, R. and G. Nielson, 1980. Smooth interpolation of large sets of scattered data, Inter-
national Journal of Numerical Methods in Engineering, 17:1691–1704.
George, S., 1992. Positive and negative bias associated with the use of EPA Method 418.1 for
the determination of total petroleum hydrocarbons in soil, in Proc. of the 1992 Petroleum
Hydrocarbon and Organic Chemicals in Ground Water: Prevention, Detection, and
Restoration Conference, National Ground Water Association, Houston, TX, pp. 35–52.
Hughes, J. and D. Lettenmaier, 1981. Data requirements for kriging: estimation and network
design, Water Resources Research, 17(6):1641–1650.
Joseph, G., 1996. Modern Visual Evidence, Law Journal Seminars Press, New York, p. 474
Journel, A. and E. Isaaks, 1984. Conditional indicator simulation: application to a Saskatchewan
uranium deposit, Mathematical Geology, 16(7):685–718.
Morrison, R., 1998. Forensic review of environmental trial exhibits, Environmental Claims
Journal, 11(1):93–107.
Morrison, R. and Erickson, R., 1995. Environmental Reports and Remediation Plans: Foren-
sic and Legal Review, John Wiley & Sons, Somerset, NJ, p. 570.
Olea, R., 1974. Optimal contour mapping using universal kriging, Journal of Geophysical
Research, 79(5):695–702.
Tufte, E., 1997. Visual Explanations: Images and Quantities, Evidence and Narrative, Graphic
Press, Cheshire, CT, p. 157.
Tufte, E., 1990. Envisioning Information, Graphic Press, Cheshire, CT, p. 126.
Tufte, E., 1983. The Visual Display of Quantitative Information, Graphic Press, Cheshire, CT,
p. 197.
Wingle, W. and E. Poeter, 1993. Uncertainty associated with semivariograms used for site
simulation, Ground Water, 31(5):725–734.
Zemo, D., Bruya, J., and T. Graf, 1995. The application of petroleum hydrocarbon fingerprint
characterization in site investigation and remediation, Ground Water Monitoring Review,
Spring:147–156.

Plate 6.1 Differences in perception due to exaggeration of the vertical scal-
ing. (Adapted from C-Tech, Environmental Visualization Systems Software, Irv-
ine, CA, 1998.)
Plate 6.2 Total petroleum hydrocarbon (TPH) results from split samples
using different analytical and extraction methods and corresponding contour maps.

Plate 6.3 Contoured concentration of TCE in soil gas.
Plate 6.4 Color and size ramping of circles to indicate benzene concentra-
tions in groundwater.

Plate 6.5 Two-dimensional contouring with color-coded data and different
contour intervals.
Plate 6.6 Computer animations based on biased data. (Adapted from C-Tech,
Environmental Visualization Systems Software, Irvine, CA, 1998.)

Plate 6.7 Examples of differences in the color range being used to mask
potential contaminent source sites.
Plate 6.8 Contaminant iso-surfaces with two different contouring confidence

levels for an identical data set.

Appendices
© 2000 CRC Press LLC

Appendix A. Sample
Calculation for the
Transport of PCE
Vapor through
Concrete Pavement
A.1 INTRODUCTION
The basic approach is to consider the diffusion of a liquid through a medium bounded
by two parallel plates with the planes at z = 0 and x = 1. After a time, a steady-state
is reached in which the concentration remains constant at all locations in the pave-
ment. The diffusion equation in one dimension, therefore, reduces to (Crank, 1985):
d2C/dx2 = 0 (Eq. A.1)
provided that the diffusion coefficient (D) is constant. On integrating with respect to
x, the following expression arises:
dC/dx = constant (Eq. A.2)
and by introducing the conditions at x = 0 and x = l and integrating, then:
[C – C1/C2 – C1] = x/l (Eq. A.3)
The previous two expressions show that the concentration changes linearly from C1
to C2 through the pavement. The transfer rate of the diffusing substance is the same
across all sections of the membrane, as described by the following expression:
F = –DdC/dx = D(C1 – C1)/l (Eq. A.4)

If the thickness (l) and the surface concentrations (C1 and C2) are known, then D can
be deduced from an observed value of F using this equation.
If the surface x = 0 is maintained at a constant concentration C1 and at x = 1, then
there is evaporation into an atmosphere for which the equilibrium concentration
immediately within the paved surface is C2, so that:
∂C/∂x + h(C – C2) = 0, x = l (Eq. A.5)
then
(C – C1)/(C2 – C1) = (hx)/(1 + hl) (Eq. A.6)
and
F = Dh(C1 – C2)/(1 + hl) (Eq. A.7)
If the surface conditions are
∂C/∂x + h1(C1 – C) = 0, x = 0; and

(Eq. A.8)
∂C/∂x + h2(C – C2) = 0, x = l
then
C = [h1C1{1 + h2(l – x)} + h2C2(1 + h1x)]/

(Eq. A.9)
[h1 + h2 + h1h2l]
A.2 SAMPLE CALCULATION
Given these relationships, the one-dimensional gas diffusion rate through a paved
surface can be approximated using variations of the previous equations. In this
example, it is assumed that a vapor cloud of PCE has accumulated within the
concrete catch basin housing a vapor degreaser. The concrete is not cracked, nor are
there expansion joints (i.e., it was poured in placed). The vapor cloud has been
allowed to accumulate and collect within the concrete catch basin over a holiday
during which the forced air system in the building is not operating. The question
therefore, is can the PCE vapor move through the concrete over the 5-day holiday
period and, if so, at what rate?
To examine this question using the diffusion mathematics outlined in Crank
(1985), a one-dimensional plane diffusion (gas or liquid) through a porous plate is
assumed. The following parameters and values are assumed in this example:
• Henry’s Law constant for PCE is 2.82 ¥ 10–2 atm m3/mol.

• PCE is absent in the concrete and in the soil below it (C2 = Co = 0).
• The concentration of PCE in the vapor above the concrete is 1.272 ¥ 10–4 g/cm3.

FIGURE A.1 Conceptual model of the transport of PCE vapor through concrete.
A graphical representation of this problem is shown in Figure A.1. In this case, the
following governing equation becomes:
•
Q t / lC1 = Dt / l 2 – 1 / 6 – 2 / p 2 Â (–1) 2 / n 2 exp(– Dn 2 p 2 t / l 2 ) (Eq. A.10)
1
For a steady-state solution where time (t) goes to infinity, the flux rate is defined as
Qt = DC1/l(t – l 2/6D) (Eq. A.11)
which has an intercept L on the t-axis described as:
L = l 2/6D (Eq. A.12)
For a small period of time, then:

•
F( t ) = 2C 1 Â (D / pt )1 / 2 exp{–(2 m + 1) 2 l 2 /( 4 D)} (Eq. A.13)
M =1
For a small period of time, this series converges rapidly to:
ln (t1/2F) = ln {2C1(D/p)1/2} – L2/4Dt (Eq. A.14)

and
t1/2F = exp [ln {2C1(D/p)1/2} – L2/4Dt] (Eq. A.15)
and
F = t–1/2 exp [ln {2C1(D/p)1/2} – L2/4Dt] (Eq. A.16)
where D = the effective diffusion coefficient. The effective diffusion coefficient is

defined as (Millington and Quirk, 1959):
De = Do(A10/3)/PT2 (Eq. A.17)
Assuming that the volumetric air content of the concrete is 0.013 – 0.023, the total
porosity is between 0.06 and 0.14, and the gas diffusion rate for PCE is 0.0785 cm2/
sec (for TCE ª 7100 cm2/day), then:
De = (0.0785 cm2/sec)((0.013 – 0.023)3.33/(0.06 – 0.14)2) (Eq. A.18)
= (0.078 cm2/sec)((2.67 ¥ 10–5) – (9.73 ¥ 10–4)) (Eq. A.19)
= (2.67 ¥ 10–6) – (7.64 ¥ 10–5) cm2/sec (Eq. A.20)
Using this range of values, the flux rate through the concrete per unit area of surface
areas at x = L is
Time Flux Rate (F)

(sec) (cm/sec)
10 0
102 0
103 0
104 (27 hr) 1.85 ¥ 10–41
105 (1.16 days) 2.07 ¥ 10–21
106 (11.6 days) 5.89 ¥ 10–10
107 (116 days) 3.68 ¥ 10–10
108 (1116 days) 1.25 ¥ 10–10
Solving for the quantity of PCE vapor that has moved through the concrete (Q1)
yields:
Dt/L2 = (7.64 ¥ 10–5 cm2/sec)(t)/(15.2 cm)2 (Eq. A.21)
and
Q1/LC1 = 0.14 at 106 sec and 0.035 at 5 exp5 sec (Eq. A.22)
and

Q = (0.14)(15.2 sec)(1.274 ¥ 10–4 g/cm3) at 106 sec (Eq. A.23)
so for a fast diffusion rate (FD1), Q = 2.71 ¥ 10–4, and 0.27% of the PCE vapor mass has
diffused through the concrete in 106 sec (277 hours or 11.6 days); for a slow diffusion
rate (FD2), Q = 1.15 ¥ 10–4, and about 0.19% of the PCE vapor mass has diffused
through the concrete pavement in 3 ¥ 107 sec or 347 days, according to the following:
FD1 = t–1/2 exp[–13.588 – 7.56 ¥ 105/t(sec)] (Eq. A.24)
and
FD2 = t–1/2 exp[–15.39 – 2.75 ¥ 107/t(sec)] (Eq. A.25)
Using the expression in Equation A.13 (Crank 1985), the numerical approximation
of the time-dependent flux of PCE vapor through the 15.2 cm of concrete pavement
where FD1 = 7.64 ¥ 10–5 cm2/sec and FD2 = 2.10 ¥ 10–6 cm2/sec is as follows:
T T FD1 Fa FD2 F
(sec) (hr/days) (cm/sec) (g/day) (cm/sec) (g/day)
103 0.278 hr 0.00 0.00 0.00 0.00

104 2.78 1.85 ¥ 10–41 2.97 ¥ 10–34 0.00 0.00
2¥ 104 5.56 3.4 ¥ 10–25 5.47 ¥ 10–18 0.00 0.00
4¥ 104 11.1 3.89 ¥ 10–17 6.25 ¥ 10–10 0.00 0.00
105 27.8 2.07 ¥ 10–12 3.32 ¥ 10–5 0.00 0.00
1.5 ¥ 105 41 2.11 ¥ 10–11 3.37 ¥ 10–4 0.00 0.00
2¥ 105 2.3 days 6.41 ¥ 10–11 1.03 ¥ 10–3 8.92 ¥ 10–70 1.43 ¥ 10–62
4¥ 105 4.6 3.0 ¥ 10–10 4.82 ¥ 10–3 4.54 ¥ 10–46 7.31 ¥ 10–33
106 11.6 5.9 ¥ 10–10 9.48 ¥ 10–3 2.36 ¥ 10–22 3.79 ¥ 10–15
2¥ 106 23 6.1 ¥ 10–10 9.78 ¥ 10–3 1.56 ¥ 10–16 2.51 ¥ 10–9
107 115 — — 4.19 ¥ 10–12 6.73 ¥ 10–5
108 1157 — — 1.57 ¥ 10–11 2.53 ¥ 10–4
a F cm/cm ¥ 1.61 ¥ 107 = F g/day.
In this sample problem, by day one about 3.3 ¥ 10–5 g have diffused through the
concrete. Steady-state conditions are reached in both instances between about 6 and
212 days. Approximately 1 to 23 days are required before any mass starts to emanate
through the 15.2 cm of concrete. The diffusion of PCE through the concrete ranges
from about 2.1 ¥ 10–6 to 7.64 ¥ 10–5 cm2/sec. This range is due to the variability of
the concrete porosity and the values of air porosity selected for this example.
REFERENCES
Crank, J., 1985. The Mathematics of Diffusion, 2nd ed., Oxford University Press, New York,
p. 345.
Millington, J. and J. Quirk, 1959. Permeability of porous media, Nature (London), 183:387–388.

Appendix B. Sample
Calculation for the
Transport of PCE Liquid
through Concrete
via Diffusion
B.1 INTRODUCTION
Liquid diffusion of a chlorinated solvent through a paved surface is an extremely

slow process. The transport of a chlorinated solvent through concrete via liquid
diffusion assumes that the paved surface is saturated and that the effective porosity
of the pavement provides a continuous pathway for the solvent dissolution. These
calculations assume an absence of cracks and expansion joints in the pavement that
could provide a preferential pathway for liquid migration into the underlying soil.
B.2 SAMPLE CALCULATION
An estimation of perchloroethylene (PCE) transport through a porous media such as

concrete via liquid diffusion can be developed based on the mathematics provided in
The Mathematics of Diffusion (Crank, 1985). The reader is encouraged to examine
this treatise when developing a liquid diffusion model, as numerous mathematical
constructs are available for various problem assumptions.
In this example, the following conditions are assumed:
• Length of the concrete is 15.2 cm.

• The diffusion rate of PCE in water = 1.5 ¥ 10–5 cm2/sec (for TCE, the water
diffusivity value ª 0.8304 cm2/day).
• The diffusion of PCE (DL) = Doq(10/3)/P 2T.
• Total concrete porosity is 0.06 to 0.14.
• Volumetric content is equal to 0.02 to 0.04%.

Given these assumptions, DL, then:
DL = 1.65 ¥ 10–5 cm2/sec [(0.02 – 0.043.33)/(0.06 – 0.14)2 (Eq. B.1)
= 1.68 ¥ 10–8 to 1.6 ¥ 10–9cm2/sec (Eq. B.2)
= 1.38 ¥ 10–3 to 1.38 ¥ 10–4 cm2/sec (Eq. B.3)
Given that the flux rate (F) is defined as (see Appendix A for a more thorough
derivation):
F = t–1/2 exp[ln (2C1(D/p))1/2] – L2/4Dt (Eq. B.4)
then the flux rates (Fcm/day) and mass (Fg/cm) for a diffusion rate of PCE in water of
1.65 ¥ 10–5 cm2/sec are
Time (days) Fcm/day Fg/cm
0.1 0.0 0.0

1.0 0.0 0.0
10 0.0 0.0
102 0.0 0.0
2 ¥ 102 2.61 ¥ 10–92 6.21 ¥ 10–86
300 4.53 ¥ 10–62 1.08 ¥ 10–56
400 5.73 ¥ 10–47 1.36 ¥ 10–41
1000 7.16 ¥ 10–20 1.70 ¥ 10–14
2000 6.35 ¥ 10–11 1.51 ¥ 10–5
2500 3.75 ¥ 10–9 0.00089
2750 1.64 ¥ 10–8 0.0039
3000 5.59 ¥ 10–8 0.0133
4000 1.59 ¥ 10–6 0.378
5000 1.16 ¥ 10–5 2.75
6000 4.2 ¥ 10–5 10.10
7000 1.07 ¥ 10–4 25.50
In excess of about 2000 days or 5.4 years are required before any appreciable (1.51
¥ 10–5 g/cm) quantity of perchloroethylene diffuses through the concrete. For a brief,
transient spill of PCE on concrete, therefore, PCE transport via liquid diffusion
through 15.2 cm of concrete is insignificant, especially when mechanisms such as
evaporation are considered.
REFERENCES
Crank, J., 1985. The Mathematics of Diffusion, 2nd ed., Oxford University Press, New York,
p. 345.

Appendix C. Properties
of Alcohol Oxygenates
and Ether Oxygenates
Properties of Alcohol Oxygenates
Property MeOH EtOH IPA BuOH GTBA
Chemical name Methanol Ethanol Isopropyl alcohol n-Butanol Gasoline grade t-butanol
Chemical formula CH3OH C2H5OH (CH3)2 CHOH C4H9OH (CH3)3 COH
Flash point
∞F 52 55 53 84 52
∞C 11 13 12 29 11
Heating value (Btu/gal) 56,800 76,000 87,400 96,800 94,100
Latent heat of vaporization 3340 2378 2100 1700 1700
(Btu/gal)
Boiling point (∞F) 149 173 180 244 176–181
Composition (%wt)
Carbon 37.49 52.14 59.96 64.82 65.0
Hydrogen 12.58 13.13 13.42 13.60 13.7
Oxygen 49.93 34.73 26.62 21.58 21.3
Molecular weight 32.04 46.07 60.09 74.12 73.5
Relative density (60∞F) 0.7963 0.7939 0.7899 0.8137 0.7810
Water solubility (70∞F)
Fuel in water (%) 100 100 100 100 100
Water in fuel (%) 100 100 100 100 100
Viscosity (mm/sec)
68∞F 0.74 1.50 3.01 3.54 7.4
–4∞F 1.44 3.58 7.43 — Solid
From Gibbs, L., in Proc. of the Southwest Focused Ground Water Conference: Discussing the Issue of MTBE and Perchlorate in Ground Water
(suppl.), National Ground Water Association, Dublin, OH, 1998. With permission.

Properties of Ether Oxygenates
Property MTBE TAME THEME ETBE TAEE DIPE
Chemical name Methyl-tertiary- Tertiary-amyl- Tertiary-hexyl- Ethyl-tertiary- Tertiary-amyl- Diisopropyl

butyl-ether methyl-ether methyl-ether butyl-ether ethyl-ether ether
Chemical formula (CH3)3COCH3 (CH3)2(C2H5) COCH3 (CH3)2(C3H7) COCH3 (CH3)3COC2H5 (CH3)2(C2H5)COC2H5 (CH3)2CHOCH(CH3)2
Flash point
∞F –14 11 — –3 — 9
∞C –26 –11 — –19 — –12
Heating value (Btu/gal) 93,500 100,600 — 97,000 — 100,000
Latent heat of vaporization 863 870 — 830 816 900
(Btu/gal)
Boiling point (∞F) 131 187 230 163 214 155
Composition (%wt)
Carbon 68.13 70.53 72.35 70.53 72.35 70.53
Hydrogen 13.72 13.81 13.88 13.81 13.88 13.81
Oxygen 18.15 15.66 13.77 15.66 13.77 15.66
Molecular weight 88.15 102.18 116.2 102.18 116.2 102.18
Relative density (60∞F) 0.7460 0.7758 0.7860 0.7452 0.7705 0.7289
Water solubility (70∞F)
Fuel in water (%) 4.8 1.15 — 1.2 0.4 —
Water in fuel (%) 1.5 0.6 — 0.5 0.2 —
Viscosity (mm/sec)
68∞F 0.47 — — — — —
–4∞F 1.44 — — — — —
From Gibbs, L., in Proc. of the Southwest Focused Ground Water Conference: Discussing the Issue of MTBE and Perchlorate in Ground Water (suppl.), National Ground
Water Association, Dublin, OH, 1998. With permission.

Appendix D. Advective
and Partitioning Transport
Equations of Radon
for Detecting Diesel
in Groundwater
D.1 INTRODUCTION
The basis of the advective and partitioning equations for radon (222Rn) as a means to
detect diesel in groundwater is described in an article by Hunkeler et al. (1977) in
Environmental Science and Technology. It is recommended that the reader interested
in this method examine this source paper in addition to references used to solve the
various solutions of Darcy’s Law (Freeze and Cherry, 1979; Wang and Anderson,
1982). The derivation of Darcy’s Law for advective transport with dispersion is
presented here, along with the partitioning derivation reported by Hunkeler et al. for
222Rn. While this approach is specific to radon, it provides interesting possibilities for
other types of contaminants.
D.2 DERIVATION
A form of Darcy’s Law for three-dimensional flow through an isotropic media can
be expressed as:
qx = –k(∂f/∂x) (Eq. D.1)
qy = –k(∂f/∂y) (Eq. D.2)
qz = –k(∂f/∂z) (Eq. D.3)

where
qx, qy, qz = specific discharge vectors (Eq. D.4)
x, y, z = Cartesian coordinate system (Eq. D.5)
k = saturated hydraulic conductivity (Eq. D.6)
The specific discharge vector with components qx, qy, qz can be expressed as qi, with
the notation (i) representing x, y, or z, and the partial derivatives ∂f/∂x, ∂f/∂y, and
∂f/∂z representing the three components of the hydraulic gradient. The hydraulic
gradient can then be written as:
∂if = [∂f/∂x), (∂f/∂y), (∂f/∂z)] (Eq. D.7)
which can be compressed in tensor notation as:
qi = –k∂if (Eq. D.8)
In the general case for three-dimensional flow, Darcy’s Law provides three equations
for motion for four unknown variables (qx, qy, qz, and f). The fourth equation (mass
balance) is required for groundwater flow and reduces to the equation of continuity
used to describe steady-state groundwater flow. This is expressed as:
∂qx/∂x + ∂qy/∂y + ∂qz/∂z = 0 (Eq. D.9)
By combining Darcy’s Law and the continuity equation together, the four equations
for the four unknown quantities can be solved. Three of the equations are eliminated
by substituting the derivative (–k∂if) for qi in the continuity equation, which yields:
∂/∂x [k∂f/∂x] + ∂/∂y [k∂f/∂y] + ∂/∂z [k∂f/∂z] = 0 (Eq. D.10)
If the saturated hydraulic conductivity (k) is treated as a constant, then Equation D.10
is reduced to (Laplace’s equation in three dimensions):
[∂2f/∂x2] + [∂2f/∂y2] + [∂2f/∂z2] = 0 (Eq. D.11)
The technique, described by Hunkeler et al. (1997), included the use of Darcy’s
equation in one dimension for solving for 222Rn in a non-aqueous phase liquid
(NAPL)-contaminated aquifer. Assumptions included:
• The average distribution of 226Ra, the parent nuclide of 222Rn, in the solid phase is
homogeneous at a macroscopic scale.
• Aquifer porosity is constant.
• 222Rn loss from the saturated to the unsaturated zone is neglected.
• Partitioning of 222Rn between the NAPL and water phase is in equilibrium.

• The partition coefficient is independent of the NAPL saturation.
• The NAPL is immobile.
• Sorption of 222Rn to the soil is neglected.
The one-dimensional advective and dispersive equation for 222Rn transport, 222Rn
release from mineral surfaces, and the 222Rn decay and partitioning of 222Rn between
the NAPL and water phase are described as:
∂/∂t [(1 – S)qA + qSANAPL] = –∂/∂x [qA – (1 – S)qD ∂A/∂x] +

(Eq. D.12)
(1 – q)rPl – [(1 – S)qA + qSANAPL]l
where
t = time in seconds.
S = the NAPL saturation of pore space (NAPL volume divided by the pore space
volume).
q = soil porosity.
A = the 222Rn activity in the water phase at location (x) at time (t).
ANAPL = the 222Rn activity in the NAPL at location (x) at time (t).
x = flow distance in meters.
q = the groundwater discharge.
D = dispersion coefficient of 222Rn in groundwater (m sec–1).
r = density of the soil (kg m–3).
P = the emanation of 222Rn decay from mineral surfaces per mass of dry aquifer
material (kBq kg–1).
l = radioactive decay constant of 222Rn (sec–1).
The partitioning of 222

Rn between the water phase and NAPL phase at equilibrium
is described by:
ANAPL = KA (Eq. D.13)
where K = the water and NAPL partition coefficient of 222Rn. Substituting Equation
D.13 into D.12 results in:
q[1 + S(K – 1)] ∂A/∂t = –∂/∂x [qA – (1 – S)qD ∂A/∂x] +

(Eq. D.14)
(1 – q)rPl – q[(1 + S)(K – 1)]Al
D.3 CONCLUSIONS
This method provides a natural tracer and requires the measurement of radon activity
only once. In order to provide the greatest degree of discrimination from monitoring
well, the wells should be installed both within the NAPL-contaminated zone and
upgradient and downgradient of the zone.

REFERENCES
Freeze, A. and J. Cherry, 1979. Appendix X, in Groundwater, Prentice-Hall, Englewood

Cliffs, NJ, p. 604.
Hunkeler, D., Hoehn, E., Hohener, P., and J. Zeyer, 1997. 222Rn as a partitioning tracer to
detect diesel fuel contamination in aquifers: laboratory study and field observations,
Environmental Science and Technology, 31:3180–3187.
Wang, H. and M. Anderson, 1982. Introduction to Groundwater Modeling: Finite Difference
and Finite Element Methods, W.H. Freeman, San Francisco, CA, p. 235.

Appendix E. Chemical
and Commercial
Synonyms for Selected
Chlorinated Solvents and
Aromatic Hydrocarbons
Solvent and Chemical Formula Chemical and Commercial Synonyms
Benzene (C6H6) Annulene; Benzeen (Dutch); Benzen (Polish); Benzin; Benzine;

Benzol; Benzole; Benzolene; Benzolo (Italian); Bicarburet of
Hydrogen; Carbon Oil; Coal Naphtha; Cyclohexatriene; Fenzen
(Czech.); Mineral Naphtha; Motor Benzol; Nitration Benzene;
Phene; Phenyl Hydride; Phrobenzol; Pyrobenzole
Bromoform (CHBr3) Bromoforme (French); Bromoformio (Italian); Methenyl

Tribromide; Tribrommethaan (Dutch); Tribrommethan
(German); Tribromometan (Italian); Tribromomethane
Carbon tetrachloride (CCl4) Carbon Bisulfide; Carbon Bisulphide; Carbon Chloride; Carbon
Disulphide; Carbon Sulfide; Carbon Sulphide; Dithiocarbonic
Anhydride; NCI-C04591; Sulphocarbonic Anhydride; UN 1131;
Weeviltox; Benzinoform; Carbona; Carbon Chloride; Carbon
Tet; ENT 4705; Fasciolin; Flukoids; Freon-10; Halon-104;
Methane Tetrachloride; Necatorina; Necatorine;
Perchloromethane; R 10; RCRA Waste Number U211;
Tetrachloormetaan; Tetrachlorocarbon;
Tetrachloromethane; Tetrafinol; Tetraform; Tetrasol;
UN 1846; Univerm; Vermoestricid

Chloroform (CHCl3) Chloroforme (French); Choroformio (Italian); Freon-20;

R 20; R 20 refrigerant; Formyl Trichloride; Methenyl Chloride;
Methyl Trichloride; Trichloroform; Trichloromethane;
Methan Trichloride: Methenyl Trichloride; Methyltrichloride;
Trichloromethane; Trichloormethaan (Dutch); Trichlormethan
(Czech.); Trichloroform; Trichlorometano (Italian); UN 1888
Chloromethane (CH3Cl) Arctic R40; Freon-40; Methyl Chloride; Monochloromethane;

UN 1063
1,1-Dichloroethane (C2H4Cl2) Chlorinated Hydrochloric Ether; Ethylidene Dinechloride;

Ethyledene Dichloride; UN 2362
1,2-Dichloroethane (C2H4Cl2) 1,2-Bichloroethane; Borer Sol; Brocide; 1,2-DCA; Destruxol

Borer-Sol; Dichloremulsion; Dichlormulsion; Dichloroethylene;
Dutch Liquid; Dutch Oil; Ethylene Dichloride; Freon-150;
EDC; ENT 1656; Glycol Dichloride; NCI-C00511; UN 1184
1,1-Dichloroethylene (C2H2Cl2) Chlorure de Vinylidene (French); 1,1-DCE; 1,1-Dichloroethene;

Sconatex; VDC; Vinylidene Chloride II; Vinylidene Chloride;
Vinylidene Dichloride; Vinylidine chloride
Dichloromethane (CH2Cl2) Aerothene; DCM; Freon-30; MM; Methylene Bichloride;

Methylene Chloride; Methylene Dichloride; Narcotil; NCI-
C50102; Solaesthin; Solmethine; UN1593
Ethylene dibromide (C2H4Br2) Alphat; beta-Dibromomethane; Bromofume; Celmide;

1,2-Dibromomethane; DBE; Dibrome, Dowfume;
40-Dowfume; Dowfume W-8; Dowfume W-90;
Dibromoethane; EDB-85; Ethylene Bromide; Ethylene
Bromide Glycol Dibromide, Fumo-Gas; Glycol Bromide;
Glycol Dibromide; Iscobrome D; Kopfume; Nephis;
Soilfume; Pestmaster; Pestmaster EDB-85; Soilbrome-40;
Soilbrome-90; Soilbrom-90C; Soilbrom-100; Soilbrome-85;
Unifume
Freon-11 (CCl3F) Algonfrene Type 1; Arcton 9; Electro-CF 11; Eskimon 11; F11;
FC 11; Fluorocarbon 11; Fluorotrichloromethane; Freon-11A;
Freon-11B; Freon HE; Freon MF; Frigen 11; Genetron 11;
Halocarbon 11; Isceon 11; Isotron 11; Ledon 11;
Monofluorotrichloromethane; Refrigerant 11;
Trichlorofluoromethane; Ucon 11; Ucon Fluorocarbon; Ucon
Refrigerant 11
Freon-113 (FCl2CCF2Cl) Arcton 63; Arklone P; Daiflon S3; Fluorocarbon 113; F-113;
FC-113; Freon® 113; Frigen 113a; TR-T; Genetron 113;
Halocarbon 113; Isceon 113; Khladeon; Kaiser Chemicals 11;
R-113; R113; Refrigerant 113; TTE; 1,1,2-Trifluoro-1,2,2-
Trichloroethane; Trichlorotrifluoroethane; 1,1,2-Trichloro-1,2,2-
Trifluoroethane; 113; Ucon-113; Ucon Fluorocarbon; Ucon
113/Halocarbon 113

Methylene chloride (CH2Cl2) Dichloromethane; DCM; Methylene Dichloride; Methylene

Bichloride; Aerothene MM; Freon-30; Narcotil; NCI-C50102;
RCRA Waste Number 84.16; RTECS; GY 4640000; Turco
5873; #5141 Chlorinated Solvent
Phenol (C6H60) Acide Carbolique (French); Baker’s P and S Liquid and

Ointment; Benzenol; Carbolic Acid; Carboilsaure (German);
Fenol (Dutch, Polish); Fenolo (Italian); Hydroxybenzene;
Monohydroxybenzene; Monophenol; Oxybenzene; Phenic Acid;
Phenol Alcohol; Phenol Molten; Phenole (German);
Phenylhydrate; Phenyl Hydroxide: Phenylic Acid; Phenylic
Alcohol
1,1,1-TCA (Cl3CCH3) a-T; a-Trichloroethane; Aerothene; Aerothene TT; Alpha-

1,1,1-trichloroethane; Alpha Trichloroethane; Amsco Solv
5620; Baltana; Blaco-Thane; Chloroethane NU; Chloroethene;
Chlorten; Crack Check Cleaner C-NF; Genklene; DEV TAP;
Devcon; Devon Metal Guard; FL-20 Flexane Primer Lube-Lok
4253; Locquic Primer T; Inhibisol; Methyltrichloromethane;
Methyl Chloroform; M-60; NCI-C04626; NU; Rapid Tap;
Perm-Ethane; PCN UCD 5620; PCN-UCD 15620; Quik Shield;
RCRA Waste Number U226; Solvent 111®; Solventclean SC-A
Aerosol; Saf-Sol 20/20; TCA; SKC-NF/ZC-73; Tri-ethane;
Turco Lock; UCD 784; VG; UN 2831; #10 Cleaner; #5141
Chlorinated Solvent
Tetrachloroethylene (Cl2Cl4) Ankilostin; Antisol; Crack Check Cleaner C-NF; Didakene;

Carbon Bichloirde; Carbon Dichloride; Dee-Sol; Didakene;
Dow-Per; Dow-Clene ECENT 1860; Ethylene Tetrachloride;
Fedal-UN; NCI-C04580; Nema; PCE; PER; PERC; Percelene;
Perawin; Perchlor; Perchlorethylene; Perchloroethylene;
Perclene; Percosolv; Perk; Persec; PerSec 1; Tetlen; Tetrophil;
Tetracap; Tetrachloroethylene; Tetrachloroethene; 1,1,2,2-
Tetrachloroethylene; Tetropil; Tetracap; Tetraleno; Tetravec;
Tetroguer; Tetropil; UN 1897; #5141 Chlorinated Solvent
1,1,2,2-Tetrachloroethylene (C2Cl4) Ankilostin; Antisol 1; Carbon Bichloride; Carbon Dichloride;

Czterochloroetylen (Poland); Didakene; Dow-Per; Ent 1.860;
Ethylene Tetrachloride; Fedal-UN; Nema; Perawin;
Perchloorethyleen Per (Dutch); Perchlor; Perchloraethylen, Per
(German); Perchlorethylene; nPerchlorethylene, Per (French);
Perclene; Perchloroetilene (Italian); Percosolve; Perkcosolve;
Perk; Perklone; Persec; Tetlen; Tetracap; Tetrachlooretheen
(Dutch); Tetrachloraethen (German); Tetrachloroethene;
Tetrachloroetene (Italian); Tetraleno; Tetralex; Tetravec;
Tetroguer; Tetropil
1,1,2-Trichloroethane (C2HCl3) Cement T-399; Ethane Trichloride; 1,2,2 Trichloroethane; d-T;

b-trichloroethane; Vinyl Trichloride

Trichloroethene (C2HCl3) Acetylene Trichloride; Algylen; Anamenth; Anameneth;

Benzinol; Blancosolv; Blacosolv; 1-Chloro-2,2-
dichloroethylene; Cecolene; Chlorylea; Chlorylen; Chorylen;
Chlorilen; Circosolv; Crawhaspol; 1,1-Dichloro-2-
chloroethylene; Densinfluat; Dow-Tri, Dow-TriPhilex;
Dukerson; Ethinyl Tri-Plus; Ethylene Trichloride; Ethinyl
Trichloride; Fleck-Flip; Flock-Flip; Fluate; Germalgene; Hi-Tri;
Lanadin; Lethurin; Narcogen; Narkosoid; Nialk; Neu-Tri; NCI-
C04546; Petzinol; Perm-a-chlor; Perm-a-clor; Petzinol;
Philex; Trichloroethylene; 1,1,2-Trichloroethylene;
Trichloroethene; Tri-Clene; Trielene; Trichloran; Trichloren;
Trimar; Trline; Trethylene; Trichloride Triad; Trimar; Turco
Surjex; Triasol (Trichlooretheen (Dutch); Trichloraethen
(German); Trichloran; Trichlorretent, Trichloroethilene, and
Trielina (Italian); tVestrol; UN 1710;Vitran; Vestrol; V-strol;
Westrosol; Zip Grip Accelerator
Vinyl chloride (C2H3Cl) Chloroethene; Chloroethylene; Ethylene Monochloride; VC;

VCM; 1-Chloroethene; 1-Chloroethylene; Ethylene
Monochloride; Monochloroethene; Monochloroethylene; MVC;
Trovidur; UN 1086; Vinyl C Monomer; Vinyl Chloride
Monomer
Xylene (C8H10) Dimethylbenzene; Ksylen (Poland); Methyl Toluene; Violet 3;

Xiloli (Italian); Xylenen (Dutch); Xylole (German); #5141
Chlorinated Solvent
REFERENCES
IARC, 1979. Monographs on the Evaluation of the Carcinogenic Risk of Chemicals to

Humans, Vol. 20, Halogenated Hydrocarbons, International Agency for Research into
Cancer, Switzerland.
MacKay, D., Shui, W., and K. Ma, 1993. Illustrated Handbook of Physical-Chemical Prop-
erties and Environmental Fate for Organic Chemicals. Vol. III. Volatile Organic Chemi-
cals, Lewis Publishers, Chelsea, MI, p. 916.
p. 271.
Pankow, J., Feenstra, S., Cherry, J., and M. Ryan, 1996. Dense chlorinated solvents in
groundwater: background and history of the problem, in Pankow, J. and J. Cherry (Eds.),
Dense Chlorinated Solvents and Other DNAPLs in Groundwater, Waterloo Press, Port-
land, OR, p. 1–46.
370.

Appendix F.
Laboratory Terms
and Definitions
Laboratory Term/
Abbreviation Definition
Accuracy The ability of a procedure to determine the “true” analyte
concentration.
Batch A group of 20 samples or less, of similar matrix type,
prepared or analyzed together if no sample preparation is
required, under the same conditions and with the same
analytical reagents. The batch must include a method blank,
laboratory control standard, and matrix quality control.
Blank (B) Indicates that the compound was detected in the sample and
blank; the sample value is usually reported without the blank
subtraction. If the sample value is less than 10¥ the blank
value times the sample dilution factor, the compound may be
present as a laboratory contaminant.
Blank result The result of analyzing a method blank (reagent water that is
subjected to the same preparation procedures as the batch
samples). The blank result is used to identify laboratory
contamination.
BNA Base-neutral/acid fraction (also called extractable semi-
volatile fraction). The BNA represents the pollutant that can
be extracted from a sample but which boils higher than 120∞C
and still passes through a gas chromatography column.
CAM California Assessment Manual; the original draft of this
manual contains California hazardous waste rules, one of
which lists 17 toxic or “CAM” metals.

Laboratory Term/
Control Control limits are determined from historical data for a
quality control parameter. The test value must be within this
acceptable range for the test to be considered in control. This
range usually corresponds to the 99% confidence interval for
the historical data.
DCS Duplicate control sample.
Dilution (D or DIL) Indicates that the sample was diluted and, as a consequence,
the surrogates were too diluted to measure accurately.
Detection limit (DL) The minimum value that can be detected in the sample with
a high degree of confidence taking into account dilution
factors and interferences. The reported detection limits are
equal to or greater than the method detection limit (MDL) to
allow for daily and instrument-to-instrument variations in
sensitivity.
EB Equipment blank.
Instrument detection limit (IDL) The smallest signal above background noise that an
instrument can detect.
Laboratory control standards (LCS) The laboratory control standard indicates the accuracy of the
analytical method. The LCS also provides verification of the
calibration because it is prepared from a different source than
the standard used for instrument calibration. A LCS is
performed by spiking laboratory-grade reagent water with
known compounds and subjecting the spiked sample to the
same procedures as the samples.
Laboratory test results (LT) The expected result, or true value, of the Laboratory Control
Standard analysis.
Limit of detection (LOD) The lowest concentration that can be determined to be
statistically different from a blank. A LOD is often equivalent
to three times the standard deviation from replicate measure-
ments of concentrations near the limit of quantitation.
Limit of quantification (LOQ) The level above which quantitative results are obtained with a
specified degree of confidence. The LOQ is often defined as
equal to 10 times the standard deviation from replicate
measurements.
Matrix quality control Quality control tests performed on client samples. For most
inorganic analyses, the laboratory uses a pair of duplicate and
spiked samples. For most organic analyses, the laboratory
uses a pair of spiked samples (also called duplicate spikes).
Matrix spike (D) Matrix spike duplicate; this refers to a quality control sample
that may be a real sample or blank sample spiked with
representative target analytes.

Laboratory Term/
Method detection limit (MDL) The minimum concentration of a substance that can be
identified, measured, and reported with a 99% confidence that
the concentration is greater than zero.
NA (1) Not analyzed, or (2) a value is not available for the
parameter, usually for a detection limit.
NC Applies to spike recovery results and RPD. The relative
percent difference (RPD) and spike recovery are not
calculated when a result value is less than five times the
detection limit or if matrix interferences are present. A spike
recovery is not calculated when the sample result is greater
than four times the spike-added concentration because the
spike-added concentration is considered insignificant.
ND (not detected) Indicates that the compound was not found in the sample at
or above the detection limit.
% error A measure of accuracy based on the analysis of a Laboratory
Control Standard. The % error is expressed in percent as the
difference between the known value and the experimental
value divided by the known value. The Laboratory Control
Standard can be a solution-based standard that confirms
calibration or a continuing calibration verification. The LCS
may also be a reference sample taken during sample
preparation and analysis.
Percent recovery The percentage of analyte recovered. For Laboratory Control
Standards, the percent recovery is equal to the Laboratory
Control value divided by the Laboratory Test result and
multiplied by100. For spiked recoveries, the percent recovery
calculation is (S Bar – R Bar)/(True – R Bar) ¥ 100.
ppm Parts per million; usually equivalent in liquids to mg/L.
ppb Parts per billion; usually equivalent in liquids to mg/L and in
the gas phase to mg/L (mL/m3).
Practical quantification limit (PQL) The level that can be reliably achieved within a specified
limit of precision and accuracy during routine laboratory
operation conditions. The PQL is a U.S. Environmental
Protection Agency interlaboratory concept that has been
estimated at 5 to 10 times the method detection limit.
Precision The reproducibility of a procedure demonstrated by the
agreement between analyses performed on either duplicates of
the same sample or a pair of duplicate spikes.
R1, R2 result The result of analyzing replicate sample aliquots, with R1
indicating the first analysis of the sample and R2 its
corresponding duplicate. R1 and R2 results are used to
determine precision.

Laboratory Term/
R Bar result The average of replicate analysis results.
Relative percent difference (RPD) This is a measure of the precision of the analysis. It is the
difference between duplicate results divided by the mean of
the duplicates. RPD is calculated by either of the following
relationships: (R1 – R2)/(R Bar) ¥ 100 or (S1 – S2)/(S Bar) ¥
100.
Reporting detection limit (RDL) A limit similar to but not the same as the method detection
limit (MDL) established via U.S. Environmental Protection
Agency guidelines. It is set by the analytical laboratory. The
RDL is not adjusted for dilution factors and may not be the
same as the sample result values.
S1, S2 result The results of the analysis of replicate spiked aliquots, with
S1 indicating one spike of the sample and S2 the second
spike. S1 and S2 test results are used to determine precision
and accuracy.
S Bar result The average of spike analysis results.
STLC Soluble threshold limit concentration; according to
California’s hazardous waste regulations, a waste is
considered hazardous if the concentration in the leachate from
the waste extraction test (WET) exceeds this limit.
Surrogates Organic compounds similar to the target analytes in chemical
composition and behavior in the analytical process, but which
are not normally found in environmental samples. All samples
are spiked with a surrogate compound(s) prior to analysis.
Surrogate percent recovery (%R) provides information about
the laboratory performance on individual samples and the
possible effects of the sample matrix on the analytical results.
TCLP Toxicity characteristic leaching procedure; according to U.S.
Environmental Protection Agency regulations, a waste is
considered hazardous if the leachate from the TCLP
extraction exceeds certain levels.
TR (trace) Indicates that the compound was observed at a value less than
the normal reported detection limit. Such values are subject to
large errors and should be considered as qualitative.
True value The theoretical, or expected, result of a spike sample analysis.
TTLC Total threshold limit concentration; according to California’s
hazardous waste regulations, a waste exceeding this
concentration is considered a hazardous waste.
VOA Volatile organic analysis; VOAs are a group of volatile
organic solvents with a boiling range from below room
temperature to about 150∞C.
WET Waste extraction test (see STLC).

Laboratory
Flags Definitions
A An analytical and/or post-digestion spike that has not been subjected to extraction or
digestion.
B A target analyte that is detected in a reagent blank but the sample results are not
corrected for the amount in the sample blank.
C An analyte has been confirmed by analysis on a second column on a gas chromato-
graph.
D Analytes detected in a secondary dilution factor. Because some compounds can
exceed the calibration range of the instrument, an analysis is performed at the
concentration of the majority of the analytes and a second analysis is performed with
the sample diluted so that high-concentration analytes fall within the calibration range
of the instrument.
E (1) The amount detected exceeds the calibration range of the instrument; (2) the
reported value was estimated because of the presence of interferences.
G A gas chromatography/mass spectrometry (GC/MS) result whose concentration
exceeds the calibration range for a specific analysis.
I A general-purpose flag defined by the individual laboratory.
J Indicates an estimated value for GC/MS data. A J flag is used when estimating a
concentration for a tentatively identified compound where a response factor of 1 is
assumed or when the mass spectral data indicates the presence of a compound that is
less than the sample quantitation limit.
M (1) Manual integration; (2) indicates that the duplicate injection precision of the
sample was not met.
N (1) Indicates presumptive evidence of a chemical found as a tentatively identified
compound based on a search of a mass spectrophotometry library; (2) indicates spike
control samples were not within control limits.
NR An analyte that was not requested by the client.
NS (1) Not sampled, or (2) an analyte or surrogate was not spiked to the sample for
analysis.
P Analyte has been confirmed on a second gas chromatograph column. A P flag is
applicable to analysis of samples from a regular sampling program as a specific
sample source.
Q A quality control standard that is outside method or laboratory specified control
limits, including matrix spike, analytical QC spikes, and surrogate recoveries.
R (1) The analyte was detected in the reagent blank and the sample results are corrected
for the amount in the sample blank; (2) indicates that the data are unusable.
S A result from a metals analysis has been obtained using the Method of Standard
Addition.
U (1) Confirmation on a second gas chromatograph column of dissimilar phase was not
requested; (2) indicates that the analyte was analyzed but not detected above the
sample detection limit.

Laboratory
Flags Definitions
UJ Indicates that the chemical was analyzed for but not detected. The associated value is
an estimate and may be inaccurate or imprecise.
X A second gas chromatograph column was used to provide confirmation but the
analyte was not confirmed and is probably a false positive.
* An analytical result that is less than five times the method-specified detection limit
and should be considered as approximate. As the method detection limit is ap-
proached, analytical uncertainty increases exponentially.
# The qualifier is out of range.

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Library of Congress Cataloging-in-Publication Data

© 2000 by CRC Press LLC

No claim to original U.S. Government works

©2000 CRC Press LLC

©2000 CRC Press LLC

©2000 CRC Press LLC

1 An Overview of the History, Chemistry,

©2000 CRC Press LLC

2 Chemistry and Transport of Petroleum Hydrocarbons

3 Identification of Biased Environmental Data

©2000 CRC Press LLC

4 Forensic Techniques Used in Environmental Litigation

©2000 CRC Press LLC

5 Contaminant Transport Modeling

©2000 CRC Press LLC

6 Forensic Review of Environmental Trial Exhibits

A Sample Calculation for the Transport of

B Sample Calculation for the Transport of

C Properties of Alcohol Oxygenates and Ether Oxygenates

D Advective and Partitioning Transport Equations

©2000 CRC Press LLC

F Laboratory Terms and Definitions

©2000 CRC Press LLC

PCE formulated by Faraday in 1821.

Chlorinated solvents are one of the most frequently encountered contaminants in

1.2 CHRONOLOGY AND USE OF

©2000 CRC Press LLC

Vapor degreasing 47.1 18.1 5.8 106.0 17.7 194.7

©2000 CRC Press LLC

©2000 CRC Press LLC

SD-15 Acra Electric; Schiller Park, IL N/A TCE, 1,1,1-TCA, PCE

Knowledge of the vapor degreaser or solvent still manufacturer is useful in

• Semiconductor wafer fabrication and assembly

Chlorinated solvents used in the semiconductor industry include 1,1,2-trichloro-

©2000 CRC Press LLC

Waycoat photoresist 85% xylene

associated with the photoresist process (California Department of Health Services,

©2000 CRC Press LLC

1.2.1 TRICHLOROETHYLENE (TCE)

©2000 CRC Press LLC

Note: Figures are in units of thousands of metric tons.

Trichloroethylene production began in Austria and the United Kingdom in 1908;

©2000 CRC Press LLC

©2000 CRC Press LLC

©2000 CRC Press LLC

1.2.3 1,1,1-TRICHLOROETHANE (1,1,1-TCA,

1,1,1-Trichloroethane was created in 1840 by the reaction of chlorine with 1,1-

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• Aragonesas and Erkimia (Spain)

Methylene chloride consumption in Western Europe decreased from about 190,000

1.3 CHEMISTRY AND PROPERTIES

1.3.1 TERMINOLOGY AND CLASSIFICATION

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Paint stripping 30 19.14

Note: Figures are percent of total usage.

• NAPL (non-aqueous phase liquid)

1.3.2 CHEMICAL STRUCTURE AND PROPERTIES

©2000 CRC Press LLC

©2000 CRC Press LLC

Trichloroethylene (TCE) 0.00937

1.3.3 HENRY’S LAW CONSTANT (KH)

KH¢ = KH/(RK) (Eq. 1.1)

KH¢ = dimensionless Henry’s Law constant.