Environmental Forensics (2000) 1, 37±46

doi:10.1006/enfo.1999.0001, available online at http://www.idealibrary.com on

Evolution of Organic Analytical Methods in Environmental

Forensic Chemistry
A. Dallas Wait*
Gradient Corporation, 238 Main Street, Cambridge, MA 02142, U.S.A.

(Received 20 January 1999, revised manuscript accepted 25 February 1999)

Over the past few decades the development of environmental regulations, advances in analytical chemistry and other
scienti®c disciplines, and increased rigor in quality control procedures have created a new discipline, environmental
forensics. The need for analytical methods that determine qualitatively and quantitatively organic compounds in the
environment, especially in drinking waters, was recognized in the early 1950s. These methods were developed gradually
by the early 1960s. The important tools of gas chromatography and mass spectroscopy that evolved in the 1970s
provided the early environmental forensic chemist for the ®rst time with the ability to produce scienti®cally sound data
that was admissible in court. By the 1990s, multivariate statistical techniques became available and accepted, including
principal component analysis (PCA) and polytopic vector analysis (PVA). These techniques, coupled with the advancing
analytical methods, have enabled forensic investigator tools to evaluate and demonstrate unique attributes of a set of
data. Analyses of marker compounds, PCBs, PCDD/Fs and petroleum hydrocarbons are all shown to be potentially
valuable in deciphering the source and fate of contamination. This paper shows how advancements in environmental
analytical chemistry provide the forensic chemist with tools to assess the source(s) of site contamination.
# 2000 AEHS

Introduction Journal of Forensic Science, and a few years later in the

All forensic investigations involve the application of
science to law. Environmental forensic investigations
often involve scienti®c testing and/or modeling to
discern attributes at a site that allows the investigator
to decipher the source(s) and fate of the contamination,
and in some instances apportion the blame. Develop-
ment of environmental regulations over the past few
decades, advances in analytical chemistry and other
scienti®c disciplines, and increased rigor in quality
control procedures have coalesced, creating an expand-
ing environmental forensic industry. Today's environ-
mental forensic studies often employ interdisciplinary
approaches involving, in part, chemical ®ngerprinting,
hydrogeology, stratigraphy, geochemistry, chemo-
metrics, and site history (Stout et al., 1998). This
paper reviews the growth and impact of analytical
chemistry developments as they relate to environmental
forensic studies, focusing on organic chemistry meth-
odologies other than radiochemical dating and stable
isotope techniques.
Regulatory Foundation
Forensic chemistry originated in criminal investi-
gations. In the 1950s and 1960s advances in the science
of substance analysis provided prosecutors with new
tools for uncovering criminal actions (e.g. Saferstein,
1982). Research documenting some of these scienti®c
advances was published as early as the mid-1950s in the
*Tel: 617-395-5000. Fax: 617-395-5001. E-mail: dwait@gradientcorp.
com
37
1527-5922/00/010037+10 $35.00/00
Journal of the Forensic Science Society. Yet the impetus
for forensic investigations relating to the environment
was the development of applicable federal regulations
(Rodgers, 1994). As shown in Table 1 (taken, in part,
from Rodgers, 1994), environmental regulations did
not proliferate until the 1970s. Federal laws to control
pollution were enacted as a response to the public
awakening in the 1960s to the deterioration of environ-
mental quality (e.g. Carson, 1962; American Chemical
Society, 1967). The formation of the United States
Environmental Protection Agency (USEPA) in 1970
provided the platform for comprehensive environmen-
tal regulations at the federal level. The Safe Drinking
Water Act of 1974, and the subsequent 1976 Consent
Decree between the USEPA Administrator and several
environmental groups, promoted regulatory analytical
chemistry methods associated with quality control
procedures which would help to produce demonstra-
tively sound scienti®c data (Lichtenberg, 1978). This is
not to suggest that data produced prior to this time
period necessarily lacked quality and integrity. By
1977, federal regulations (Section 304h of Publication
92-500 [Federal Water Pollution Control Amend-
ments], and the Interim Drinking Water Regulations)
speci®cally required use of USEPA-approved analysis
methods. However, in the late 1970s dramatic environ-
mental incidents such as Love Canal, Times Beach, and
the Valley of Drums (e.g. Colton and Skinner, 1996), as
well as high-pro®le marine oil spills such as the Ixtoc I
Well Blowout in the Gulf of Mexico (e.g. Boehm et al.,
1982) accelerated the need for rigorous regulatory
testing methods and forensic capabilities to support
enforceable environmental investigations.
# 2000 AEHS
38 A.D. Wait

Table 1. Some major United States environmental regulations Data Quality and Integrity
Date Regulation The reputation and credibility of environmental
forensics depends entirely upon the integrity of the
1899 River and Harbors Act (RHA) analytical results, as de®ned and discussed by Maney
1902 Reclamation Act (RA) and Wait (1991). Regardless of how technically
1910 Insecticide Act (IA) advanced an analytical chemistry method may be, if
1911 Weeks Law (WL)
1934 Taylor Grazing Act (TGA) the resultant data does not meet prescribed levels of
1937 Flood Control Act (FCA) quality, and if the data cannot be replicated and
1958 Fish and Wildlife Coordination Act (FWCA) defended, then the data become useless in the context
1964 Wilderness Act (WA) of forensic usability (Worthington, Luka and Haney,
1965 Solid Waste Disposal Act (SWDA)
1965 Water Resources Planning Act (WRPA)
1991; Berger, McCarty and Smith, 1996). However,
1966 National Historic Preservation Act (NHPA) even when good quality control programs exist, data
1968 Wild and Scenic Rivers Act (WSRA) integrity can be jeopardized by misuse of systems, long-
1969 National Environmental Policy Act (NEPA) term system bias, systemic problems with computer-
1970 Clean Air Act (CAA)
1970 Occupational Safety and Health Act (OSHA)
resident data, and deliberate corruption of data
1972 Water Pollution Control Act (WPCA) (Maney and Wait, 1991). The most heinous issue,
1972 Marine Protection, Research and Sanctuaries Act involving fraudulent data manipulation, has been
(MPRSA) (e.g. Zurer, 1991) and continues to be a problem (e.g.
1972 Coastal Zone Management Act (CZMA) USEPA, 1997a). It bene®ts the forensic investigator to
1972 Home Control Act (HCA)
1972 Federal Insecticide, Fungicide and Rodenticide Act ensure data integrity prior to use of the data (Wallin,
(FIFRA) Hamilton and Wait, 1994). Another problem is the lack
1972 Parks and Waterways Safety Act (PWSA) of quali®ed senior-level environmental forensic che-
1972 Marine Mammal Protection Act (MMPA) mists and scientists. Both an increasing environmental
1973 Endangered Species Act (ESA)
1974 Deepwater Port Act (DPA)
forensic business and an expanding technology base
1974 Energy Supply and Environmental Coordination Act have left a dearth of technically quali®ed chemistry
(ESCA) experts who can logically assess environmental con-
1976 Toxic Substances Control Act (TSCA) tamination problems in a sound scienti®c manner.
1976 Federal Land Policy and Management Act (FLPMA)
1976 Resource Conservation and Recovery Act (RCRA)
The value and concepts of quality control and
1977 Clean Air Act Amendments (CAAA) quality assurance in analytical chemistry have been
1977 Clean Water Act (CWA) recognized for many decades (e.g. Lundell, 1933). It
1977 Surface Mining Control and Reclamation Act (SMCRA) was not until regulatory methods were established,
1977 Soil and Water Resources Conservation Act (SWRCA) however, that formal quality control procedures
1978 Endangered Species Act Amendments (ESAA)
1978 Environmental Education Act (EEA) became a mandatory element of environmental inves-
1980 Comprehensive Environmental Response Compensation tigations. USEPA con®rmed the importance of quality
and Liability Act (CERCLA) assurance programs and quality control procedures at
1982 Nuclear Waste Policy Act (NWPA) the analytical (USEPA, 1979) and project (USEPA,
1984 Resource Conservation and Recovery Act Amendments
(RCRAA)
1980) levels. Coinciding with regulatory promulgation
1984 Environmental Programs and Assistance Act (EPAA) of quality control programs, professional organizations
1986 Safe Drinking Water Act Amendments (SDWAA) such as the American Society for Testing and Materials
1986 Superfund Amendments and Reorganization Act (SARA) (ASTM) and the Association of Ocial Analytical
1990 Clean Air Act Amendments (CAAA)
Chemists (AOAC) were also proposing quality assur-
ance guidelines. For example, in 1978 the American
Chemical Society (1980) convened a group of respected
analytical chemists to establish guidelines for data
One signi®cant regulatory response that arose from acquisition and data quality evaluation in environ-
these incidents was CERCLA (``Superfund''), sup- mental chemistry. At the same time, guidance was
ported by data integrity systems developed by the beginning to emerge which detailed criteria for collec-
USEPA National Enforcement Investigation Center tion of forensic data (ASTM, 1977, 1980, 1982).
(NEIC). The regulations promulgated under CERCLA USEPA established a structured planning process
aggressively instituted sound analytical methods which identi®ed data quality objectives (USEPA, 1984,
couched in rigorous quality control protocols, and 1994) for accuracy, precision, sensitivity, representa-
document control and chain-of-custody systems, which tiveness, comparability and completeness. Data quality
require one to recreate all aspects of data generation objectives are of value to the forensic investigator,
and demonstrate data integrity (USEPA, 1986). regardless of whether promulgated or non-routine
During the 1980s, more cases of environmental con- methods are employed. In the latter case, forensic
tamination that could jeopardize human health, such chemists must utilize their expertise and understanding
as the infamous drinking water contamination case in of site-speci®c data quality objectives to design and/or
Woburn, Massachusetts, peaked public pressure for implement an analytical procedure which will with-
enforcement (e.g. Harr, 1995). Compared to the stand scienti®c and litigation scrutiny (Wait and
explosive growth of environmental regulations in the Douglas, 1995). Analytical variability, detection limits
1970s and 1980s, the regulatory framework in the and false positive/false negative errors are examples of
United States today has matured, with many remaining the types of issues which must be considered (Koorse,
issues associated with liability (Farer, 1998; Tripp, 1989). Brilis and Worthington (1998) have discussed
1998), where environmental forensics plays a key role. factors a€ecting the admissibility of environmental

data into the courtroom, citing the Daubert Rule
where applicable (Daubert v. United States
[113S.Ct2786(1992)]). These admissibility consider-
ations continue to evolve.
Development of Organic Analytical Methods
The ®rst tests for organic constituents in the environ-
ment were for both water and sewage. These were
general methods and involved measuring the amount
of oxygen consumed by organic materials as they
degraded in water. This was measured either by bio-
logical oxidation or by chemical reaction with potas-
sium permanganate, with the ®rst procedure published
at least 120 years ago by Tidy (1879). These two tests
became known as chemical oxygen demand (COD)
and biological oxygen demand (BOD). These were
important parameters to measure in the early days of
sanitary analysis because it de®ned how putrescible a
sample was, which in turn showed how polluted a
waterway had become. By the 1930s numerous classical
test procedures existed for speci®c industrial organic
compounds, usually involving gravimetric and volu-
metric procedures (e.g. Jacobs, 1941).
Phenols and phenolic substances were the earliest
speci®c compounds for which scientists developed a
test devoted to their detection in environmental
samples, primarily because of their in¯uence on the
taste and odor of water. These tests were typically
colorimetric. Reagents were reacted with phenols in
solution to form colored compounds, generally azo or
indophenol dyes. The dyes, which had characteristic
colors, were compared visually with standards to deter-
mine the quantity of phenol. These methods were
subject to many interferences and were not speci®c to
just phenols. In 1946, the U.S. Public Health Service
(1946) adopted a 1 ppb standard for phenols in drink-
ing water, which may be the ®rst federal environmental
regulatory testing standard for a speci®c organic
compound.
The need to have analytical methods which could
analyze qualitatively and quantitatively for organic
compounds in the environment, especially drinking
water, was recognized in the early 1950s, and espoused
and developed in the early 1960s. This evolution was
ultimately critical to forensic science, which requires
selective analytical methods for data to be useful in
litigation. By 1951, Braus, Middleton and Walton
(1951) of the U.S. Public Health Service had qualitat-
ively analyzed raw and ®ltered surface waters for
classes of organic chemicals. In 1953, Melpolder,
War®eld and Headington of the Atlantic Re®ning
Company were able to analyze for speci®c aliphatic
volatile petroleum hydrocarbons in water down to
10 ppb using a mass spectrometer. Similarly, in 1954,
chemists of Standard Oil Company (Schmauch and
Grubb, 1954) were also analyzing re®nery wastewaters
for phenols down to 10 ppb using a spectrophoto-
metric method. By 1955, Rosen and Middleton (1955)
had re®ned their 1951 analytical procedures speci®cally
for organics in petroleum re®nery wastewaters. These
studies by both industry and the government indicate a
growing appreciation for understanding the organic
content of industrial and natural waters. The analytical
methods, however, still did not meet the standards for
Evolution of Organic Analytical Methods 39
speci®city and quality that would enable them to be
used for environmental forensics.
By the early 1960s, a coalition of industrial, aca-
demic, and government scientists focused their atten-
tion on the detection of ``trace'' levels of organic
chemicals in the environment. Methods for the analysis
of trace organic contamination were beginning to be
discussed on a national scale. For example, in 1961 at a
Groundwater Contamination Symposium sponsored
by the U.S. Department of Health, Education, and
Welfare (Division of Water Supply and Pollution
Control), Middleton and Walton (1961) presented
research for the analysis of trace levels of speci®c
organic compounds in groundwater in parts per billion
( ppb) concentrations (e.g. phenol at 20 ppb). In 1963,
Ryckman, Burbank and Edgerley (1964) of the School
of Public Health at Washington University presented a
paper at the annual American Water Work Association
(AWWA) meeting indicating various methods for
analyzing organics in ppb and parts per trillion
( pptr) concentrations were becoming available, includ-
ing gas chromatography, and argued that these
methods were necessary to monitor water quality. At
the same conference Weiss, Johnson and Kwon (1963)
of the University of North Carolina demonstrated the
utility of gas chromatography analysis of trace organics
in groundwater using a ¯ame ionization detector.
Coincidentally with these research e€orts, academic
journals likewise began to focus their content on the
developing analytical technologies. Although analyti-
cal chemistry journals such as the Analytical Edition of
Industrial Engineering and Chemistry (now Analytical
Chemistry) and Analytica Chimica Acta were published
in the ®rst half of the century, it was not until 1967 that
the ®rst issue of Environmental Science and Technology
was published, which was dedicated, in part, to
disseminating research on technologies to analyze
environmental samples.
Advances in separation sciences that began in the
1950s and 1960s laid the groundwork for the dramatic
breakthrough in the technologies of environmental
analytical chemistry in the 1970s (American Chemical
Society, 1994). The analysis of organic compounds
involves isolation of the compound(s) from the sample
matrix and each other, and then accurately detecting
the compound(s), both qualitatively and quantitatively.
Separation procedures are necessary because physical
and chemical properties suited for measurement are
typically shared by more than one compound.
To successfully isolate a speci®c organic compound
or group of compounds, it is necessary to acquire a
sample whose composition represents the bulk of the
material sampled, prepare a measured quantity of the
sample, and remove components which may interfere
with the ®nal measurement. In addition, if possible, it
is often necessary to concentrate compounds to ensure
detection limits conducive to the objectives of the
analysis. In the 1950s and 1960s, these procedures
typically involved solvent extraction (e.g. Soxhlet),
distillation ( fractional, steam, vacuum), countercurrent
extraction, adsorption, and column, paper and thin-
layer chromatography techniques.
In the 1960s, adsorption chromatography with activ-
ated carbon, a technology initially developed in the
early 1950s at the Robert A. Taft Sanitary Engineering
40 A.D. Wait
Center in Cincinnati, was routinely used for separating
and concentrating organic compounds from surface
waters and certain industrial e‚uents (Mancy, 1972).
In fact, in the early 1960s, the Federal Water Pollution
Control Administration (FWPCA), a predecessor to
the USEPA, implemented a national surveillance
system for surface waters. FWPCA methods employed
carbon absorption, a procedure which requires proces-
sing large volumes of water for each sample, to isolate
synthetic organic compounds, speci®cally pesticides
(FWPCA, 1966). Today, over 30 years later, many of
these same pesticides, such as chlordane, are implicated
in environmental forensic investigations.
Development of purge and trap technology in the
early 1970s at USEPA's Methods Development and
Quality Assurance Laboratory in Cincinnati provided
dramatic improvements in the isolation and concen-
tration of volatile organic compounds in water
samples, distinctly lowering detection limits for a
reasonable size sample (Bellar and Lichtenberg,
1974). This advance ultimately resulted in a routine,
ecient analytical method which could be imple-
mented in commercial laboratories on a large scale.
As a direct result of the application of this new method,
by the late 1970s, volatile organic compounds, namely
solvents, were found to be pervasive in the nation's
aquifer and surface water systems, as well as in local-
ized soil environments where dumping or accidental
spills had occurred. These discoveries launched, in
part, massive site investigations throughout this
country, resulting in much of today's forensic liability
investigations.
Advances in isolation and concentration technol-
ogies for semi-volatile organic compounds over the
past 30 years has not been as dramatic as those for
volatile organic compounds. Most advances are
re®nements of established methods. For example, use
of di€erent solvents improved extraction eciencies for
certain target compounds, and new column chroma-
tography techniques have been useful in removing
interferences (e.g. cleanup of samples prior to analysis
of pesticides) or fractionating sample extracts into
di€erent compound classes (e.g. petroleum hydrocar-
bons) for separate analysis. Some technological break-
throughs included supercritical ¯uid extraction,
sonicator extraction, and gel permeation chromatog-
raphy (e.g. Charpentier and Sevenants, 1988). These
methods generally improved preparation and extrac-
tion eciencies for dicult sample matrices, particu-
larly for wastes.
Clearly the most important advance in the detection
of environmental organic compounds is the advent of
instrumental chromatography. Chromatography is a
physical method of separation in which the com-
ponents to be separated are distributed between two
phases; a stationary phase and a mobile phase. The
chromatography process occurs through repeated
sorption/desorption reactions as the mobile phase
passes over the stationary phase. Both gas chromatog-
raphy (mobile phase is gaseous/stationary phase is
solid) and liquid chromatography (mobile phase is
liquid/stationary phase is solid) are integral technol-
ogies for today's environmental forensic studies. The
development of gas chromatography was rapid. From
its inception in 1951, gas chromatography had changed
from a novel method of separation to a standard
analytical technique for many laboratories by 1960
(Scott, 1995). In contrast, in 1960, liquid chromatog-
raphy lagged far behind gas chromatography even
though liquid chromatography had been discovered
half a century earlier (Scott, 1995).
Modern analytical chromatography requires a
sample introduction system (typically an injection
port), a mobile phase (gas or liquid), a column used
to separate compounds, a detector, and a recorder
(data system). In the 1970s, signi®cant advances in all
aspects of this instrumentation produced chromato-
graphic analysis of a quality useful for environmental
site investigation and forensic liability data admissible
in court (Schomburg, 1983; Lee, Yang and Bartle,
1984).
Advances in electronics and valve technology
allowed for re®ned control of the mobile phase such
that analyses were accurately reproducible for
both interlaboratory and intralaboratory studies. In
addition, improved quality of the mobile phase, both
gaseous and liquid, signi®cantly lowered background
interferences.
Developments in column technology for gas
chromatography were dramatic during the 1970s,
proceeding from packed columns to sophisticated
glass and fused silica high resolution capillary columns
within a few short years (Jennings, 1980; Blomberg,
1982, 1984; Novotny, 1989). Lautamo, Schirmer and
Jennings (1998) recently summarized column develop-
ments over the past half century. Applications were
quickly being found for fuel analysis, determination of
combustion products, environmental sciences, natural
product research, food and aroma analysis, and
biochemical and biomedical research (Novotny, 1978;
Lee, Yang and Bartle, 1984).
Capillary column technology dramatically improved
the resolution of compound separation such that
previously unresolved organic compounds were more
discernible and identi®able. Increased resolution also
improved chromatography peak shape, which, in turn,
improved the accuracy of the quanti®cation measure-
ments. These improved attributes of ``selectiveness''
and reliability are crucial to an emerging environmen-
tal forensics capability.
Advances in detector technology were also critical in
the 1960s and 1970s. Detector technology for gas
chromatography advanced more rapidly than for liquid
chromatography due, in part, to problems associated
with liquid ¯uid ¯ow through the detector. The most
important early detector for gas chromatography was
the thermal conductivity (TC) cell, a nonselective
detector with relatively poor response for many
analytes of forensic interest. In the 1960s, the ¯ame
ionization detector (FID) provided increased sensitiv-
ity and linear range, but was still relatively non-
selective. Over the next few years, a series of selective
detectors were manufactured. These detectors include
the electron capture detector (ECD), the Hall electro-
lytic conductivity detector (HECD), the nitrogen±
phosphorus detection (NPD), and the ¯ame photo-
metric detector (FPD). Attributes of each of these
detectors have been published elsewhere (e.g. Drushel,
1983; Sta€ord, 1992). Druschel (1983) has also
summarized liquid chromatography detectors available

in the early 1980s. In spite of all these improvements,
identi®cation and selectivity of these chromatographic
methods were dependent on the time of elution
(retention time) for compound identi®cation.
Clearly the mass spectrometer was the main tech-
nology advance in detectors that paved the way for a
viable environmental forensic industry. The combin-
ation of the separation capabilities of gas chromatog-
raphy with the identi®cation properties of mass
spectroscopy provided the forensic investigator with
an invaluable qualitative and quantitative analytical
chemistry tool. Gas chromatography/mass spectro-
metry (GC/MS) provided a unique combination of
retention times with compound speci®c fragmentation
patterns and accurate molecular ion measurements,
creating an organic analytical tool of unprecedented
``selectivity''.
In 1959, Gohlke published his classic research on the
utility of GC/MS. Over the following decade advances
in gas chromatography and mass spectroscopy tech-
nology improved the overall performance of GC/MS
systems, but was still considered a novel technique,
often requiring days to identify a single compound
(Keith, 1991). The next big GC/MS breakthrough
related to data processing using computers. Hites and
Biemann's (1968) classic paper on mass spectrometer
computer systems ®nally provided researchers with the
knowledge to process vast amounts of data, such as the
ability to continually record spectra, calculate peak
centers and intensities, and secondary storage of
magnetic disks provided space for large amounts of
mass spectra data. A vast amount of text and literature
have been published over the past three decades
documenting advances in GC/MS technology and its
application to environmental sample analyses (e.g.
Budde and Eichelberger, 1979).
Finally, advances in data systems for all chromato-
graphic analyses were key to producing analytical
results which can be properly assessed and stored so
that the results can be recreated at a later date. Until
the mid-1970s, strip chart recorders were standard
equipment on a gas chromatograph. For a few years in
the late-1970s digital integrators replaced strip chart
recorders, but this was short-lived as computers
quickly became the accepted data recorders since the
1980s.
Chromatography has been an integral part of a
criminal forensic chemist's arsenal of analytical chem-
istry tools over the past 30 years (e.g. Doms and Lott,
1982; Saferstein, 1982; Ho, 1990; Tebbett, 1992).
Chromatographic data often met the criteria of
admissibility in litigation and have historically sup-
ported criminal investigations such as arson, explo-
sives, and illicit drugs (e.g. Smith, 1982; Jayatilaka and
Poole, 1994). More recently chromatography has been
an integral component to many environmental forensic
cases.
Realizing Environmental Forensic Chemistry
Organic geochemists led the way in the 1960s in
applying state-of-the-art analytical chemistry to
various environmental media. Organic geochemistry
is the study of the fate and distribution of carbon
compounds in ancient sediments and contemporary
Evolution of Organic Analytical Methods 41
environments. These activities were spurred on by such
diverse interests as the search for deposits of fossil fuels
(e.g. Philippi, 1965; Welte, 1965), deciphering the
origins of life (Calvin, 1969), and the prospective
chemical analysis of the surfaces of other planets and
lunar samples (e.g. Studier, Hayatsu and Anders,
1968). Obviously, these are di€erent motives to the
environmental regulatory drivers which promoted
environmental forensic investigations. In 1969, Eglin-
ton and Murphy (1969) published a landmark text
which summarized much of the environmental ana-
lytical chemistry capabilities of that time, particularly
for soils, sediments, and rocks.
Scientists recognized in the late-1960s and 1970s that
some organic compounds were the complex bio-
chemical products of ancient organisms that had
survived in sedimentary formations for relatively long
periods of time (biological markers), often with little or
no transformation of their molecular structure
(Blumer, 1973; Eglinton, 1973). Using advanced gas
chromatography methods, detection of biological
markers provided information on the origin of the
organic matter and the paleoenvironmental conditions
of sedimentation (Albrecht and Ourisson, 1971; Philp,
Maxwell and Eglinton, 1976; Didyk et al., 1978). For
example, signi®cant concentrations of b-carotane are
likely from bacteria in arid hypersaline environments,
while phyllocladanes are attributable to conifers in
terrestrial environments (Peters and Moldowan, 1993).
Organic geochemists also studied modern sediments to
understand depositional mechanisms (e.g. Eglinton
et al., 1979), which provided a prelude to their
involvement in environmental contamination investi-
gations.
The tenet that recognizable organic remnants could
be used as a stratigraphic correlation parameter was
often mentioned by organic geochemists (Reed and
Mankiewicz, 1975), and later demonstrated (e.g. Wait
and Abell, 1982). In the 1970s, organic geochemists
used unique biological markers and distribution
patterns of hydrocarbons, such as alkanes (e.g. Carbon
Preference Index), fatty acids, and isoprenoid/alkane
ratios, to evaluate depositional environments, correlate
strata, and evaluate potential petroleum source rocks.
These beginning concepts of ``uniqueness'' and
``®ngerprint patterns'' are the same type of techniques
used by today's environmental forensic chemists. In a
much narrower context, however, regulatory analytical
methods of the 1980s focused on certain target
compounds which were determined, in part, by their
prevalence in the environment and perceived potential
for harm to public and ecological health. Hites and
Budde (1991) provided a useful summary of regulatory
water methods for this time period. Although these
types of target-analysis methods may have some utility
to today's environmental forensic chemist, their
attributes are not often conducive to the fate and
transport chemistry being forensically investigated. In
e€ect, target analytes, considered rather ubiquitous in
the environment, often do not satisfy the unique
distribution attributes sought by the forensic chemist.
The analytical chemistry advances in the 1970s and
1980s, speci®cally chromatography and mass spec-
troscopy, ®nally provided researchers the ¯exibility and
capabilities to structure a site speci®c chemistry
42 A.D. Wait
program using nonstandard methods. In addition,
more recently multivariate statistical techniques have
become available, such as principal component
analysis (PCA) and polytopic vector analysis (PVA),
which have aided the forensic investigator in evaluating
and demonstrating unique attributes to a set of data.
Today's environmental forensic chemists may focus
their investigations on certain marker compounds, but
more often become involved with multi-component
distribution analysis of complex mixtures such as
polychlorinated biphenyls (PCBs), polychlorinated
dibenzodioxins and furans (PCDD/Fs), and petroleum
hydrocarbons. A brief synopsis of the forensic chem-
istry application of these contaminants follows.
Marker compounds
Organic geochemists have found biological marker
compounds extremely useful in deciphering deposi-
tional environments and evaluating petroleum source
rocks (Peters and Moldowan, 1993). For the forensic
chemist biomarkers have limited utility other than for
petroleum hydrocarbon product identi®cation. How-
ever, synthetic organic chemicals, particularly those
that are proprietary, can be extremely valuable in an
environmental forensic study as marker compounds.
For example, in the mid-1980s, Eganhouse and Kaplan
(1985) proposed that a-tocopheryl acetate (vitamin E
acetate), a compound produced industrially for com-
mercial products, may be a marker compound indica-
tive of the contribution of municipal waste to the
contamination of southern California coastal marine
sediments. More recently methyl tertiary butyl ether
(MTBE), which since the late 1970s has been used as
an octane enhancer in gasoline (USEPA, 1997b;
McCarthy and Tiemann, 1998), has been a key marker
compound for evaluating gasoline contamination in
groundwater, surface waters, and soils. For example,
Reuter et al. (1998) evaluated the sources of MTBE in
Donner Lake, California, a multiple-use lake in the
Sierra Nevada mountains. The researchers evaluated
potential transport pathways (e.g. highway runo€,
atmospheric deposition), temporal variations, and
lake usage. Motorized watercraft were determined to
be the main source of the MTBE in the lake.
Even if marker compound identi®cation cannot be
discerned, mass spectral interpretation of unknowns
by experienced mass spectroscopists can produce
information helpful in determining sources of con-
tamination. Swallow, Shifrin and Doherty (1988) were
able to successfully compare mass spectra of unidenti-
®ed non-priority pollutant compounds to distinguish
potential leakage from a RCRA facility and known
leakage from an adjacent CERCLA site.
Polychlorinated biphenyls (PCBs)
From 1929 to 1979, polychlorinated biphenyls (PCBs)
had numerous industrial uses, including hydraulic
¯uids, solvents, plasticizer, printing inks, paints, and
dielectric ¯uids in capacitors and transformers (Frame
et al., 1996; Erickson, 1997). PCBs were manufactured
by catalytic chlorination of biphenyl to produce
complex mixtures, with each PCB mixture containing
60 to 90 di€erent congeners and a speci®ed weight
percent of chlorine (Frame et al., 1996). There are 209
possible congener structures (Erickson, 1997). Federal
and state agencies have focused their investigations on
seven commercial PCB mixtures (Aroclor 1016, 1221,
1232, 1242, 1248, 1254, 1260), although two other
Aroclor mixtures (1262 and 1268) are also known as
environmental contaminants in the United States (e.g.
Kannan, Maruya and Tanabe, 1997).
Prior to 1970, analytical limitations precluded
accurate detection of PCBs in environmental samples
(Shifrin and Toole, 1998). Even with the advent of
today's reliable gas chromatography technology,
analysis of PCBs remains a dicult problem for
analytical chemists. These problems are caused, in
part, by small variances in the formulation of PCB
mixtures, variable physical and chemical properties for
each PCB congener, diculties in accurately quantitat-
ing a PCB mixture, coextraction and coelution of other
organic compounds, commingling of di€erent PCB
mixtures, and until recently an inability to completely
resolve all PCB congeners. In addition, ``weathering''
e€ects of PCBs in the environment can preferentially
degrade certain PCB congeners, thereby making it
more dicult to discern PCB ®ngerprint patterns.
Shifrin and Toole (1998) have reviewed historical PCB
analytical chemistry developments over the past 30
years, and discuss how some of these problems have
been resolved.
Until the 1990s, most environmental PCB data were
identi®ed and reported as a total Aroclor value. This
was of some bene®t to the forensic chemist in
discerning source identi®cation if the PCB chromato-
gram was not degraded, and if the types of PCBs from
di€erent sources were signi®cantly dissimilar. With the
advent of high resolution capillary GC columns,
resolution and identi®cation of PCB congeners has
become realistic in environmental samples. In fact, a
series of high resolution columns were recently used to
calibrate all 209 PCB congeners (Frame, Cochran and
Bowadt, 1996; Frame, 1997a,b). USEPA is also
starting to promulgate methods designed to analyze
for certain PCB congeners. PCB congener analysis
a€ords the forensic chemist an increased ability to
®ngerprint PCB congener distribution for source
identi®cation. For example, Hwang et al. (1993) used
PCB congener patterns of a known point source of
contamination and compared it to the pattern found in
a variety of ®sh collected in the St Lawrence River. In
another example, Rachdawong and Christensen (1997)
used principal component analysis (PCA) of PCB
congeners to decipher major sources of PCB con-
tamination of sediments in the Milwaukee Harbor
Estuary. Thus, in the 1990s, environmental forensic
chemistry is providing analytical tools to assess
potential contamination sources in locales such as the
Milwaukee Harbor and St. Lawrence River.
Polychlorinated dibenzo dioxins and furans (PCDD/Fs)
Polychlorinated dibenzo-p-dioxins (PCDDs) and
dibenzofurans (PCDFs) are chlorinated tricyclic planar
aromatic compounds, with 75 PCDD and 135 PCDF
isomers (congeners) possible. The supposed toxicity of
certain PCDD/Fs isomers make the origins of certain
environmental ``hot spots'' of interest. As such, the

source of these materials and associated liability makes
these compounds useful for forensic investigations.
Prior to the development of high resolution gas
chromatography and high resolution mass spec-
troscopy, these compounds were dicult to identify
and quantify at low concentrations typical in environ-
mental samples. PCDD/Fs are not industrial products,
but are released into the environment in trace con-
centrations via various combustion processes. They are
also formed as unwanted byproducts from various
chlorinated formulations, such as pentachlorophenol
(Rappe, 1994; Alcock and Jones, 1996). A large pre-
ponderance of PCDD/Fs in the environment are from
combustion sources, mainly from incineration of mun-
icipal solid waste (Rappe, 1994; Alcock and Jones,
1996), but also from sources as diverse as chimney soot
from wood burning (Bacher, Swerev and Ballschmitter,
1992). Kominsky and Kwoka (1989) suggest that the
ratio of PCB to PCDF in building ®re samples can be
diagnostic of the source. The massive air pathway for
PCDD/Fs has made these compounds ubiquitous
globally. In fact, these compounds often migrate into
common everyday materials such as plastic packaging
and are found in vacuum cleaner dust (Berry, Luthe
and Voss, 1993).
Finding the source of such ubiquitous compounds at
low levels is a challenge. The pattern of isomers within
a homolog group and the pro®le of isomer distribution
across di€erent degrees of chlorination can be used as
valuable ®ngerprint tools by the forensic chemist
(Swerev and Ballschmitter, 1989). However, this
pattern can be complicated by the ubiquitous distri-
bution of PCDD/Fs at low levels. The forensic chemist
must ensure no contamination is occurring during
sample collection and analysis, and that background
levels are well characterized.
One example of source identi®cation is a study
conducted by Huntley et al. (1998) to discern sources
of PCDD/Fs in Newark Bay Estuary sediments. High
resolution GC/MS was used to analyze 17 2,3,7,8-
substituted PCDD/F congeners. In addition, polytopic
vector analysis, radioisotope dating techniques and
historical information were employed. The researchers
found three source-speci®c PCDD/F ®ngerprint pat-
terns consistent with combustion sources, sewage
sludge, and PCBs. This example indicates the useful-
ness and sophistication of integrating various forensic
tools to discern sources of contamination.
Petroleum hydrocarbons
Petroleum hydrocarbon and polynuclear aromatic
hydrocarbon (PAH) analytical chemistry practices
were well-established in the environment during the
1970s. This was due, in part, to the research done by
organic geochemists, as well as the results of a series of
high-pro®le marine oil spills which produced robust
investigations to evaluate the environmental impact of
the spills.
Analyzing for petroleum hydrocarbons is a more
dicult task than for PCBs and PCDD/Fs discussed
above. The degree of diculty in this analysis is the
result of variable physical and chemical properties of
di€erent petroleum distillation products ranging from
gasoline to asphalt, as well as di€ering chemistries of
Evolution of Organic Analytical Methods 43
the same types of starting materials for some of these
products, such as crudes (e.g. API, 1994). In addition,
many petroleum products contain hundreds, if not
thousands, of organic compounds, many of which are
unresolved and unidenti®able.
Many, if not most, environmental investigations in
the United States are predicated on petroleum hydro-
carbon contamination. This is due, in part, to the
pervasive use of petroleum-derived materials in all
aspects of our society. Petroleum contamination can
result from various sources, such as leaking under-
ground storage tanks, accidental spills, and burial of
waste products which are often commingled. Evalu-
ation of the sources of these contaminants can be
confounded by other sources which may contain
similar compounds, such as PAHs, or in the marine
environment by natural petroleum seeps (Reed and
Kaplan, 1977; MacDonald, 1998).
The forensic chemist's ability to analyze for petrol-
eum hydrocarbons was greatly enhanced with the
advent of high resolution gas chromatography and the
mass spectrometer in the 1970s. Prior to these
advances, oil was measured gravimetrically (``oil and
grease''), and more recently using an infrared spectro-
photometer (e.g. USEPA Method 418.1). Both of these
methods are nonspeci®c, are prone to interferences,
and therefore are of little use to the forensic investi-
gator. Today's forensic chemist, dealing with product
di€erentiation and source allocation, often have to
implement a sophisticated tiered analytical chemistry
program (Uhler, Stout and McCarthy, 1998). Tech-
niques often employed include GC/FID ®ngerprinting
( pattern recognition), GC/MS analysis for both
volatile and semi-volatile organic compounds, bio-
marker GC/MS analysis, as well as ancillary methods
such as stable isotope techniques. Semi-volatile
GC/MS analysis typically involves analysis for PAHs,
alkylated PAHs and heterocyclics; compounds useful
for source-speci®c diagnostic ratios (Stout, Uhler and
McCarthy, 1998). Biomarkers such as steranes, diter-
panes, and triterpanes can also be useful to character-
ize petroleum hydrocarbons (Peters and Moldowan,
1993). As with PCBs and PCDD/Fs, principal
component analysis (PCA) of petroleum hydrocarbons
such as PAHs can be useful to delineate possible
sources of contamination (e.g. Burns et al., 1997).
One example of the use of pattern recognition and
source-speci®c diagnostic ratios was demonstrated by
Page et al. (1995) to allocate PAH sources in the
sediments of Prince William Sound, Alaska, found
following the Exxon Valdez oil spill. This study
successfully discriminated biological PAHs, combus-
tion product PAHs, natural petrogenic background
PAHs (seeps), and petroleum PAHs associated with a
tanker spill. As another example, Douglas et al. (1996)
demonstrated certain alkylated dibenzothiophene and
alkylated PAH ratios can be useful to discern the
source of petroleum contamination despite substantial
weathering of the oil since its release.
Future Trends
Many of today's waste sites are now involved in clean-
up activities (USEPA, 1997c); however, nearly 1800 of
44 A.D. Wait
the 3036 sites in USEPA's database of possible NPL
sites are still likely to be included on the NPL list
(USGAO, 1998). This is one indicator that contami-
nation liability issues will remain pertinent in the
foreseeable future. Lacking a technical breakthrough in
instrumental chromatography or other analytical
methods, we can expect additional re®nements of
established environmental forensic methods into the
21st century. Data processing, data storage and chemo-
metric capabilities will likely continue to improve
signi®cantly, further aiding the forensic chemist's
ability to demonstrate unique attributes of a set of
data. Modi®cation of current methods will likely be
necessary to address new chemicals of concern which
warrant an assessment of environmental liability. For
example, health experts are beginning to assess
thousands of environmental contaminants as sources
of endrocrine disrupters, which, in turn, may present a
whole new realm of environmental liability concerns
(USEPA, 1997d).
One issue of interest to environmental forensic
investigators is the time of release of a spill. Although
there are some approaches, such as modeling and
historical use practices (e.g. Smith, Eng and Mill,
1994), which can be useful to approximate the age of
the release, most methods can be inadequate. There are
numerous unquanti®able factors linked to the degra-
dation rate for organic compounds in the environment
that cannot be addressed by standard organic analyti-
cal methods. If progress is to be made on quantifying
the time of release of a spill, it will likely be with
ancillary methods. For example, Hurst, Davis and
Chinn (1996) have shown the utility of isotopic analysis
of lead additives in gasoline to improve the estimate of
the ages of leaks and spills.
With regard to quality assurance, practitioners of
regulated analytical methods may face the same con-
undrum of the forensic chemist using nonstandard
methods (Wait and Douglas, 1995). There has been a
recent movement within many of USEPA's oces to
adopt performance-based measurement systems
(PBMS). PBMS will allow a commercial laboratory
to adopt a certain level of ¯exibility in the methods it
employs, so long as quanti®able quality assurance
goals are met. Concern has been raised by many
investigators regarding the legal uncertainties and lack
of case law for PBMS, potential liabilities for the
laboratory, and comparability of historical data with
new results (Mills, 1998, 1999). For PBMS to be
successful, it is critical that experienced senior-level
chemists be involved with developing clear data quality
objectives prior to initiation of the investigation,
overseeing the implementation of methods, and eval-
uating the integrity and usability of the results.
Today's environmental litigation activities have
bene®ted by advances made in organic analysis tech-
nologies over the past 30 years, as well as with quality
assurance systems that support the results. The
e€ectiveness of forensic data to discern sources of
contamination, and the success of admissibility of the
data in court, should improve as the analytical chemist
becomes more savvy regarding the needs of forensic
investigations.
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