Environmental Forensics (2000) 1, 175195

doi:10.1006/enfo.2000.0018, available online at http://www.idealibrary.com on

Critical Review of Environmental Forensic Techniques: Part II

Robert D. Morrison*
R. Morrison & Associates Inc., 201 East Grand Avenue, Escondido, CA 92025, U.S.A.
(Received 28 April 2000, Revised manuscript accepted 1 August 2000)
A multitude of forensic techniques are available for age dating and source identication, including aerial photography
interpretation, corrosion models, the commercial availability of a chemical, chemical associations with discrete types of
equipment, chemical proling, degradation models and contaminant transport models. The success of these techniques
in environmental litigation and their applicability to a particular fact situation is rarely discussed in the literature. When
these techniques are introduced as scientic evidence, their governing assumptions and the adequacy of the underlying
data are rigorously scrutinized and often, successfully challenged. The purpose of this paper is to review selected forensic
techniques and discuss their merits so that the user can select the technique or combination of techniques most
# 2000 AEHS
appropriate for the factual elements of the case.
Keywords: degradation model; reverse groundwater modeling; backward extrapolation modeling; inverse model;
chemical ngerprinting; chemical pattern recognition; proprietary additives; alkyl-lead.

Introduction

isotope analyses, weathering patterns, biomarkers, and

degradation models.

Identication of the origin of a contaminant release, the

timing of the release, and its distribution in the
subsurface are common issues in environmental litigation. Forensic techniques used to investigate these
issues include, in part, aerial photography interpretation, underground storage tank corrosion models,
identifying the date when a chemical or additive became
commercially available, association of a particular
chemical with a manufacturing process, chemical proling (ngerprinting), chemical degradation models,
and contaminant transport modeling. Part I of this
series discusses a review of aerial photography
interpretation, corrosion models, associations of chemicals with specic manufacturing activities or equipment, and chlorinated solvent applications for age
dating and source identication. Part II discusses the
use of petroleum hydrocarbon age dating and associated source identication techniques, stable isotope
analysis and contaminant transport modeling using
chlorinated solvents (especially TCE), polychlorinated
biphenyls (PCBs), and petroleum products to demonstrate the applicability of the methods. Discussions of
these techniques are included in the literature (Zemo,
Bruya and Graf, 1995; Kaplan and Galperin, 1996;
Kaplan, Galperin and Lee, 1997; Morrison, 1999a,c;
2000d) and in conference proceedings (University of
Wisconsin, 2000; International Business Communications, 2000).

Fingerprinting
Petroleum hydrocarbon ngerprinting or pattern
recognition allows identication of discrete fuel types
(i.e. diesel, gasoline, jet fuels, marine fuel, kerosene,
etc.) (Zemo, Bruya and Graf, 1995). If sucient spill
release information is available, this technique can
often discriminate whether a chemical release was a
single event, a series of events, or a continuous release
of a single or multiple products. This determination is
accomplished through pattern recognition or matching
of gas chromatogram traces (Rohrbach, 1998). Compounds used in pattern recognition analysis include
(Harvey, 1997; Stout, 1999; Stout, Uhler and
McCarthy, 1999; Stout et al., 1999a,b):
. light petroleum products (BTEX and heavier
aromatics, alkylate parans);
. diesel fuels and distillates (normal alkanes and
isoprenoid parans);
. 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).
The use of chromatographic pattern recognition is
frequently argued as a means to develop qualitative
estimates regarding the age of the petroleum hydrocarbon, or to assign a range of years (i.e. within a
10-year window, etc.), that is based upon the degree of
sample weathering. Frequent challenges to this argument include that there are substantial dierences in
weathering which are attributable to the subsurface
environment (anaerobic v. aerobic transformation) and
soil texture (e.g. moist clay v. moist sand). Additionally,

Petroleum Hydrocarbons
Forensic techniques available for age dating and source
identication of petroleum hydrocarbons include
hydrocarbon pattern recognition, use of proprietary
additives, alkyl-lead speciation, oxygenates, dyes, stable
*E-mail: bob@rmorrison.com

175
1527-5922/00/040175+20 $35.00/00

# 2000 AEHS

176 R. D. Morrison

there are uncertainties associated with the degree of

hydrocarbon weathering that occurred prior to a
release. Chromatographic age dating may be a useful
tool when there are chromatographic patterns available
for comparison, and when those chromatograms are
patterns of a similar product that was released into the
same environment at a known time. It is the author's
observation that pattern recognition is most useful
when used as a comparative tool between samples, and
not for age dating.

Proprietary Additives
Proprietary additives are blended with rened products,
such as fuels. Additives are frequently associated with
discrete time periods corresponding to when they were
blended with a product (i.e. polybutene additive was
present in the Chevron detergent F-310 in gasoline in
1982). The use of additives for hydrocarbon ngerprinting requires a prior knowledge of the additive
package, and the ability to detect an additive that is not
masked by other chemicals or obscured by environmental degradation. In practice, the chemical identication of an additive is not always straightforward. Many
additives contain oxygen in their molecular structure
and are highly soluble and/or biodegradable; they may
degrade and/or transform rapidly in the subsurface.
Some polymers, for example, rapidly depolymerize into
their respective monomers making it dicult to identify
the parent compound (Galperin, 1997). Additives are
sold to reneries with little or no chemical alteration by
the renery. As a result, the same additive may be
present in the parent compounds of multiple fuels and
those fuels may become commingled in the groundwater (Kram, 1988; Gibbs, 1990, 1993; Harvey, 1997;
Ethyl Corporation, 1998; Morrison, 1998a,b,
1999a,b,c,d). The composition of additive packages
for rened products varies with time. A typical mixture
for automotive gasoline in the 1980s consists of about
62% tetraethyl-lead, 18% ethylene dibromide, 18%
ethylene dichloride, and 2% inactive ingredients such
as dyes, antioxidants, petroleum solvents, and stability
improvers (Kaplan et al., 1997). Additives are also
blended with diesel and jet fuels. Additive packages for
diesel include diesel ignition compounds (alkyl nitrates
and nitrites, nitro-, nitroso-compounds and peroxides),
anti-oxidants (N,N-dialkylphenylenediamines, 2,6-dialkylphenols, 2,4,6-trialkylphenols), cold ow improvers
(ethylene vinyl acetate copolymers, ethylene vinyl
chloride copolymers, polyolens, chlorinated hydrocarbons), metal deactivators (N,N-disalicylidene-alkyldiamines), surfactants (alcohols, amines, alkylphenols,
carboxylic acids, sulfonates, succinamides) and combustion catalysts/deposit modiers (organometallics of
barium, calcium magnesium, iron, manganese). Ethylene glycol monomethyl ether, is present in some diesel
fuels to prevent clogging of fuel lines by microorganisms (Central Regional Water Quality Control Board,
1997). The jet fuel, JP-4, for example, contains icing
inhibitors (carboxylates, alcohols, dimethylformamide,
ammonium dinonylnaphthalene), metal deactivators
(N,N-disalicylidene-1,2-propanediamine, N,N-disalicylidene-1,2-cyclohexanediamine, N,N-disalicylidene1,2-ethanediamine) and anti-oxidants (alkyphenols,

N,N-di-sec-butyl-p-phenylendiamine) (Potter et al.,

1998).
Issues raised frequently when relying upon
petroleum additives for age dating and/or source
identication include product swapping between jobbers with dierent additive packages, the inability to
detect most additives unless phase separate-product is
present, commingling of fuels in the subsurface,
multiple releases of product with dierent additive
packages at the same location, and an incomplete
knowledge of the original additive package. In
addition, many fuel additives are proprietary.

Alkyl-leads
Chronologies based on the blending of alkyl-leads with
other additives into fuel products and their presence in
environmental samples is frequently cited as evidence
for age dating a product release. This approach is often
predicated on the documented changes in the use of
alkyl-leads and/or knowledge of the composition and
availability of additive packages (Gibbs, 1990; Harvey,
1998; Morrison, 2000a,b,c). Alkyl-leads were initially
added to gasoline to suppress spark knock and to
increase the octane number, although they also serve as
a valve lubricant by forming a protective coating on the
exhaust valve seat (EPA, 1999).
Lead additive packages often contain multiple
combinations of tetraethyl-, triethylmethyl-, methyldiethyl- and tetramethyl-leads, as well as redistribution
reaction mixtures of tetraethyl- and trimethyl-leads.
Redistribution reactions of equimolar amounts of
tetraethyl- and tetramethyl-leads can also produce
trimethyl-, trimethylethyl-, dimethyldiethyl- and
methyltriethyl-leads (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 (Stout et al., 1999b). A typical commercial
reaction mixture from the use of equimolar amounts of
tetraethyl-lead and trimethyl-lead is 3.8% trimethyllead, 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 used to suppress pre-ignition and
to improve the octane rating of the fuel. It is not
present in condensates, distillates, or naphtha (Bruce
and Schmidt, 1994). Older gasolines contain tetraethyllead and the lead scavengers ethylene dibromide and
ethylene dichloride (1,2-dichloroethane). Tetraethyllead was blended with gasoline prior to about 1985 at
concentrations of about 400 to 500 mg/L.
The presence of organic lead in gasoline is frequently
argued as evidence of a pre-1985/86 gasoline release,
while the presence of only tetraethyl-lead is indicative
of a post-1980 release. The presence of non-tetraethyl
leads such as methyldiethyl-, tetramethyl-, dimethyldiethyl-, tetramethyl- or trimethyl-lead is then argued
as evidence of a pre-1980 release. Hurst, Davis and
Chinn (1996), for example, reported that ``The speciation of lead additives has changed, with tetraethyl lead
being the only alkyl-lead additive in leaded fuels after

Review of Environmental Forensic Techniques 177

of manganese-based substances, including MMT. In

1998, this law was abolished and MMT is currently an
additive in Canadian gasoline. Given this hiatus in
MMT usage, it is dicult to use MMT as an age
diagnostic technique beyond its introduction in Canada
prior to 1976.
The lead scavengers ethylene dibromide (EDB) and
ethylene dichloride (EDC) were introduced in
19271928 to alleviate problems with metal corrosion
in engines caused by the formation of lead oxide in the
combustion chamber that resulted in damaged spark
plugs and exhaust valves (Kaplan et al., 1997). EDB
and EDC minimized the precipitation of lead oxides in
the engines by forming the relatively volatile lead
bromide, or lead chloride, that passed through the
engine with the exhaust. The concentration of EDB and
EDC in leaded gasoline has changed over the years. The
quantity of EDB and/or EDC in a lead package is
determined by the amount of alkyl-lead present. A
sucient amount of scavenger is added to theoretically
react with all the lead, which is termed one theory, with
1.0 to 1.5 theories typically used. EDB is currently
added to fuels used in aviation piston engines (Central
Regional Water Quality Control Board, 1997).
EDB and EDC are moderately soluble (4.32 and
8.69 g/L at 208C, respectively). Given that alkyl-leads
are strongly adsorbed to soil and tend to be hydrolyzed, the presence of lead scavengers may be the only
residue of a leaded gasoline release. For phase-separate
leaded gasoline in contact with groundwater, the
contact time between the two uids and the resulting
scavenger dissolution into the groundwater has been
used for age dating. Challenges to this argument
include the potential for the re-dissolution of alkylleads or lead scavengers into non-leaded gasoline
migrating through the location of an earlier release,
and uctuating EDB and EDC concentrations due to a
rising and falling groundwater that is in contact with
the gasoline-impacted soil (Morrison, 2000b).
The distribution and ratios of alkyl-leads and lead
scavengers in phase-separate samples can be used to
identify the locations of multiple releases. Figure 1
depicts the ratio of total alkyl-lead and EDB in phaseseparate gasoline in monitoring wells located downgradient of a documented release (Morrison, 2000c).
The decrease in the total alkyl-lead/EDB ratio v. the
distance from the spill, to a distance of about 500 to
600 feet, is consistent with a single documented release.
The abrupt increase in the total alkyl-lead/EDB ratio
Documented release

Suspected release location

100
Total alkyl
lead/EDB ratio

1980. Hence, analyses of alkyl-lead species present in

free products can help date the time of a release.''
Other literature, suggests that the phasing out of
tetraethyl-lead continued into the early to late 1980s
(Kaplan, 2000a; Peterson, 2000; Clark, no date). Care
is therefore required when extrapolating generalized
alkyl-lead chronologies. Additional complications
include the re-mobilization and dissolution of tetraethyl-lead by subsequent gasoline releases with or
without additive packages migrating through the same
soil. The tested sample may therefore be a composite of
several releases containing multiple additive packages.
Regulatory changes in the allowable alkyl-lead
concentrations in gasoline in conjunction with lead
concentration data are frequently forwarded as evidence for age dating a release. In 1982, the maximum
lead concentration in gasoline was 4.2 g/gallon. In 1984,
the Environment Protection Agency set a maximum of
0.1 g/gallon. This concentration applies to the average
quarterly production from a renery or a pool
standard. The pool standard is the total grams of lead
used by a renery in a given time period divided by the
total amount of gasoline manufactured in the same time
frame. A typical challenge to this argument includes
uncertainties associated with the original lead content.
An example of 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 not reect any true renery amount due
to lead accounting practices (leads credits are bought or
sold) that are usually averaged quarterly. In addition,
multiple releases of gasoline with low lead concentrations from 1985 to 1991 can result in an accumulated
lead concentration of 0.5 g/gallon that can be misinterpreted as evidence of a pre-1985 gasoline release.
Non-lead alkyl additives in fuels with alkyl-leads
may provide additional forensic evidence by providing
resolution for age dating the product. Examples
include nickel carbonyl, dicyclopentadienyl-iron, iron
pentacarbonyl, methylcyclopentadienyl manganese tricarbonyl (MMT), and lead scavengers. MMT was used
as an octane improver in unleaded gasoline (Zayed,
Hong and L'Esperance, 1999). MMT synonyms and
trade names include CL-2, Combustion Improver-2,
manganese tricarbonyl-methylcyclopentadientyl, and
2-methylcyclopentadientyl. MMT was introduced as
an antiknock and alkyl-lead supplement in the United
States in about 1958/59 by Ethyl Corporation as
AK-33X, and was available until about 1977/78
(Harvey, 1998; Bruya, 2000; Peterson, 2000) although
a few reneries used it until 1985 (Kaplan, 2000b).
MMT was also blended with tetraethyl-lead as a
supplement (Gibbs, 1990; Hurst, Davis and Chinn,
1996; Ethyl Corporation, 1998).
While the detection of MMT may be age diagnostic,
it was not routinely added by all manufacturers and has
dierent usage histories throughout the world. MMT
was blended in gasoline in Canada, for example, since
1976. MMT usage increased substantially when it
replaced lead in gasoline in 1990 (Zayed, Hong and
L'Esperance, 1997). In 1997, Canada adopted law C-29
that banned the inter-provincial trade and importation

10

200
400
600
800
1000
Distance from documented release (feet)

Figure 1. Total alkyl lead/EDB ratio as a function from a known and

suspected leaded gasoline release from monitoring wells containing
phase-separate gasoline (after Morrison, 2000a).

178 R. D. Morrison

at a distance of about 600 feet, however, is consistent

with a second release. Corroborative evidence was
subsequently obtained to verify the location of this
second suspected release.
Challenges to this interpretation include the possibility that dierences in alkyl-lead and lead scavenger
concentrations are attributable to dierences in subsurface weathering patterns and product commingling
rather than multiple releases. An additional complication may include sampling and analytical variations
in the alkyl-lead and lead scavenger concentrations as a
function of the gasoline thickness. A discontinuous thin
gasoline layer, for example, is exposed to greater water
washing per volume of product than a layer of gasoline
several feet thick. A sample collected from a thicker
gasoline layer may therefore exhibit higher EDB and/or
EDC and EDB/EDC mass concentrations as a function
of product thickness. Graphing product thickness v. the
total alkyl-lead/EDB ratio may therefore provide
insight as to whether this is a reasonable explanation.
In older releases, the alkyl-leads may be absent as they
are strongly adsorbed to soil and quickly hydrolyze
upon contact with groundwater. In such cases, only the
lead scavengers may be present.

Oxygenates
Oxygenates are blended with gasoline to increase the
oxygen content and reduce carbon monoxide emissions. The American Society for Testing and Materials
denes an oxygenate as ``An oxygen-containing,
ashless, organic compound, such as an alcohol or
ether, which can be used as a fuel or fuel supplement''
(Gibbs, 1998). In the United States, ethanol was
blended with gasoline 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 as a fuel extender.
Tertiary-butyl alcohol (TBA) was available in 1969 and
was blended with methanol in 1981, although methanol blends are no longer used (Gibbs, 1998). Examples
of alcohols and ethers used as octane enhancers and/or
oxygenates include methanol, ethanol, isopropyl alcohol (IPA), tertiary-butanol, di-isopropyl ether (DIPE),
ethyl tertiary-butyl ether (ETBE), tertiary-amylmethyl
ether (TAME), and tertiary-amyl ethyl ether (TAEE).
(Central Regional Water Quality Control Board, 1997).
Atlantic Richeld Company (ARCO) synthesized
methyl tertiary butyl ether (MTBE) in 1979 via the
catalytic reaction of isobutylene ((CH3)2C55CH2) and
methanol (CH3OH) (American Petroleum Institute,
1998). MTBE usage increased rapidly in the 1980s at
about 40% per year (Suita and Mormile, 1993;
Stean et al., 1997). In 1992, the actual production
of MTBE in the United States was 9.1 billion pounds.
By 1999, MTBE was the most widely used oxygenate in
the United States although TAME, ETBE and DIPE
were also blended with gasoline. In addition to this
domestic production, Alberta Envirofuels in Canada
and Citgo in Argentina have imported MTBE into the
United States.
MTBE was initially added as an octane-enhancing
replacement for tetraethyl-lead since the mid-1980s. It
was later used as a fuel oxygenate to decrease the
amount of carbon monoxide in automobile emissions,

and to improve the tolerance of gasoline for moisture

(Day, 2000). Currently, MTBE is used as evidence to
discriminate between multiple spills of gasoline and as
an indicator of a pre- and post-1979 release (Morrison,
2000; Davidson and Creek, 2000). MTBE is not,
however, contained in all post-1980 gasoline. MTBE
was blended with reformulated gasoline for severe
ozone non attainment areas that did not meet federal
ozone ambient air quality standards with concentrations of 15% (Oxy-fuels) while many states used
MTBE as an octane booster at up to 8% by volume.
MTBE was introduced to East Coast, Gulf and
Midwest gasolines after 19791980 and into West
Coast gasoline after about 19861987 (Squillance et al.,
1996; Davidson and Creek, 2000). Since the 1990s, it
was used in gasoline in over 15 states to meet the
Federal Clean Air Act of 1990 requirements for
oxygenates in wintertime oxygenated gasolines (beginning in 1992), and in Federal reformulated gasolines in
1995 to meet carbon monoxide ambient air quality
standards (California Environmental Protection
Agency, 1996). Table 1 is a chronology of oxygenate
usage Gibbs, 1998; Harvey, 1998; Morrison, 1999d,
Morrison, 2000a,c).
MTBE is about 25 times more soluble in water
( 42,000 mg/L) than benzene, and is not retarded by
soil as it travels in groundwater. MTBE is therefore
frequently detected at the leading edge of a groundwater plume in the absence of the benzene, toluene,
ethylbenzene, and xylenes (BTEX). As a result of this
behavior, MTBE may be used as a qualitative indicator
of the length of the downgradient plume.
MTBE plumes in groundwater are generally longer
than BTEX plumes. In eld studies of unconned
sandy aquifers, MTBE migrated at the same rate as
groundwater while BTEX migrated at about 90%,
75% and 67% of the groundwater velocity, respectively. At a site in South Carolina, MTBE in gasoline
was transported at the same rate as groundwater while
benzene was transported about 80% of the same
distance (Landmeyer et al., 1998).
When MTBE is used for age dating and source identication, it is important to examine whether potential
biases are present that can impact the interpretation.
Examples of biases include the following:
. potential false positives (13%) in laboratory
testing when EPA Method 8020/8021 is used because
various methyl-pentanes co-elute with MTBE
(Davidson, 2000a; Uhler et al., 2000; Rhodes and
Verstuyft, no date);
. potential contributions from non-point sources must
be identied (Delzer et al., 1996);
. incidental blending and/or mixing of additives in
gasoline suppliers as gasoline without deposit control additives is exchanged or traded amount
producers to meet contract requirements and to
improve transportation logistic;
. cross contamination from one fuel to another,
especially in pipelines and tanker trucks;
. dierences in MTBE concentrations or absence of
MTBE due to seasonal reformulations;
. product swapping by the gasoline jobbers, or via
exchange agreements between reneries or bulk

Review of Environmental Forensic Techniques 179

Table 1. Chronology of oxygenate usage
Date

Description of oxygenate usage and history

1842
1907
1930
1933
1937
1940
1943
1950s
1968
1969
1973
1974
1975
1976
1979

MTBE synthesized by English chemist (Faulk and Gray, 2000).

tertiary-Amyl methyl ether produced.
Agrol, alkylgas, ethanol fuels used in Nebraska.
tertiary-Alkyl ether synthesis patent in the United States is issued.
Germany uses methanol (Harvey, 1998).
Alkyl-Gas (ethanol blend) marketed in Nebraska.
Patents relating to MTBE led (U.S. Patent No. 1,968,601).
American Petroleum Institute literature references the applicability of using MTBE in gasoline (Drogos, 2000).
Chevron taxicab eld test of MTBE/TAME
ARCO Corporation blends tertiary butyl alcohol in gasoline (Harvey, 1998; Drogos, 2000; Peterson, 2000).
MTBE used in commercial gasoline in Italy (Hart/IRI Fuels, 2000).
Clean Air Act Amendment requires waivers.
Nebraska gasohol (ethanol blend) program commences.
EPA waiver issued for 10% by volume for ethanol (Gibbs, 1998).
MTBE produced by ARCO Corporation in the United States (Davidson and Creek, 2000; Bruya, 2000). EPA waiver issued for 7%
volume for MTBE. 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 for octane enhancement (McKinnon and Dyksen, 1984; Garrett, Moreau and Lowry,
1986; Weaver et al., 1996; Davidson, 2000b).
1980s
Experimentation with MTBE, methanol (M85) and ethanol as octane boosters conducted (Harvey, 1998). Transmission pipelines
on the East Coast of the United States pump MTBE. EPA's Substantially Similar rule issued with 2% by weight oxygen maximum
limit (11% by volume for MTBE).
1982
Documented use on the East Coast of the United States (Kaplan and Galperin, 1996; Kaplan et al. 1997).
1987/1988 Denver begins rst wintertime oxygenated gasoline program in the United States using MTBE to reduce vehicle carbon monoxide
emissions (ethanol subsequently used) (American Petroleum Institute, 1998; Harvey, 1998; Drogos, 2000). EPA waiver issued for
15% by volume for MTBE as the maximum amount; MTBE is among the top 50 chemical manufactured in the United States
(Uhler et al., 2000).
1989
Phoenix, Las Vegas, Reno, and Alburquerque begin wintertime oxygenated gasoline program using MTBE (ethanol used later).
Clean Air Act Amendments enacted. The Substantially Similar Rules increases the maximum oxygen limit 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 requires 2.7% by weight minimum oxygen in 39 carbon monoxide non-attainment areas.
1993
Tertiary amyl methyl ether and ethyl tertiary butyl ether usage comes into general use (Peterson, 2000). Reformulated gasoline
ozone non-attainment areas. Federal reformulated gasoline program requires 2.0% by weight minimum oxygen content. California
Phase 2 requires reformulated gasoline and requires 1.82.2% by weight oxygen. Ninety-ve percent of all gasoline sold in
California contains MTBE. MTBE is the most widely used oxygenate in the United States (Reisch, 1994).
1995
TAME added to California fuels since 1995 (Central Regional Water Quality Control Board, 1997) .
1997
Approximately 8 billion kilograms of MTBE is produced in the United States (Hitzig, Kostecki and Leonard, 1998).
1998
California Health and Environmental Assessment of MTBE report recommends the gradual phase-out of MTBE in California
gasoline; 3.8 billion gallons of MTBE used in the United States (Drogos, 2000). TOSCO blends ethanol into California gasoline as a
pilot project in response to reports of widespread MTBE contamination on groundwater.
1999
Chevron and TOSCO begin gradual phase-out of MTBE in unleaded gasoline. Town of South Lake Tahoe, California bans MTBE
because of concerns about its potential impact on the town's drinking water supply.
2000
California bans the use of MTBE with a complete phase-out by 31 December 2002 (Brown and Clark, 1999). 20 March 2000,
California Department of Health Services establishes an MCL for MTBE at 13 mg/L; a secondary MCL standard is set at 5 mg/L,
eective on 18 May, 2000.

storage facilities (Hitzig, Kostecki and Leonard,

1998; Rhodes and Verstuyft, no date).
Given the high volatilization potential (245 mm Hg @
258C) the solubility of MTBE in water, its presence in
groundwater may not be indicative of a liquid release.
The presence of MTBE in groundwater may originate
from a non point source, especially at concentrations of
less than 10 mg/L (Pankow et al., 1997). Non-point
sources of MTBE include storm water runo
(015 mg/L) and surface water sources such as watercraft (040 mg/L) (Davidson, 1999). The United States
Geological Survey, for example, detected MTBE in
6.9% of 592 water samples collected from storm water
in 16 cities and metropolitan areas at concentrations
ranging from 0.2 to 8.7 mg/L (Delzer et al., 1996).
Eighty-three percent of the MTBE detections occurred
in storm water that was collected from October
through March (19911995) and corresponded to the
seasonal use of oxygenated gasoline which happens
when carbon monoxide exceeds established air-quality
standards.

Cross-contamination of non gasoline products with

MTBE can occur during 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,
presumably due to cross-contamination (Hitzig,
Kostecki and Leonard, 1998). In Connecticut, 27 of
37 heating oil spill sites had MTBE detected in the
groundwater at concentrations from 1 to 4100 mg/L
(Davidson, 1999).
Biodegradation studies of MTBE in shallow aquifers
indicate that MTBE is biodegradable under anaerobic
and aerobic environments although it is considered
recalcitrant relative to BTEX compounds (Mormile,
Liu and Suita, 1994; Landmeyer et al., 1998;
Ramsden, 2000). A suspected MTBE degradation
pathway is shown on Figure 2.
While the author has not encountered a case
where MTBE and degradation product ratios are
used for age dating and/or source allocation, a greater
understanding of the kinetics associated with these
pathways may provide a means for developing this

180 R. D. Morrison
CH3
CH35 C
Lactate

CH3
CH3

OH

CH3

C
CH3
MTBE

OH

CH

Intermediary
metabolism

TBA
CH3

CH3
CH3

2-Propanol

CH3
O2 + 2H+

CH3

CH3

CH

OH

Methylacrylate
H2O
CH2O
Formaldehyde

C1 Metabolism

Figure 2. Simplied methyl tertiary butyl ether (MTBE) oxidation pathway (after Drogos, 2000; Ramsden, 2000; Jacobs et al., 2000).

argument. A potential diculty is that while TBA is a

primary metabolite of MTBE via atmospheric and
microbial oxidation, it is also a by-product of MTBE
synthesis and is often present as an impurity with
MTBE in the 0.1 to 1% range (Drogos, 2000). TBA
may also be added to MTBE up to 5% by volume
(Brown, 2000). The detection of TBA with MTBE may
therefore be independent of its degradation relationship with MTBE (Wilson et al., 2000; Ian Kaplan, pers.
comm.). MTBE has also been proposed as a tracer for
use in inverse groundwater modeling applications.

Dyes
The inclusion of dyes in gasoline was the result of an
agreement concerning tetraethyl-lead between Ethyl
Corporation and the United States Surgeon General in
1926. The agreement required that a sucient amount
of dye be added to impart staining qualities to leaded
gasoline to deter its usage for cleaning or other
purposes. Dyes are used by some states to determine
whether the highway tax was paid and/or if the
gasoline is used for non highway (agricultural) applications and blended by reners to distinguish between
grades of fuel. For example, yellow/gold and pink/red
dyes are added to gasoline to distinguish between
dierent grades of gasoline. Blue, yellow, and red dyes
are used to dierentiate octane ratings in aviation
gasoline (Ward, 1984). Common dyes include red
(alkyl
derivative
azobenzene-4-azo-2-naphthol),
orange (benzene-azo-2-naphthol), yellow ( para-diethyl
aminoazobenzene), and blue (1,4-di-isopropyl-aminoanthraquinone) (Kaplan and Galperin, 1996;
Kaplan et al., 1997). Typical concentrations for a dry
dye range from 0.7 to 1.3 grams per 100 gallons
(Younglass et al., 1985). Commercial dyes used in
gasoline (15 mg/L) are usually part of a lead
antiknock package containing lead scavengers that

are added at the renery at the in-line blender or the

nished fuel-blending tank.
The high-resolution mass spectral chromatograms
for 21 commercial dyes suggested azo-, diazo-, and
anthraquinone-type structures (Younglass et al., 1985).
In some cases the dye was multi-component (e.g. a
bronze dye). Dyes in gasoline are analyzed with either
thin layer chromatography or by ultraviolet or visible
absorption spectroscopy (Touchstone, 1992). Speciality 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, little information exists on dyes other than in
patent disclosures. Furthermore, the subsurface
migration of a fuel containing dye can result in the
alteration of the original color. For example, red and
orange dyes can assume a dark brown color after the
fuel has migrated a short distance through soil (Kaplan
et al., 1997). Other challenges include the diculty in
distinguishing between dyes when several gasoline
blends commingle (red and orange dyes become dark
brown), the rapid biodegradation of the dyes in the
subsurface ( probably due to hydrogenation and
subsequent destruction of the conjugated structure),
and their high water solubility (Galperin, 1997).

Stable Isotope Analysis

Radioactive isotopes are used for source identication
of petroleum hydrocarbons and chlorinated solvents
and to estimate contaminant transport travel times,
especially for single component spills (Philp, 2000).
Isotope ratios are less aected by weathering than are
many chemical concentration ratios, and isotope ratios
of lighter fractions are more susceptible to weathering
than heavier fractions. Numerous opportunities exist
for age dating and source identication of petroleum
hydrocarbons with isotope analysis. An advantage in

Review of Environmental Forensic Techniques 181

using isotope analysis for petroleum hydrocarbon

ngerprinting is that the isotopic results are similar to
the original hydrocarbon and can be used to
complement gas chromatography and/or gas
chromatography/mass spectrometry ndings (Mansuy,
Philip and Allen, 1997). The stable carbon isotope
composition has been used to distinguish between
gases from dierent sources and whether they are of
microbial or thermogenic origin (Philp, 1998). Another
application of isotope analyses was reported for
C29/C30 ratios and S C31-C35/C30 ratios to distinguish
Middle Eastern v. South East Asian petroleum in the
Straits of Malacca, Malaysia (Zakaria et al., 2000).
Lead isotope analysis is used for age dating and
source identication of gasoline releases. Lead radioactive isotopes are usually reported as ratios of 206Pb/
204
Pb, of 206Pb/207Pb, or as a delta notation (d). Isotope
ratios are assigned a negative notation if the sample
value is lower than the standard value (arbitrarily given
as 0%), or they are reported as a positive value if the
sample ratio is greater than the standard value. An
example of delta notation is (Hurst, 1998a,b):
d206 Pb 1000206 Pb=207 Pbsample
206 Pb=207 Pbstandard =206 Pb=207 Pbstandard :

The most frequent lead isotope ratios used for age

dating are 206Pb/207Pb and 206Pb/204Pb (Hurst, Davis
and Chinn, 1996). When 206Pb/207Pb ratios for tetraethyl-lead are plotted as a function of time between the
late 1960s and the late 1980s, for example, a systematic
trend is observed that is alleged to be a result of
manufacturers shifting their source of lead. A technique relying upon this approach is the Anthropogenic
(i.e. gasoline derived) Lead Archeostratigraphy Model
(ALAS) that is used for source identication and age
dating a gasoline release(s). This approach 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 United States gasoline and aerosols were measured
and observed to reect a characteristic isotopic
signature (Rosman et al., 1994). Dierences in the
isotope ratios of the ores used for gasoline lead
packages provide the basis to compare lead isotope
ratios from environmental samples for age dating and
source identication.
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 United
States shifted to younger ores mined in Missouri that
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. Since
1984, 206Pb/207Pb ratios decreased to about 1.18, and to
1.2 in 1989/1990 (Stukas and Barrie, 1987).
Evaluation of lead isotope ratios and lead concentrations provides the basis for comparison with the ALAS
model calibration curve. By plotting isotope ratios, or a
lead isotope ratio v. lead concentration, patterns of

data can allegedly be identied and used for source

identication. It is reported that this technique allows
one to establish the time of formulation to within 1 to 5
years. This ability is dependent upon the slope of the
ALAS model curve, the calibration sample scatter, and
that the sample is an end member and not a mixed
isotope signal due to the preferential removal of
anthropogenic lead relative to natural lead (Hurst,
2000). The degree of resolution for age dating is
reported to be +1 year for releases from 1965 to 1980,
and +1.52 years for 1980 to 1990, with the larger
deviations occurring for post-1985 results (Cline,
Delno and Rao, 1991; Hurst, 1998a,b, 1999a,b).
After 1990, when gasoline became unleaded in the
United States, age estimates can only be stipulated as
post-1990. Parts per billion ( ppb) levels of lead
detected in unleaded gasoline post-1990 are assumed
to be attributable to inherited lead from the crude oil
and rening process (Hurst, 1998a). In instances where
206
Pb/207Pb ratios are indistinguishable, the use of
206
Pb/204Pb ratios may provide the necessary discrimination.
Unleaded gasoline can contain lead concentrations
in ppb range. The concentrations detected are assumed
to be representative of the geologic formation from
which the lead was obtained that is contained within an
additive package as well as from the renery where the
gasoline was produced (Hurst, Davis and Chinn, 1996).
The ALAS approach assumes that the lead additive
producers, Ethyl Corporation and E.I. DuPont de
Nemours, used similar ore feedstock for their alkyllead additive packages, and that the same lead additive
proportions were similar for any given year. Another
assumption is that the environmental sample is not a
mixture of multiple gasoline releases with dierent lead
additives (Hurst, Davis and Chinn, 1996). Other
challenges include whether the standard used in the
ALAS model discriminates between industrial lead
originating from unleaded gasoline v. lead from other
industrial sources. For example, lead concentrations in
organic industrial sewage particles range from 500 to
1200 mg/kg (dry weight) that can be introduced into
sediments in addition to lead originating from automobile exhaust that are used as a standard for dating a
gasoline release (Patterson and Settle, 1976). Potential
challenges and responses are summarized in Table 2
(after Hurst, 2000).
Carbon and hydrogen isotope analysis is also used
for crude oil and for aromatic compounds (BTEX)
source identication. The low 13C values of fuels and
chlorinated solvents manufactured from fossil fuels can
dier with the dissolved inorganic carbon in natural
groundwater. The d13C of the dissolved organic and
inorganic carbon provide a basis of contrast in areas
impacted by chemicals produced from fossil fuels. If
each renery processes crude oil from a particular
geographic area or oil basin for an extended period of
time, the isotope ratios for the corresponding rened
product are expected to be similar. If dierent crude oil
stocks are blended at the renery, small changes in the
carbon isotope ratios of the rened fuels can result.
The changes in the isotope ratios usually occur during
the production of the light gases that tend to
concentrate heavy isotopes in the product (Kaplan
and Galperin, 1996).

182 R. D. Morrison
Table 2. Challenges and responses to use of the Anthropogenic Lead Archeostratigraphy Model (ALAS) for age dating and source identication of
gasoline releases
Challenge to ALAS model

Response

Lead concentrations in soil and groundwater that do not exceed a

certain threshold concentration are not attributable to background
concentrations and are indistinguishable from anthropogenic lead.

High precision lead isotopic ratio analyses can discriminate between

natural and anthropogenic lead at the lower ppb concentrations.

Single, dilute acids used in sample preparation for soils preferentially

leaches anthropogenic lead.

Soil samples can be subjected to multiple sequential extractions with

the results interpreted via rigorous mixing models to accurately identify
the lead isotopic-concentration characteristic of each end member.

Lead isotopes fractionate or biodegrade, thereby compromising their

application for age dating and source identication.

Mass dierences in lead isotopes are small (0.52%) thereby

precluding fractionation via physiochemical and biological processes.

Commingling of hydrocarbon releases homogenizes lead isotope

ratios.

When lead concentrations are greater than about 10 ppb and watersoluble gasoline compounds are present, the lead isotopic signature in
the groundwater is virtually identical to the anthropogenic lead
derived via hydrocarbon/groundwater lead isotopic exchange.

Lead is absent in unleaded gasoline.

Lead can be present in unleaded gasoline at levels from tens of

hundreds of ppb. The origin of this lead is the crude oil from which the
product gasoline was produced and from the rening process.

Dierences in sulfur isotopes (32S, 33S, 34S, and 36S)

provide an opportunity to distinguish between dierent
sources of crude oil or product. 32S and 34S are the
most commonly used isotopes for this purpose and can
be combined with a peak-to-peak polynuclear aromatic
(PNA) analysis to distinguish between multiple sources
of crude or rened products. PNA analysis, with or
without stable isotope analysis, can assist in distinguishing between pristine and used motor oil as
used motor oil contains more PNAs. Used motor oil
may also be diluted with fuel (1 to 10%), especially
with engines with worn piston rings thereby complicating the interpretation of this data (Rhodes, 2000).
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 dierent sources as well as natural
background sources of hydrocarbons.
Pentane extraction of a groundwater sample and
subsequent analysis of the d13C via high sensitivity gas
chromatograph/combustion/isotope ratio mass spectrometry (GC/C/IRMS) may be appropriate for source
discrimination of BTEX in groundwater as isotope
ratios of d13C remain constant as a function of the
concentration of the BTEX in dissolved or free product
samples (Dempster, Lollar and Feenstra, 1997). GC/C/
IRMS analysis of pure phase BTEX indicates that
dierent manufacturers produce chemicals with distinct d13C compositions probably attributable to
dierent feedstocks and rening processes. Crossplots of deuterium and hydrogen ratios may similarly
provide a means to distinguish between multiple BTEX
sources. A similar technique for source identication is
to spatially examine enrichment of d13C values in the
BTEX compounds in a commingled plume.
When reviewing d13C values for the BTEX compounds for source identication, it is important to
examine the overall pattern of isotopic variation (e.g.
individual BTEX plots). A characteristic d13C signature

for a compound such as benzene, for example, may not

be clearly associated with a particular manufacturer.
Compound specic isotope analysis for all of the
BTEX compounds may therefore provide a more
quantiable basis to distinguish between multiple
sources as contrasted with using a single compound
(Dempster, Lollar and Feenstra, 1997).

Weathering and Biomarkers

Petroleum hydrocarbon weathering processes include
evaporation, water washing, adsorption and/or sequestration, chemical precipitation, biodegradation, and
advective transport. Water washing is the preferential
transfer of the BTEX and light hydrocarbons into
groundwater. The merit in examining weathering
patterns among samples is that it may provide a basis
to: (1) associate products/fuels originating from a common source; and (2) provide a qualitative basis for
age dating. Toluene, for example, is generally considered to be more biodegradable than other hydrocarbons in gasoline and can therefore indicate
microbial degradation when preferentially removed
relative to benzene and the C8 aromatics (Peterson,
2000).
The presence of the gases isobutane, n-butane, isopentane, and n-pentane can provide a qualitative basis
to determine the relative age of a sample contaminated
with gasoline. The presence of these gases in a sample
may indicate a fresher sample while their absence is
argued as indicative of an older or more weathered
sample. Fresh gasoline also contains n-hexane and
n-heptane in higher concentrations than methylcyclohexane (MCH) and n-octane. As gasoline weathers, the
MCH concentration increases relative to n-hexane, and
C7 normal parans, thereby providing a relative means
for comparison between samples. Forensic geochemists
often disagree as to the validity of using weathering for
age dating gasoline, especially given the many site
specic variables such as volatilization and water
washing eects (Peterson, 2000).
Biomarkers are dened as ``organic compounds
present in oils and source rocks having carbon

Review of Environmental Forensic Techniques 183

skeletons related to their functionalized precursors

which occur in the original source material'' (Philp,
1998). Most crude oil and Bunker C fuel, for example,
contain biomarkers such as terpanes and steranes that
are highly resistant to biodegradation (Walker, Colwell
and Petrakis, 1976; Kaplan et al., 1995). The molecular
distributions of terpanes and steranes and carbon
isotope values, for example, was used to dierentiate
Exxon Valdez-derived oil from California oils that
were introduced into the Alaskan region prior to the oil
spill. In another application, hopane and sterane
distributions, in addition to microscopic characterization, were used to identify road asphalt particles as a
source of contamination in river sediments from
Alsace-Lorraine (Faure et al., 2000). Individual biomarkers and ratios used for source identication of
hydrocarbons
include
C2-debenzothiophenes/C2phenanthrenes, C3-dibenzothiophene/C3-chrysene, and
C29 a, b-pentacyclic hopanes/C30 , a, b-pentacyclic
hopanes, C23 tricyclic hopanes/C24 tricyclic hopanes,
and 4-methyldibenzothiophene/2- and 3-methyldibenzothiphenes ratios (Wang, Fingas and Sergy, 1994;
Wang and Fingas, 1995; Douglas et al., 1996). The C30
pentacyclic terpane (hopane) and certain tricyclic
terpanes are among the most stable biomarkers in
crude oil (Peters and Maldowon, 1993). Of the
tetracyclic steranes, the diasteranes are the most stable.
In environmental litigation, pentacyclic triterpanes
(C27 C35) and steranes (C27 C30) are commonly used,
although they are relegated to use for distinguishing
between crude oil or heavy distillate fuels due to their
high molecular weight (Stout et al., 1999a). For middle
distillate fuels, biomarkers using gas chromatography/
mass spectrometry-selected ion monitoring techniques
are used to distinguish dierent fuels. Biomarkers
identied with this instrument include bicyclic sesquiterpanes (C14 C16), acyclic regular isoprenoids
(C13 C25), tricyclic diterpanes (C17 C20), aromatic
diterpenoids (C18C20), tricyclic terpanes (C19 C25),
and various polycyclic aromatic hydrocarbons such as
naphthalenes and phenanthrenes (Stout, Uhler and
McCarthy, 1999; Stout et al., 1999a). Dibenzothiophenes are associated with the sulfur content of the fuel
and can vary signicantly between sources.
Crude oil and most mid-range distillates contain an
abundant number of PNAs including naphthalene,
uorine, phenanthrene, pyrene, and chrysene (Kaplan,
2000a). Manufactured gas plant residues containing
PNAs include lamp black, tar and/or spent oxides
(usually composed of sulfur, cyanide and ammonia
compounds bound with iron). The 1984 Edison
Electric Company's Handbook of Manufactured Gas
Plant Sites describe the composition of a coke plant's
coal tar consisting of 5% light oil (boiling points up to
2008C), 17% middle oil (2002508C), 7% heavy oil
(2503008C), 9% anthracene oil (3003508C), and
62% pitch (43508C). The presence or absence of a
PNA may therefore provide an indication of a
distillation or pyrogenic process that is unique to the
material and can be used to distinguish between residue
materials containing the PAHs. Care is required when
performing this analysis, as the chemical composition
of the coal and tars used as feedstock vary signicantly,
including dyestu feedstock chemicals (e.g. phenols,
creosols, xylenes, parent and alkylated PNA), oil cuts

(e.g. light oil, naptha, heavy naptha, naphthalene oil,

wash oil), and residual materials (e.g. light creosote,
creosote, heavy creosote and pitches). A comparison of
the PNAs present in a sample may provide insight to
distinguish between sources that used dierent feedstocks (e.g. crude oil, coal-tar, oil tar, etc.) (Haeseler
et al., 1999).
When using biomarkers for age dating and/or source
identication, it is important to examine the background concentrations of those compounds selected as
biomarkers (Stout, Uhler and McCarthy, 2000). The
rening process may also aect the use of biomarkers
to some degree. For straight-run distillate products,
biomarkers are impacted only by the distillation
temperature, while in cracked and hydrotreated products, biomarkers are aected by temperature, catalysts, and hydrogen. The potential impact, if any, of the
rening process on a selected biomarker therefore
requires examination.

Degradation Models
Degradation models used for age dating are based
upon a data set for which a particular degradation rate
is postulated. This degradation rate is then used to
predict the known concentration of compound for an
earlier period of time (Ram et al., 1999).
A popular degradation model is based on the half-life
of a compound. The basis of this approach is reliance
on the biodegradation half-life. For example, numerous
degradation rate models exist for age dating BTEX
compounds. Assumptions used in rst-order BTEX
biodegradation models include (Odermatt, 1994):
. a uniform degradation rate;
. a rst-order degradation rate independent of the insitu microbial population;
. omission of the contaminant loading rate and the
toxic eects of the contaminant on the microbial
population (e.g. rst-order degradation rates may
only be valid over a portion of a concentration
range);
. a rst-order biodegradation process that is instantaneous and 100% eective regardless of location.
An example of a method used to estimate the
degradation (l) of a compound in a one-dimensional
idealization is described by (Buscheck and Alcantar,
1995; Brown et al., 1997; Westervelt et al., 1997):
l vc =4ax 1 2ax k=vx 2 1

where vc is the contaminant velocity along the

x-direction (adjusted for retardation), ax is the
longitudinal dispersivity coecient, k is the attenuation rate in units of time, and vx is the linear
groundwater velocity. The term (k/vx) describes the
slope of the regression line t to the log contaminant
concentration data as a function of distance along the
centerline of the contaminant plume (McNab and
Dooher, 1998). The diculty 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 small numbers of data
points, it is often possible to t a straight line through

184 R. D. Morrison

log concentration v. distance data with a high degree of

correlation even when degradation is insignicant or
absent. A linear trend in log concentration values as a
function of distance from the contaminant source,
however, does not constitute proof of the existence of
transformation processes. Other factors that can
account for the linear trend in log concentration as a
function of distance from the contaminant source
include the assumption that steady-state conditions
exist, uctuations in source strength with time, nonFickian dispersion of solutes, strongly heterogeneous
ow and transport, well locations that are not aligned
with the contaminant plume centerline, dilution eects
due to well screen length, sampling and analytical bias,
and a nonuniform degradation rate distribution
(McNab and Dooher, 1998).
The use of rst-order reaction rates to describe
hydrocarbon biodegradation may not be universally
appropriate. Examination of 1029 leaking underground storage tank sites in California found that the
applicability of rst-order degradation rates was
appropriate in only about 625 instances. The authors
recommended carefully examining rst order
approximations if the maximum benzene concentration
is greater than or equal to 1 ppm (Bekins, Warren and
Godsy, 1998; McNab and Dooher, 1999).

examined; these C17/pristane ratios were 1.95 with a

standard deviation of +0.29. A C17/pristane ratio of a
rened product such as diesel is greater than 2.0, while
crude oil values range from about 2.0 to 2.1.
When evaluating the ratio of normal heptadecane to
pristine for age dating diesel No. 2 fuel oil, it is
valuable to examine whether there is a scientic basis in
assuming that there are constant degradation rates for
pristine and n-C17 , and that pristine degrades slower
than n-C17 (Smith, 2000a). Another area of inquiry is
whether the Christensen and Larsen C17/pristane ratios
for diesel in Denmark and the Netherlands is valid for
a site specic distillate, lubricating oil or diesel release
in the United States (Schmidt, 1998). In one instance, a
known release of hydrocarbons to groundwater was
sampled from 1993 to 1996 and compared to the age of
the release using the n-C17 ratio (Smith, 2000a).
Considerable dierences between the known age of
the spill and the estimated age occurred when using this
method, especially as the fuel weathered. Signicant
challenges exist regarding the scientic validity of this
method and a careful review of these issues is
recommended when considering its use for age dating
and/or source identication (Brassell et al., 1981).

Pristane/Phytane Ratios

BTEX ratios are used for age dating and source

identication (Odermatt, 1994; Kaplan et al., 1997).
BTEX ratio data is usually combined with MTBE,
alkyl-lead or pristane/phytane analysis as evidence for
a particular interpretation. BTEX ratio techniques
are qualitatively based on the sequence of BTEX
volatilization and biodegradation. The sequence of
BTEX loss in groundwater generally begins with
benzene because it diuses rapidly from phase-separate
gasoline and partitions into groundwater, followed by
toluene, ethylbenzene and xylenes. The reverse
sequence occurs with BTEX in soils. Toluene, ethylbenzene, and xylenes are preferentially retained by soil
relative to benzene. Ethylbenzene and xylenes are also
more resistant to degradation than benzene or toluene.
The initial BTEX concentrations in gasoline vary
and initial BTEX ratio values in the product are
rarely available. A technique that addresses these
initial concentration variations and the challenges
that these processes preferentially remove benzene
from the groundwater is to use a cumulative BTEX
ratio. The cumulative BTEX ratio is dened as Rb
B T=E X and assumes that the ratio decreases
exponentially with time after a release, according to
(Montgomery, 1991; Kaplan et al., 1995, 1997):

Pristane and phytane are isoparans known as

isoprenoids whose ratio has been used to dierentiate
between sources of crude oil (Zakaria et al., 2000).
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-paran 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 that
results in the pristane and phytane peaks becoming
more pronounced on the chromatogram. Examination
of the C17/pristane and C18/phytane is therefore argued
as a qualitative basis for determining the degree of
degradation and hence weathering, primarily for diesel
(Kaplan and Galperin, 1996). A linear relationship
extending for about 20 years is described by:
Tyear 8:4n-C17 =Pr 19:8

where an average initial value for [n-C17/Pr] ratio in

dispensed diesel fuel is about 2.3 for No. 2 diesel fuel
(Kaplan et al., 1995, 1997).
The pristane/phytane method was used to estimate
the age of a No. 2 diesel in Denmark and the
Netherlands (Christensen and Larsen, 1993). The
authors analyzed 11 diesel fuels from ve dierent oil
companies using dierent laboratories and analytical
methods. The peak heights were used for ratios (e.g.,
peak heights from a baseline can be dierent for
dierent GC/FIC systems and methods) (Smith,
2000b). The authors concluded that the average C17
ratios was 1.98+2.0. The authors concluded that an
analysis of the C17/pristane ratios provided a means to
age date the diesel. The ratios for 26 rened and fresh
distillates and motor oils from the United States were

BTEX Ratios

Rb 6:0exp0:308 t :

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. A value between 1.5 and 6.0 is generally
interpreted as indicative of a release that occurred
within the last 1 to 5 years, while a value less than 0.5 is
indicative of a release of greater than 10 years (Kaplan
and Galperin, 1996). The ratio of benzene plus toluene/
ethylbenzene xylenes decreases with time due to the
higher solubility in water of the benzene and toluene

Review of Environmental Forensic Techniques 185

relative to ethylbenzene and xylenes. The accuracy of

this technique is improved by using a best-t regression
line from historical site data.
Challenges to BTEX ratio analyses include variations in the rate of BTEX transformation due to
variations in soil texture, soil mineralogy, microbial
diversity, and electron acceptor availability. The
volume of the release, groundwater chemistry and
hydrodynamic characteristics are additional variables
(Alvarez, Heathcote and Powers, 1998; Landmeyer
et al., 1998; Peterson, 2000). Other issues include the
uncertainty regarding the initial gasoline composition
and chromatographic separation of the BTEX components during migration through the subsurface. The
initial BTEX concentration in gasoline is signicant
because the composition of gasoline varies with the
octane rating and with the time of year when the
gasoline was formulated. In colder climates, the gasoline composition changes so that the Reid Vapor
Pressure is high in wintertime to provide easy startup,
and low in summertime to prevent vapor lock. The
gasoline grade also aects the initial BTEX composition. Premium gasoline with an antiknock additive
package generally has a higher fraction of benzene
since it has a higher octane rating. Regulatory changes
also impact the historical composition in gasoline. The
Clean Air Act Amendments of 1990, for example,
restricted benzene concentrations in gasoline to 1.6%
by volume. Gasoline blended prior to 1990, for
example, generally contains more benzene (6% by
volume)
than
post-1990
gasoline
(Johnson,
Kemblowski and Colthart, 1990).
Separation (i.e. individual BTEX compounds are
transported at dierent velocities through the soil and/
or groundwater) can aect BTEX concentrations and
hence ratios. The assumption that dierences in BTEX
concentrations are due exclusively to biodegradation
when separation is occurring may be invalid. The
location of a sample relative to the source can impact
BTEX values as samples farther from the release are
more susceptible to separation than those closer to the
release.
BTEX ratios in dissolved groundwater samples are
aected by the volume and changes in water in contact
with the phase-separate gasoline. Greater volumes of
water available to water wash the BTEX from the
gasoline results in accelerated changes in the BTEX
composition. The preferential leaching of benzene and
toluene from gasoline decreases the B/X and
(B T=E X) ratios in phase-separate product
relative to its presence in groundwater. Reported B/X
ratios of 0.2 to 0.9 for water equilibrated with
weathered gasoline, for example, are lower than the
majority of B/X ratios (Hinchee and Reisinger, 1987).
Another challenge to the use of BTEX ratios for age
dating and source identication is that the biodegradation of gasoline, and especially the BTEX components,
is highly variable with abrupt changes occurring on
micro and macro scales. Under anaerobic conditions,
for example, toluene can degrade faster than benzene.
These uncertainties result in a wide range of ratios for
identically aged spills, especially in dierent soils.
Another issue to consider when the BTEX compounds
are within a mixture of contaminants is that some of
the non-BTEX compounds may impact BTEX

degradation rates (Johnston, Borden and Barlaz,

1996; Berg et al., 1999). Variations in the organic
matter in the aquifer can also result in variations in the
degradation rates of BTEX compounds. In aquifers,
BTEX biodegradations rates are normally assumed to
occur via rst order kinetics where the rate (dC/dt) is
proportional to the contaminant concentration
described as lC dC/dt. Given dierences in the
subsurface environment, this assumption may be
invalid.
BTEX degradation rates vary according to whether
they are measured in situ or in the laboratory (Chapelle
et al., 1996). Laboratory measured biodegradation rate
estimates are sensitive to ambient redox conditions and
must be matched to eld conditions to obtain reliable
results. The assumption that BTEX components
degrade via rst-order kinetics may also be inappropriate when extrapolating laboratory-derived to eldscale degradation rates (Bekins, Warren and Godsy,
1998).

Contaminant Transport Models

Contaminant transport models are used for age dating,
for source identication, and for cost allocation
purposes. While models are available for contaminant
transport in the air, soil and groundwater, the
following text deals only with soil and groundwater.
The transport of a contaminant through the subsurface
is presented according to whether it migrates through a
paved surface, soil, or groundwater.
Paved surfaces
A frequent issue in environmental litigation is whether
a solvent migrated through a paved surface such as
asphalt, concrete, crushed rock, or compacted soil, and
if so, the time required for its transport. Ideally, a
representative pavement core sample is collected, a
representative liquid sample is ponded on the pavement
in a manner consistent with the circumstances of the
release, and the time required for the liquid to transit
the sample is measured. Absent these direct measurements, contaminant transport equations are frequently
used for estimating the transit time. In order to select
the most appropriate equation(s) that mirror the
release event(s), the most likely transport mechanism
(e.g. liquid advection, gas diusion, liquid diusion,
and/or evaporation) must be identied.
Liquid transport through a monolithic pavement is
assumed to be rapid. This assumption is true if the
pavement is cracked allowing unrestricted ow or if the
release occurs over an expansion/control or isolation
joint lled with permeable wood, oakum or tar.
Expansion joints are normally located at the junction
of the oor and walls, or foundation columns and
footings. Isolation joints 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 premolded joint llers. Testing the joint material for
contaminants of interest can often establish if a
contaminant migrated through the joint material.
Absent direct measurements or the presence of
preferential pathways, a mathematical model requiring

186 R. D. Morrison

numerous input variables is used to estimate when a

liquid penetrated a paved surface. Modeling assumptions representative of the release circumstances and
uid are required for this modeling approach and often
include the following input parameters:
. the temporal nature of the release (steady state or
transient);
. a representative saturated and/or unsaturated
hydraulic conductivity value(s) for the paved surface;
. physical properties of the contaminant (density,
viscosity, vapor pressure);
. chemical properties of the liquid ( phase separate,
dissolved or mixed);
. air temperature at the time of the release;
. the volume of the release;
. the evaporative ux of the liquid into the ambient
air.
An understanding of the circumstances of the release
and pavement composition is important for developing
a realistic conceptual model. For example, if the model
omits a value for evaporative loss and assumes a
constant liquid thickness on the pavement, the time
estimated for liquid transport is shorter than if
evaporation is included. Similarly, if cleanup activities
are performed coincident with the release (e.g. sawdust,
green sand, absorbent socks, Sorball, crushed clay,
etc.) or if the spill occurred in a building with forced
air, these competing activities need to be incorporated
into the model as they result in a slower calculated
transport rate through the pavement.
Variables describing the physical condition of the
paved surface include:
. whether the surface is treated with an epoxy coating
to prevent corrosion from acid releases (common in
metal plating shops);
. whether additives such as Dow Latex No. 560 was
mixed with the concrete to reduce its permeability to
chemicals;
. pavement thickness, porosity, composition and
slope;
. the nature of the surface prior to the release (i.e. was
it impregnated with oils and dirt, smooth v. pitted,
sloped toward a drain, etc.).
Ideally, a pavement sample is available for directly
measuring its porosity and hydraulic conductivity with
a uid similar to the liquid released onto the surface. If
direct measurements are unavailable, estimated values
for these properties are available in the literature. Once
representative values for these properties and the
circumstances of the release are dened, a realistic
conceptual model can be constructed.
The contact time of the liquid with the pavement is
important. If phase-separate PCE accumulates in a
blind concrete sump, neutralization pit or clarier, for
example, the residence time and hydraulic gradient
may be sucient for penetration through the concrete.
If the liquid is thinly distributed on the pavement,
however, evaporative loss may be sucient to eliminate
the possibility of liquid migration through the pavement. One example of how the evaporative loss is
estimated is the case of an assumed semi-innite region

with a uniform initial concentration and mass transfer

at the surface given by (Choy and Reible, 1999):
@cA =@t DAeff =Rf @2 cA =@z2

z 2 0; 1 3

DAeff @cA =@zjz0 ka cA z; tjz0

t 4 0 4

cA z; tjz!1 cA0

t 4 0 5

cA z; tjt0 cA0

z 2 0; 1 6

The concentration prole is given by:

p
cA z; t cA0 ferfRf z= 4DAeff Rf t
expka z=DAeff k2a t=DAeff Rf erfc
p
p
 Rf z= 4DAeff Rf t ka t=DAeff Rf g
z 2 0; 1; t 4 0:

The surface ux out of the system is described by:

jA tjz0 ka cA0 expk2a t=DAeff Rf erfc
p
t40
 rka t=DAeff Rf

where ka is the surface mass transfer coecient, cA0 is

the concentration of species A in the air phase per unit
volume, DA(e) is the eective diusion coecient of
species, Rf is the retardation factor, jA is the mass ux of
the component, z is the depth of position, and t is time.
Numerous models are available to calculate the rate
of transport of a liquid through pavement (Ghadiri
et al., 1992; Selima, 1998). For saturated ow, a
simplied one-dimensional expression for the vertical
transport of a liquid using Darcy's Law is available.
This expression denes the downward velocity (v) of
the liquid as equal to the downward ux (q) divided by
the porosity of the pavement. The downward ux is the
saturated hydraulic conductivity multiplied by the
vertical gradient. Saturated hydraulic conductivity
and porosity values for paved materials are measured
directly or can be obtained from published values. This
calculation results in a value in units of length over
time that is divided into the pavement thickness to
estimate the transport time.
Pavement transport models using Darcy's Law
assume that the pavement is saturated with liquid
prior to the release. If the pavement is unsaturated,
liquid transport may be dominated by unsaturated ow
resulting in contaminant velocities several times slower
than for saturated ow and the use of unsaturated zone
equations such as Richard's equation may be more
appropriate (Richards, 1931). A one-dimensional
expression for unsaturated ow is:
C@c=@t @=@zK@c=@z @K=@z

where C is the specic water capacity or change in

water content in a unit volume of soil per unit change
in the moisture content, w equals the suction head (i.e.
matric potential), and K is the unsaturated hydraulic
conductivity value for the soil.

Review of Environmental Forensic Techniques 187

An additional consideration for either saturated or

unsaturated ow through a paved surface for a phaseseparate hydrophobic uid, such as TCE, is that the
ambient hydrophobic pore water in the pavement
repels TCE. While the extent of repulsion is dicult to
quantify, the net result is some degree of TCE
retardation.
An estimate of whether a contaminant vapor cloud
has migrated through a paved surface is a common area
of inquiry, especially when equipment such as vapor
degreasers are present. Vapor degreasers are often
installed in a concrete catch basin to capture any liquid
spills. While catch basins are eective at mitigating
liquid spills, they exacerbate the potential for vapor
transport through the concrete because they act as an
accumulator for the vapor and minimize the potential
for vapor dilution with the ambient air. Given this spill
scenario, the selection of a model assuming that vapor
transport is the primary transport mechanism may be
more representative than those that assume liquid
transport. In many cases it is dicult to reconstruct
the most dominant contaminant transport phase.
Vapor transport models used to estimate the time
required for a chemical to migrate through a paved
surface usually include the following input variables;
vapor density, vapor source ux (constant or transient)
above the pavement, the Henry's Law constant for the
contaminant, pavement thickness, porosity and moisture content at the time of the release, and the
concentration of the vapor above, within and below
the pavement prior to the release (Choy and Reible,
1999). Numerous equations are available to estimate
the travel time of vapor through pavement (Crank,
1985; McCoy and Rolston, 1992). Equation 10 describes
one approach for the unsteady, diusive radial ow of
vapor from a source (Cohen, Mercer and Matthews,
1993):
@2 Ca =@r2 1=r@Ca =@r Ra D*@Ca =@t

10

where the air lled porosity (na) is assumed to be

constant (see equation (12)), Ra is the soil vapor
retardation coecient, Ca is the computed concentration of the vapor in air, r is the source radius and the
eective diusion coecient, D*, ( for TCE 3
2 
10 6 m2 =sec and 0.072 cm2/sec for PCE) (Lyman,
Reehl and Rosenblatt, 1982) is equal to:
D* Dta

n2
333
=n2t
a

11

surfaces x 0 and x 1 are maintained at a constant

concentration specied as C1 and C2 , respectively.
After a time, steady state conditions are reached and
the contaminant concentration is assumed to be
constant at all locations in the pavement. The diusion
equation in one dimension reduces to the following
equation (Crank, 1985):
d2 C=d2x 0

if the diusion coecient (D) is assumed to be

constant. On integrating with respect of x, the
following expression arises:
dC=dx constant

Ra 1 nw =na KH rb Kd =na KH

12

where nw is the bulk water content, na is the air-lled

soil porosity, rb is the soil bulk density, Kd is the
distribution coecient, and KH is the dimensionless
Henry's Law constant.
Another approach is to conceptually consider the
diusion of a vapor through a medium bounded by
two parallel plates. This approach assumes a pavement
thickness (l) and a diusion coecient (D) whose

14

and by introducing the conditions at x 0, x 1, and

integrating, then:
C C1 =C2 C1 x=l:

15

The concentration changes linearly from C1 to C2 as

the liquid migrates through the pavement. The transfer
rate of the diusing substance is the same through the
pavement described by:
F DdC=dx DC1 C1 =l:

16

If the pavement thickness (l) and the surface

concentrations C1 and C2 are known, D is deduced
from an observed value of F. If the surface x 0 is
maintained at a constant concentration C1 and at
x 1, evaporation into the atmosphere is assumed for
which the equilibrium concentration immediately
within the paved surface is C2 , so that:
@C=@x hC C2 0; x l

17

C C1 =C2 C1 hx=1 hl

18

F Dh*C1 C2 =1 hl

19

then

and

and
@C=@x h1 C1 C 0; x 0

and

n2t

where ta
and
is the total soil porosity
which is the sum of the air lled porosity and the
volumetric water content. The soil vapor retardation
factor (Ra) is equal to:

13

@C=@x h2 C C2 0; x l

20

where
C h1 C1 f1 h2 l xg h2 C2 1 h1 x
=h1 h2 h1 h2 l:

21

Numerous challenges to liquid and vapor transport

of contaminants through a paved surface are available.
While these challenges are highly site and model
specic, generic categories include the following:
. variability of the model parameters;
. accuracy of the known circumstances of the spill
event(s);

188 R. D. Morrison

. environmental conditions at the time of the release(s)

(e.g. thickness of the spill, composition, air temperature, etc.);
. consistency of the modeled results with measured
contaminant results under the paved surface (if
available);
. impact of potential short circuiting pathways, such
as expansion joints and/or cracks on the conceptual
model.
Soil
Hundreds of models describing the transport of a
chemical through soil are available. A one-dimensional
equation describing the transport of a single compound via advection and diusion in the unsaturated
zone is (Jury, Sposito and White, 1986; Jury and Roth,
1990):
R1 @C1 =@t Du @2 C1 =@z2 V@C1 =@z lm R1 C1

22

where C1 is the pore water concentration in the vadose

zone, lm is the decay constant, R1 is the liquid
retardation coecient, Du is the eective coecient,
and V is the inltration rate.
The retardation coecient (R1) is estimated by:
R1 rbu Kdu um fm um KH

23

where rbu is the soil bulk density, Kdu is the

distribution coecient for the contaminant of interest,
fm is the soil porosity, um is the soil moisture content,
and KH is the Henry's constant for the contaminant of
interest. The distribution coecient (Kdu) of the
contaminant is:
Kdu 0:6foc;u Kow

24

where Foc,u is the fraction of organic carbon in the soil

and Kow is the octanol-partition coecient of the
contaminant of interest. The degradation rate constant
is estimated by:
lm ln2=T1=2m

25

where T1/2m is the degradation half-life of the contaminant of interest. The eective diusion coecient:
Du tL DLM KH tG DGM

26

where DLM is the molecular diusion coecient in

water, tL is the soil tortuosity to water diusion
coecient, DGM is the molecular diusion coecient in
air, and tG is the soil tortuosity to air diusion. The
tortuosity value associated with the diusion of a
compound in water and air is described by the
Millington expression as:
10=3
2
tL u10=3
=f2m :
m =fm and tG fm um

27

If present, the impact of articial or natural

transport pathways on a model requires scrutiny as
they can represent a signicant source of uncertainty in
the model results. Examples of articial and natural
transport mechanisms include dry wells, foundation

borings, utility trenches, sewer or storm water backll,

cisterns and septic lines, discrete layers of high
permeability soils, and mechanical disturbance.
The condence level of model parameters can be
performed via a probabilistic analysis such as the
likelihood (e.g. used for nonlinear models) and Monte
Carlo method. Monte Carlo simulations provide a
numerical method for generating simulated data using
random numbers and assumed probability distributions. This approach also allows the identication
of parameters that inuence the calculated groundwater
contaminant concentration, and provide an uncertainty
analysis for the most sensitive input variables.
Groundwater
The rate of contaminant transport in groundwater is
routinely used as evidence in insurance litigation for
source identication, age dating and for cost allocation
purposes. This type of modeling has been primarily
limited to the realm of environmental consultants,
although some peer-reviewed literature is available on
the subject (Gorelick, Evans and Remson, 1983;
Unk, 1989; Bagtzoglou, Doughery and Thompson,
1992; Wagner, 1992; Skaggs and Kabala, 1994, 1995;
Woodbury and Ulrych, 1996; Snodgrass and Kitanidis,
1997; Neupauer and Wilson, 1999). Models used in
litigation to date contaminant releases range in
sophistication from a straight line drawn between an
alleged source and the leading edge of a contaminant
plume to sophisticated three-dimensional contaminant
transport models.
The origin of inverse modeling for contaminant
transport in groundwater is predated by research in the
heat transfer literature (Bayo et al., 1992; Huang and
Ozisik, 1992; Silva-Neto and Ozisik, 1993). Governing
equations in the heat transfer literature, for example,
are similar to the advection-dispersion equations used
in groundwater models, except that the advection term
is seldom used in inverse heat conduction problems
(Lattes and Lions, 1969; Alifanov and Artyukhin,
1976; Tikhonov and Arsenin, 1977). Issues regarding
parameter condence are also addressed in many heat
transfer equations (Beck and Arnold, 1977; Alifanov
and Nenarokomov, 1989; Marquardt and Auracher,
1990; Carasso, 1992).
Inverse models
The term ``backward extrapolation model'' was
reported in 1991 by Allen Kezsbom and Alan Goldman in an article describing the Sterling v. Velsicol
Chemical Corporation case (855 F.2d 1188 6th Circuit
Court, 1988) (Kezsbom and Goldman, 1991; Kornfeld,
1992). Subsequent authors describe this approach with
the term ``reverse or inverse modeling'' (Erickson and
Morrison, 1994; Woodbury and Ulrych, 1996; Morrison, 1999c; Parker, 2000) and ``backward random walk
problem'' (Chandrasekhar, 1943). In its simplest
application, inverse modeling relies upon measured
properties or contaminant concentrations to extrapolate to some early point in time the age and location
of a contaminant release, most frequently by geostatistical and optimization approaches (Gorelick and
Remson, 1982; Khachikian and Harmon, 2000).

Review of Environmental Forensic Techniques 189

Examples include inverse models for reconstructing

complex, multi-parameter release histories with known
source locations from spatially distributed plume
concentration data (Skaggs and Kabala, 1994, 1995,
1998; Woodbury and Ulrych, 1996).
One of the earliest applications of inverse modeling
for contaminants in groundwater used a least squares
regression and linear programming to identify the
location and discharge rates of contaminants that
were simultaneously migrating from ve disposal sites
over a 5-year period (Gorelick, Evans and Remson,
1983). Other approaches include identifying the contaminant source location with backward probability
models to establish the most likely of several release
sites. Bagtzoglou, Doughery and Thompson (1992), for
example, described the use of a reverse time random
particle method to estimate the probability that a
particular site was the source of a contaminant plume.
These probability approaches assume a single point
source release (Birchwood, 1999). In another application, the vertical concentrations of PCE and TCE in
an aquitard were evaluated to reconstruct a release
history; only diusion and sorption were assumed to
aect mass transport in the aquitard (Ball et al., 1997;
Liu and Ball, 1999). Dimov, Jaekel and Vereecken
(1996) used the adjoint formulation of the onedimensional advection-dispersion-deposition equation
for source identication and loading rate. Another
approach modeled contaminants from a constant
source concentration using two-dimensional diusion
to estimate source characteristics and transport
parameters from head and concentration data
(Sonnenberg, Engesgaard and Rosjberg, 1996).
Sidauruk, Cheng and Ouazar (1997) developed a set
of analytical procedures for contaminant source identication that relied upon contaminant concentrations
measured within a two-dimensional contaminant
plume. Contaminant ow was assumed to be homogeneous and groundwater velocity was uniform for
instantaneous and continuous releases. The authors
noted the limitations of certain parameters that can
only be uniquely determined by sampling at a minimum
of two dierent times. Skaggs and Kabala (1994) used
Tikhonov regularization (Tikhonov and Arsenin, 1997)
to transform the inverse problem into a minimization
problem with a unique solution as well as using the
method of quasi-reversibility to solve the problem
(Skaggs and Kabala, 1995). It is assumed that the
location of the source is known. Wagner (1992)
proposed a deterministic approach for the combined
estimation of model parameters and source characteristics. Bagtzoglou, Doughery and Thompson (1992)
used backward location probabilities to identify contaminant sources. Probability maps were then developed using a random walk method by reversing the ow
eld and assuming that dispersion was constant.
The foundational advection/dispersion equation
used in traditional groundwater models is also used
for backward extrapolation modeling (Wilson and
Linderfelt, 1991; Wilson and Rao, 1992; Liu, 1995).
An example of one expression used to run an
advection-dispersion one-dimensional model backward
in time (similar to backward particle and front

tracking) (Shafer, 1987) is described by Wilson and

Liu (1995) by:
@g=@t D@2 g=@x2 V@g=@x

28

where g is a probability density or cumulative

distribution function of interest, D is the dispersion
coecient, t is time and x is the upgradient distance to
the source. The authors hypothesized that by selecting
appropriate initial and boundary conditions, equation
(28) can solve the desired probability function to create
travel time and location probability maps when the
location of the release is unknown. Neupauer and
Wilson (1999) describe the solutions for source and
time probabilities for a pumping well as:
@fx =@t D@2 fx =@x2 n@fx =@x

29

where fx ! 0 as x ! 1, and
nfx D@fx =@x 0 at x 0 and fx x; 0
dx xd

where t is backward time (t td t, where td is the

detection time), xd is the detection location at a
pumping well (xd 0), D is the dispersion coecient,
n is the groundwater velocity, fx is the location
probability, and d is the Dirac delta function. The
solution for equation (29) provides the backward
probability for a detection at xd 0, as given by
Neupauer and Wilson (1999) by:
p
fx x; t 1= ptexpfx nt2 =4Dtg n=2Dexp
p
 fnx=Dgerfcx nt= 4Dt: 30
For a contaminant parcel removed at the pumping
well (xd 0), equation (30) describes the probability
density function of the location of the contaminant
parcel at time t before it was observed at the pumping
well. The backward model for the travel time
probability map is then (Wilson and Liu, 1995):
@ft =@t D@2 ft =@x2 n@ft =@x

31

where ft ! 0 as x ! 1, and nft D@fr =@x

ndt at x 0, and ft(x, 0) 0, and where D and n
are constant and the pumping well is assumed to be at
xd 0. The solution to equation (31) is the backwardin-time time probability from location x to a detection
at xd 0 is (Wilson and Liu, 1995):
p
ftx; t 1= ptexpfx nt2 =4Dtg
n2 =2Dexpfnx=Dgerfc
p
 x nt= 4Dt:

32

For a contaminant detected at the pumping well,

equation (32) describes the probability density function
of the travel time from an upgradient source location
(x) to the pumping well at xd 0.
In cases where light nonaqueous phase liquids
(LNAPLs) are of interest, models using the direct
estimate and nonlinear parameter estimation method
have been proposed. The direct estimation approach
involves the estimation of a release date from a single

190 R. D. Morrison

measurement of travel distance. The direct estimation

method assumes that all parameters in the model are
known. Only one measurement of the plume distribution (e.g. travel distance Ls at a given time Dtx) is
known. An advantage of the direct estimation method
is that only a single observation of the travel distance is
required.
The nonlinear parameter estimation method involves
the simultaneous estimation of when a contaminant
release occurred. Additional unknown model
parameters can also be estimated from multiple
measurements of travel distances at various time
steps. Mean values of the estimated variables and
their condence limits are determined using nonlinear
regression methods.
If an inverse model is used to simulate the migration
of a phase-separate uid, dierent governing equations
and parameters are needed (Parker and Lenhard, 1990;
Butcher and Gauthier, 1994). The solution of the
inverse problem for identifying NAPL location
involves estimating dissolution parameters in addition
to conventional ow and transport modeling
parameters (Khachikian and Harmon, 2000). A key
variable for phase-separate models is whether the
three-phase (air, water, and NAPL) expression describing the pressure distributions between these uids is
representative of the site. LNAPL models normally
assume that the phase-separate liquid is continuous
and/or connected. If this assumption is incorrect, the
LNAPL volume in the subsurface can be overestimated. If monitoring wells are separated by
hundreds of feet and the LNAPL thickness is thin
(less than a foot), the possibility that the LNAPL is not
continuous is highly probable. Other challenges
include the accuracy of LNAPL or DNAPL uid
viscosity values, the selected interfacial tension values
for the dierent liquids, the values used to represent the
soil texture, and the accuracy of any phase-separate
measurements. Fluid viscosity and density measurements are rarely measured and are more commonly
obtained from the literature. These published numbers
can, therefore, deviate from the eld values due to
weathering and/or commingling of the LNAPL with
other compounds.
Challenges to inverse models
The successful review of an inverse model includes an
analysis of model parameters and conceptual framework. Examples of model parameters incorporated
into many inverse models and which represent
potential sources of uncertainty include:
. the accuracy of the eective porosity value(s)
selected;
. the consistency of the groundwater ow direction
and velocity over time;
. the validity of the selected hydraulic gradient(s)
values over time and distance from the release (e.g.,
in Anderson v. Cryovac the court found that ``. . .
given the tiny gradients present here, uncertainties in
the metage of water levels likely concealed the true
direction of groundwater ow'');
. the number of data points and time interval during
which the data was collected (Mahar and Datta,

.
.

.
.
.
.
.

1997). In Renaud v. Martin Marietta Corporation

1990, the expert hydrogeologist for the plainti
constructed a chemical fate and transport model
using only one data point to describe a continuous
release of contaminants over an 11-year period;
the nature of the release (steady v. non-steady);
the loading rate (in the Veliscol case, plainti's
groundwater model assumed a loading rate when
production records were available to establish a
loading rate, which were used by the defendants);
the value(s) selected for aquifer(s) thickness (model
specic);
the horizontal and transverse dispersivity values;
contaminant retardation and/or degradation rates
(Davidson and Creek, 2000);
identication of the leading edge of the contaminant
plume (model specic);
the eect of recharge/discharge rates (if applicable)
of water into the system and its impact on plume
geometry and contaminant velocity. In the Velsicol
case, for example, the court wrote, ``. . . the district
court rejected the defendant's water model as
inaccurately under representing the extent of chemical contamination in the groundwater supply. In
refuting the defendant's model, the court reasoned
that Velsicol had failed to factor in the massive
dumping of liquid waste, the ponding of water in the
trenches, and the draw down on the aquifer caused
by new homes.''

Some inverse models require an accurate value for the

contaminant plume length, the location of the release,
or the determination of when a contaminant rst
entered a monitoring well downgradient from the
source. If the source location and/or the plume length
is assumed, signicant variations in the estimated age
of the release can occur.
Another issue is whether the compound or class of
compounds (i.e. total volatile organic compounds,
TCE, PCE, MTBE, etc.) used to determine the plume
length biases the measurement. The use of benzene, for
example, may reect a stabilized or decreasing length
while the use of MTBE for the same plume may
indicate an expanding plume, depending on the source
strength. A similar dilemma exists for transformation
products. Among likely parentdaughter compound
combinations for chlorinated solvents, distances
between the respective maximum concentration
locations were found to be in the order of 1025% of
the maximum plume length at most sites (McNab and
Dooher, 1999). For multiple releases, compound
selection, release location, and potential co-solvation
impacts require scrutiny (Morrison, 1999b). Examples
of possible challenges or areas of inquiry when
evaluating inverse models include (Morrison 2000b):
. adjustment of the model-input parameter, within a
reasonable range, that produce results consistent
with measured values but inconsistent with the
alleged released date. For example, the distribution
of simulated head measurements depends to some
degree on the recharge rate to saturated hydraulic
conductivity value ratio. Recharge and hydraulic
conductivity value combinations can be selected to
produce modeled head distributions that are not
representative of the site;

Review of Environmental Forensic Techniques 191

. determination of the condence level associated

with simulated or assumed model parameters
(e.g. groundwater velocity, analytical bias, temporal
and spatial variations of the data, time interval
between sampling dates, etc.);
. collection of 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. As stated by an expert in
United States v. Hooker Chemical & Plastics
Corporation (1985) ``The accuracy of these equations
[referring to those used in a mathematical model] is
tested by comparing them with what actually occurs
within the groundwater system'';
. identication of whether the water mass balance is
conserved. A well-calibrated model exhibits a small
dierence in the water balance and is often included
as output to the model;
. evaluation of model calibration via the preparation
of scattergrams comparing values for measured
heads with the simulated heads for each well. If the
calibration is perfect, the data sets should fall along
a 45-degree line. Data points farther from this line
reect a greater deviation from actual ow conditions. Plotting the residuals (the dierence between
the simulated and observed heads) can also provide
insight regarding model calibration;
. comparison of the input parameters with those used
for other site models (e.g. models used for designing
a remediation system, health risk models used for
site closure, etc.). It is not uncommon that physical
and chemical parameters used in a model in support
of a Risk Based Corrective Action (RBCA) study are
dierent than those used for inverse modelings.
Inverse models rarely incorporate the time required for
the contaminant to ow through a paved surface. If the
depth to groundwater is shallow, or the contaminant is
introduced quickly into the groundwater via a preferential pathway (i.e. a dry well, cistern, well casing,
etc.), age dating the release with an inverse model may
be a reasonable approach for estimating the age and/or
location of the release. If the release occurred at the
surface, the subsurface soils are not transmissive and/
or the depth to groundwater is signicant (greater than
50 feet) , the cumulative time required for contaminant
migration through the soil column can be signicant.
Ignoring this portion of the conceptual model with an
inverse model can under-estimate the age of the release.
In the Velsicol case, the plaintis' experts assumed that
carbon tetrachloride and chloroform entered the
aquifer almost immediately after commencement of
disposal in October 1964 which was inconsistent with a
United States Geological Survey study in 1967.

Conclusions
The application of the forensic techniques presented in
this article for age dating and source identication
should be carefully selected to determine the probability that the information will be useful. In the
context of environmental litigation, the results from
each technique should be coupled with other groups of
evidence but not congured so as to jeopardize other

lines of evidence. The results of the forensic techniques

should be able to withstand intense scientic scrutiny
relative to the purpose for which the data was collected.

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