Marine Pollution Bulletin 47 (2003) 423–452

www.elsevier.com/locate/marpolbul

Development of oil hydrocarbon fingerprinting and

identification techniques
1
Zhendi Wang *, Merv F. Fingas
Emergencies Science and Technology Division, ETC, Environment Canada, 3439 River Road, Ottawa, Ont., Canada K1A 0H3

Abstract

Oil, refined product, and pyrogenic hydrocarbons are the most frequently discovered contaminants in the environment. To ef-
fectively determine the fate of spilled oil in the environment and to successfully identify source(s) of spilled oil and petroleum
products is, therefore, extremely important in many oil-related environmental studies and liability cases. This article briefly reviews
the recent development of chemical analysis methodologies which are most frequently used in oil spill characterization and iden-
tification studies and environmental forensic investigations. The fingerprinting and data interpretation techniques discussed include
oil spill identification protocol, tiered analytical approach, generic features and chemical composition of oils, effects of weathering
on hydrocarbon fingerprinting, recognition of distribution patterns of petroleum hydrocarbons, oil type screening and differenti-
ation, analysis of ‘‘source-specific marker’’ compounds, determination of diagnostic ratios of specific oil constituents, stable isotopic
analysis, application of various statistical and numerical analysis tools, and application of other analytical techniques. The issue of
how biogenic and pyrogenic hydrocarbons are distinguished from petrogenic hydrocarbons is also addressed.

2003 Published by Elsevier Ltd.

Keywords: Fingerprinting; Oil fingerprinting; Biomarkers; Diagnostic ratios; Oil analysis; Spill identification; Oil forensic analysis; Oil composition

1. Introduction gallons (10,000 tonnes) of heavy fuel oil spilled, and an

Oil spill occurs everyday worldwide. A historical re-
view and analysis of reported oil spills over 10,000 gal-
lons in the International Oil Spill Database (Etkin,
1998) shows that since the early 1960s, nearly 300 mil-
lion gallons of oil have spilled into US marine waters
which occurred in 826 incidents involving tankers, bar-
ges, and other vessels, and about 200 million gallons of
oil onto US soil from land pipeline spills (on average, 99
land pipeline spills per year). An estimated 500 million
and over 200 million gallons of oil have spilled from
tankers in Europe and Pacific Asia since 1965, respec-
tively.
The most recent example of a large-scale spill is the
‘‘Erika’’ spill. The Maltese tanker Erika broke into two
during a fierce storm on December 12, 1999 about 110
km south of Brest, France. An estimated 2.8 million
*
Corresponding author. Tel.: +1-613-990-1597; fax: +1-613-991-
9485.
E-mail addresses: zhendi.wang@ec.gc.ca (Z. Wang), merv.fingas@
ec.gc.ca (M.F. Fingas).
1
Tel.: +613-998-9622; fax: +613-991-9485.
0025-326X/$ - see front matter
2003 Published by Elsevier Ltd.
doi:10.1016/S0025-326X(03)00215-7
equal amount remained aboard the sunken stern. A
deadly storm after the spill hurled the sticky, heavily
emulsified oil from the Erika ashore, churning tar into
sandy beaches, splattering cliffs, roads, and car parks.
This incident became FranceÕs most damaging oil spill in
20 years, causing an environment of devastation on the
French Coast.
Oil spills cause extensive damage to marine life, ter-
restrial life, human health, and natural resources.
Therefore, to unambiguously characterize spilled oils
and to link them to the known sources are extremely
important for environmental damage assessment, un-
derstanding the fate and behaviour and predicting the
potential long-term impact of spilled oils on the envi-
ronment, selecting appropriate spill response and taking
effective clean-up measures. In addition, successful fo-
rensic investigation and analysis of oil and refined
product hydrocarbons in contaminated sites and recep-
tors yield a wealth of chemical ‘‘fingerprinting’’ data.
These data, in combination with historic, geological,
environmental, and any other related information on the
contaminated site can, in many cases, help to settle legal
liability and to support litigation against the spillers.
424 Z. Wang, M.F. Fingas / Marine Pollution Bulletin 47 (2003) 423–452
This paper briefly reviews the recent development of
chemical analysis methodologies which are most fre-
quently used in oil spill characterization and identifica-
tion studies and environmental forensic investigations.
The fingerprinting and data interpretation techniques
discussed include oil spill identification protocol, a tiered
analytical approach, generic features and chemical
composition of oils, effects of weathering on hydrocar-
bon fingerprinting, recognition of distribution patterns
of petroleum hydrocarbons, oil type screening and dif-
ferentiation, analysis of ‘‘source-specific marker’’ com-
pounds, determination of diagnostic ratios of specific oil
constituents, stable isotopic analysis, application of
various statistical and numerical analysis tools, and
application of other techniques in the oil forensic in-
vestigations. The issue of how biogenic and pyrogenic
hydrocarbons are distinguished from petrogenic hydro-
carbons is also addressed.
2. Development of oil hydrocarbon fingerprinting tech-
niques
Petroleum contains thousands of different organic com-
pounds. Successful oil fingerprinting involves appropriate
sampling, analytical approaches and data interpreta-
tion strategies. A wide variety of instrumental and non-
instrumental techniques are currently used in the analysis
of oil hydrocarbons, which include gas chromatography
(GC), gas chromatography–mass spectrometry (GC–MS),
high-performance liquid chromatography (HPLC), size-
exclusion HPLC, infrared spectroscopy (IR), supercritical
fluid chromatography (SFC), thin layer chromatography
(TLC), ultraviolet (UV) and fluorescence spectroscopy,
isotope ratio mass spectrometry, and gravimetric methods
(Wang et al., 1999a). Of all these techniques, GC tech-
niques are the most widely used. Compared to the mole-
cular measurements two decades ago, GC methods have
now been enhanced by more sophisticated analytical
techniques, such as capillary GC–MS, which is capable of
analyzing the oil-specific biomarker compounds and
polycyclic aromatic hydrocarbons. The accuracy and pre-
cision of analytical data has been improved and optimized
by a series of quality assurance/quality control measures,
and the laboratory data handling capability has been
greatly increased through advances in computer technol-
ogy. Several reviews (Sauer and Boehm, 1991, 1995; Krahn
et al., 1993; Whittaker et al., 1995; Lundanes and Grei-
brokk, 1994; Kaplan et al., 1996, 1997; Wang et al., 1999a;
Stout et al., 2002) have been published on the analytical
methodologies for characterization and identification of oil
hydrocarbons using various analytical techniques.
Depending on chemical/physical information needs, the
point of application and the level of analytical detail, the
methods used for oil spill study can be, in general, divided
into two categories: non-specific methods and specific
methods for detailed component analysis. In the non-
specific methods such as the US EPA methods 1614 and
418.1, only groups or fractions of chemical hydrocarbons
(for example, measurement of total petroleum hydrocar-
bons (TPH) and EPA priority PAHs) are determined.
In response to the oil spill identification need and
specific site investigation needs, attention has focussed
on the development of flexible, tiered analytical ap-
proaches which facilitate the detailed compositional
analysis by GC–MS, GC-FID, and other analytical
techniques that determine a broad range of individual
petroleum hydrocarbons. A variety of diagnostic ratios,
especially ratios of PAH and biomarker compounds, for
interpreting chemical data from oil spills have been
proposed for oil source identification and monitoring of
weathering and biological degradation processes.
2.1. Selected US EPA methods and the limitations of
these methods for oil analysis
Table 1 summarizes selected EPA methods, major
applications and limitations of these methods for oil
analysis (EPA Methods, 1983, 1986, 1997, 1999). These
EPA methods have been used as routine procedures for
determination of volatile and semivolatile aromatic hy-
drocarbons presented in spilled oil and petroleum
product samples. However, these methods were origi-
nally designed for waste water and industrial waste. The
fundamental shortcoming with these methods is that
they can not provide information on detailed chemical
components which comprise the complex spill oil sam-
ples. The data generated from these methods are gen-
erally insufficient to answer the fundamental questions
(such as type and source, weathering status of spilled oil,
potential spillers, and so on) raised in an oil spill in-
vestigation. Of the more than 160 priority-pollutant
compounds determined by these methods, only 20 are
petroleum-related. Further, only half of these 20 com-
pounds are found in significant quantities in oils and
petroleum products. Also, the PAH compounds in oils
are dominated almost exclusively by the C1 to C4 al-
kylated homologues of the parent PAH, in particular,
naphthalene, phenanthrene, dibenzothiophene, fluorene
and chrysene, none of which are measured by the stan-
dard EPA methods. Other important classes of petro-
leum hydrocarbons (e.g., aliphatics and biomarkers) are
not measured by these methods at all. Another example
is the use of the EPA 418.1 method to determine TPH
content. The EPA 418.1 method, based on measuring
the absorption of C–H bond in the 3200–2700 wave-
number range, was originally intended for use only with
liquid waste but had been one of the most widely used
methods for the determination of TPH in soils before its
demise because of the use of a chloro-fluoro carbon
extractant. For some site assessments, Method 418.1
was the sole criterion for verification of site cleanup.
 Z. Wang, M.F. Fingas / Marine Pollution Bulletin 47 (2003) 423–452 425

Table 1
Major applications and limitations of standard EPA methods for oil analysis
EPA standard method Target compounds and application Limitation for oil work
EPA 418.1 TPH by IR spectroscopy ––Inherent in accuracy of the method (positive
or negative bioses)
––Subject to various interference
––Lack of effective reference standards
EPA 1664 n-Hexane extractable materials and silica ––Only measures total extractable materials in
gel treated n-hexane extractable material by aqueous matrices
extraction and gravimetry ––Heavy interference
––Low molecular weight hydrocarbons could be
lost during distillation

EPA 600 series (method standards for

waste water)
602 Purgeable aromatics, by GC/FID ––600 and 8000 series cannot provide detailed
composition information of spilled oil
610 16 polynuclear aromatics, by HPLC/GC
624 Purgeable volatiles, by GC/MS ––Only BTEX measured, do not measure over 100
important oil hydrocarbons
625 Semivolatiles and pesticides, by GC/MS ––Do not measure dominated alkylated PAH
homologues, aliphatics and biomarker

8000 series (method standards for solid

waste, SW 846)
8015B Non-halogenated volatiles by GC/FID
8020A Aromatic volatiles by GC
8100 Volatiles by capillary GC/MS
8260A 24 PAHs by GC/FID
8270 B Semi

TPH: Total petroleum hydrocarbons; PAH: polycyclic aromatic hydrocarbons.

However, there were some problems associated with this
method such as inherent inaccuracy in the method (i.e.,
positive or negative biases caused by various factors)
and the lack of effective reference standards when
working with an unknown.
In recent several years, many EPA and ASTM
methods have been modified to improve specificity and
sensitivity for measuring spilled oil and petroleum
products in soils and waters (EPA Methods, 1997;
ASTM Method, 1997a,b,c), such as the EPA Method
8270 has been modified to increase analytical sensitivity
and to expand the analyte list to include petroleum-
specific compounds such as the alkylated PAHs and bio-
marker compounds. The principal modification to EPA
Method 8270 is the use of the GC–MS selected-ion-mode
(SIM) analysis that offers increased sensitivity relative to
the full-scan mode. The modified EPA Method 8270,
combined with column-cleanup and rigorous QA mea-
sures, has been used to identify and quantify low levels of
hydrocarbons by many environmental laboratories.
2.2. Selection of source-specific target analytes
In addition of groups or fractions of oil hydrocarbons
(such as contents of asphaltenes and resins, TPH, total
saturates, total aromatics, and EPA priority PAHs) are
determined (Jokuty et al., 1999; Wang et al., 1998c) oil
spill identification requires further elaboration of oil
target analytes to include identification of the individual
specific target compounds and isomeric groups. The
selection of appropriate target oil analytes is dependent
mainly on the type of oil spilled, the particular envi-
ronmental compartments being assessed, and on ex-
pected needs for current and future data comparison. In
general, the major petroleum-specific target analytes
that may be needed to be chemically characterized for
oil source identification and environmental assessment
include the following:
• Individual saturated hydrocarbons including n-alk-
anes (C8 through C40 ) and selected isoprenoids pris-
tane and phytane (in some cases, another three
highly abundant isoprenoid compounds farnesane,
trimethyl-C13 , and norpristane are also included);
• Volatile hydrocarbons including BTEX (benzene, tol-
uene, ethylbenzene, and three xylene isomers) and
alkylated benzenes (C3 - to C5 -benzenes), volatile par-
affins and isoparaffins, and naphthenes (mainly cyclo-
pentane and cyclo-hexane compounds);
• EPA priority parent PAHs and, in particular, the
petroleum-specific alkylated (C1 –C4 ) homologues of
selected PAHs (that is, alkylated naphthalene, phe-
nanthrene, dibenzothiophene, fluorene, and chrysene
series). These alkylated PAH homologues (Table 2)
426 Z. Wang, M.F. Fingas / Marine Pollution Bulletin 47 (2003) 423–452

are the backbone of chemical characterization and
identification of oil spill assessments;
• Biomarker terpane and sterane compounds (Table 3).
Analysis of selected ion peaks produced by these
characteristic, environmentally persistent compounds
generates information of great importance in deter-
mining source(s), weathered state and potential treat-
ability; and
• Measurements of total petroleum hydrocarbons, the
unresolved complex mixtures (UCM), and stable car-

Table 2
Source-specific target PAHs and alkylated homologous PAHs for oil spill studies
Compound Code Ring numbers Target ions
Oil-characteristic alkylated PAHs
Naphthalenes
C0 -naphthalene C0 N 2 128
C1 -naphthalenes C1 N 2 142
C2 -naphthalenes C2 N 2 156
C3 -naphthalenes C3 N 2 170
C4 -naphthalenes C4 N 2 184
Phenanthrenes
C0 -phenanthrene C0 P 3 178
C1 -phenanthrenes C1 P 3 192
C2 -phenanthrenes C2 P 3 206
C3 -phenanthrenes C3 P 3 220
C4 -phenanthrenes C4 P 3 234
Dibenzothiophenes
C0 -dibenzothiophene C0 D 3 184
C1 -dibenzothiophenes C1 D 3 198
C2 -dibenzothiophenes C2 D 3 212
C3 -dibenzothiophenes C3 D 3 226
Fluorenes
C0 -fluorene C0 F 3 166
C1 -fluorenes C1 F 3 180
C2 -fluorenes C2 F 3 194
C3 -fluorenes C3 F 3 208
Chrysenes
C0 -chrysene C0 C 4 228
C1 -chrysenes C1 C 4 242
C2 -chrysenes C2 C 4 256
C3 -chrysenes C3 C 4 270

Other EPA priority PAH pollutants

Biphenyl Bph 2 154
Acenaphthylene Acl 3 152
Acenaphthene Ace 3 153
Anthracene An 3 178
Fluoranthene Fl 4 202
Pyrene Py 4 202
Benz[a]anthracene BaA 4 228
Benzo[b]fluoranthene BbF 5 252
Benzo[k]fluoranthene BkF 5 252
Benzo[e]pyrene BeP 5 252
Benzo[a]pyrene BaP 5 252
Perylene Pe 5 252
Indeno[1,2,3-cd]pyrene IP 6 276
Dibenz[a,h]anthracene DA 5 278
Benzo[ghi]perylene BP 6 276
Surrogates and internal standard
[2 H10 ]Acenaphthene 164
[2 H10 ]Phenanthrene 188
[2 H12 ]Benz[a]anthracene 240
[2 H12 ]Perylene 264
[2 H14 ]Terphenyl 244
 Z. Wang, M.F. Fingas / Marine Pollution Bulletin 47 (2003) 423–452 427

Table 3
Source-specific target biomarker terpane and sterane compounds for oil spill studies
Peak Compound Empirical formula Target ions
Terpanes
1 C19 tricyclic terpane C19 H34 191
2 C20 tricyclic terpane C20 H36 191
3 C21 tricyclic terpane C21 H38 191
4 C22 tricyclic terpane C22 H40 191
5 C23 tricyclic terpane C23 H42 191
6 C24 tricyclicterpane C24 H44 191
7 C25 tricyclic terpane C25 H46 191
8 C24 tetracyclic terpane + C26 tricyclic terpanes C24 H42 + C26 H48 191
9 C28 tricyclic terpane C28 H52 191
10 C28 tricyclic terpane C28 H52 191
11 C29 tricyclic terpane C29 H54 191
12 C29 tricyclic terpane C29 H54 191
13 Ts 18a(H),21b(H)22,29,30-trisnorhopane C27 H46 191
14 17a(H),18a(H),21b(H)-25,28,30-trisnorhopane C27 H46 191
15 Tm: 17a(H),21b(H)22,29,30-trisnorhopane C27 H46 191
16 17a(H),18a(H),21b(H)-28,30-bisnorhopane C28 H48 191
17 17a(H),21b(H)-30-norhopane C29 H50 191
18 18a(H),21b(H)-30-norneohopane C29 H50 191
19 18a(H) and 18b(H)-oleanane C30 H52 191
20 17a(H),21b(H)-hopane C30 H52 191
21 17b(H),21a(H)-hopane C30 H52 191
22 22S-17a(H),21b(H)-30-homohopane C31 H54 191
23 22R-17a(H),21b(H)-30-homohopane C31 H54 191
24 Gammacerane C30 H52 191
25 17b(H),21b(H)-hopane (Internal standard) 191
26 22S-17a(H),21b(H)-30,31-bishomohopane C32 H56 191
27 22R-17a(H),21b(H)-30,31-bishomohopane C32 H56 191
28 22S-17a i(H),21b(H)-30,31,32-trishomohopane C33 H58 191
29 22R-17a(H),21b(H)-30,31,32-trishomohopane C33 H58 191
30 22S-17a(H),21b(H)-30,31,32,33-tetrakishomohopane C34 H60 191
31 22R-17a(H),21b(H)-30,31,32,33-tetrakishomohopane C34 H60 191
32 22S-17a(H),21b(H)-30,31,32,33,34-pentakishomohopane C35 H62 191
33 22R-17a(H),21b(H)30,31,32,33,34-pentakishomohopane C35 H62 191

Steranes
34 C20 5a(H),14a(H),17a(H)-sterane C20 H34 217 & 218
35 C21 5a(H),14b(H),17b(H)-sterane C21 H36 217 & 218
36 C22 5a(H),14b(H),17b(H)-sterane C22 H38 217 & 218
37 C27 20S-13b(H),17a(H)-diasterane C27 H48 217 & 218
38 C27 20R-13b(H),17a(H)-diasterane C27 H48 217 & 218
39 C27 20S-13a(H),17b(H)-diasterane C27 H48 217 & 218
40 C27 20R-13a(H),17b(H)-diasterane C27 H48 217 & 218
41 C28 20S-13b(H),17a(H)-diasterane C28 H50 217 & 218
42 C29 20S-13b(H),17a(H)-diasterane C29 H52 217 & 218
43 C29 20R-13a(H),17b(H)-diasterane C29 H52 217 & 218
44 C27 20S-5a(H),14a(H),17(H)-cholestane C27 H48 217 & 218
45 C27 20R-5a(H),14b(H),17b(H)-cholestane C27 H48 217 & 218
46 C27 20S-5a(H),14b(H),17b(H)-cholestane C27 H48 217 & 218
47 C27 20R-5a(H),14a(H),17a(H)-cholestane C27 H48 217 & 218
48 C28 20S-5a(H),14a(H),17a(H)-ergostane C28 H50 217 & 218
49 C28 20R-5a(H),14b(H),17b(H)-ergostane C28 H50 217 & 218
50 C28 20S-5a(H),14b(H),17b(H)-ergostane C28 H50 217 & 218
51 C28 20R-5a(H),14a(H),17a(H)-ergostane C28 H50 217 & 218
52 C29 20S-5a(H),14a(H),17a(H)-stigmastane C29 H52 217 & 218
53 C29 20R-5a(H),14b(H),17b(H)-stigmastane C29 H52 217 & 218
54 C29 20S-5a(H),14b(H),17b(H)-stigmastane C29 H52 217 & 218
55 C29 20R-5a(H),14a(H),17a(H)-stigmastane C29 H52 217 & 218
Monoaromatic steranes 253
Triaromatic steranes 231
428 Z. Wang, M.F. Fingas / Marine Pollution Bulletin 47 (2003) 423–452
bon isotope ratio (d13 C) are also included in many
cases.
Another potentially valuable hydrocarbon group for
oil spill identification is nitrogen and oxygen hetero-
cyclic hydrocarbons. These heterocyclic hydrocarbons
are generally only present in oils at quite relatively low
concentrations compared to PAHs. However, they be-
come enhanced with weathering because they are bio-
refractory and persistent in the environment. Most
organic nitrogen hydrocarbons in crude oils are present
as alkylated aromatic heterocycles with a predominance
of neutral pyrrolic structures over basic pyridine forms.
They are chiefly associated with high boiling fractions,
much of the nitrogen in petroleum being in asphaltenes.
Individual and alkyl homologues of carbazole, quino-
line, and pyridine have been identified in many crude
oils. These compounds may provide important clues for
potential sources of hydrocarbons in the environment
and for tracing petroleum molecules back to their
biological precursors. Compared to the PAHs and
biomarkers, the application of nitrogen and oxygen-
containing heterocyclic hydrocarbons in source iden-
tification is still in its infancy, and more research is
needed.
2.3. Oil spill identification protocol
The oil spill identification system currently used is
largely based on GC-FID and GC–MS techniques. Data
produced from these two methods are used to compare
spill samples with samples taken from suspected sources
(Wang et al., 1999a). Very recently, SINTEF Applied
Chemistry of Norway and Battelle of the USA pub-
lished the ‘‘Improved and standardized methodology for
oil spill fingerprinting’’ (Daling et al., 2002), which in-
cludes four tiered ‘‘levels’’ of analyses and data treat-
ment. The recommended methodology approach is a
result of documented and analytical improvements and
a more quantitative treatment of analytical data from
GC-FID and GC–MS and the operational experiences
over past few years among the participating forensic
laboratories. Fig. 1 presents the modified ‘‘Protocol/
decision chart for the oil spill identification methodol-
ogy’’. The final assessment are concluded by the four
operational and technical defensible identification terms:
positive match, probable match, inconclusive or non-
match.
2.4. Tiered analytical approach
Tiered analytical approaches have been increasingly
applied for oil spill identification in recent years. De-
pending on the needs of spilled oil characterization,
support for biological studies, monitoring weathering
effects on chemical composition changes, or source dif-
ferentiation, the tiered analytical approaches may vary.
In the comprehensive study of the fates and effects of the
Exxon Valdez oil spill in Prince William Sound (PWS)
of Alaska, Boehm et al. (1998) and Page et al., 1995
have applied various tiered analytical approaches to
obtain hydrocarbon fingerprints in thousands of sedi-
ment and biological samples and to allocate complex
hydrocarbons to multiple sources. Wang et al. have re-
ported application of a tiered analytical approach
for identification of the source(s) of various unknown
spilled oil samples (Wang et al., 1997b, 1998b, 1999c,
2002). The tiered approach they used includes the fol-
lowing:
• Tier 1, determination of hydrocarbon groups in oil
residues;
• Tier 2, product screening and determination of n-alk-
anes and TPH;
• Tier 3, distribution pattern recognition of target
PAHs and biomarker components (sometimes the
volatile hydrocarbons are monitored);
• Tier 4, determination and comparison of diagnostic
ratios of the ‘‘source-specific marker’’ compounds
with the potential source oil and with the correspond-
ing data from database; and
• Tier 5, determination of weathered percentages of the
residual oil.
Stout et al. (2002) recently proposed a similar tiered
analytical approach to hydrocarbon forensic analysis,
which is summarized in Fig. 2. This tiered approach
gives environmental forensic investigator the flexibility
to gather information necessary to address site- or in-
cident-specific questions about the nature and extent,
and ultimately source(s), of hydrocarbon contamina-
tion.
2.5. Quality assurance
In order to support spilled oil forensic investigations,
well-defined quality management (including quality as-
surance and quality control procedures) must be a fun-
damental element of any analytical lab program. The
chemical measurements must be conducted within the
framework of highly stringent, defensible and reliable
QA and QC program.
Besides the routine quality control measures required
by standard EPA and ASTM methods such as instru-
ment calibration, surrogate spiking, procedural blanks,
matrix spike recoveries, replicate analyses, some refine-
ments have been further implemented by many oil spill
analysis laboratories in order to achieve improved ana-
lytical precision and accuracy (Page et al., 1995; Short
et al., 1996; Wang et al., 1994a; Stout et al., 2002). The
key refinements include the following:
 Z. Wang, M.F. Fingas / Marine Pollution Bulletin 47 (2003) 423–452 429

Fig. 1. Protocol/decision chart for the oil spill identification (from Daling et al., 2002).

• To establish 5-point calibration curves that demon-
strate the linear range of the analysis.
• To analyze quality control standards prepared from
the National Institute of Standards and Technology
(NIST) certified standard reference materials (SRMs)
with the sample batches for accuracy assessment.
• To apply more rigorous calibration check standards
of ±15%.
• To determine relative response factors (RRFs) of tar-
get analytes of interest from authentic standards.
• To manually set the baselines for alkylated PAHs at
various alkylation levels.
• To estimate the method detection limits (MDLs) for
each target analytes using the procedure described
in Appendix B, 40CFR (Code of Federal Regula-
tions) Part 136.
• To increase sample size and to reduce the sample ex-
tract pre-injection volume for those sediment samples
with very low concentrations of hydrocarbons.
3. Oil and petroleum product type screening and differ-
entiation
Crude oil is a complex mixture of thousands of dif-
ferent organic compounds formed from a variety of
organic materials that are chemically converted under
differing geological conditions over long periods of time.
430 Z. Wang, M.F. Fingas / Marine Pollution Bulletin 47 (2003) 423–452

Fig. 2. Tiered analytical approach to hydrocarbon fingerprinting (from Stout et al., 2002).

Crude oils contain primarily carbon and hydrogen
(which form a wide range of hydrocarbons from light
gases to heavy residues), but also contains smaller
amounts of sulfur, oxygen and nitrogen as well as metals
such as nickel, vanadium and iron. The infinitely vari-
able nature of these factors results in distinct chemical
differences between oils. Refined petroleum products are
fractions usually derived by distillation of crude oil.
Because of dissimilarities in characteristics of crude oil
feed stocks and variations in refinery processes, refined
oil products differ in their chemical compositions. Thus,
all crude oils and petroleum products, to some extent,
have chemical compositions that differ from each other.
This variability in chemical compositions results in un-
ique chemical ‘‘fingerprints’’ for each oil and provides a
basis for identifying the source(s) of the spilled oil.
Generally, the type and identity of fresh to mildly
weathered oils and petroleum products can be readily
revealed from their GC-FID traces, especially where the
spilled oil or petroleum product is heavy and back-
ground hydrocarbon levels are low in an impacted en-
vironment. In addition to measuring TPH in samples,
GC-FID chromatograms provide a distribution pattern
of petroleum hydrocarbons (e.g., carbon range and
profile of UCM), fingerprints of the major oil compo-
nents (e.g., individual resolved n-alkanes and major
isoprenoids), and information on the weathering extent
of the spilled oil. Comparing biodegradation indicators
(such as n-C17 /pristane and n-C18 /phytane) for the spil-
led oil with the source oil can be also used to monitor
the effect of microbial degradation on the loss of hy-
drocarbons at the spill site for short time periods.
 Z. Wang, M.F. Fingas / Marine Pollution Bulletin 47 (2003) 423–452 431

3.1. General chemical composition features of crude oils
Crude oil compositions vary widely. Depending on
the sources of carbon from which the oils are generated
and the geologic environment in which they migrated
and from which reservoir, they can have dramatically
varied compositions in the C5 –C40 carbon range such as
relative amounts of paraffinic, aromatic and asphaltenic
compounds, large differences in the n-alkane distribu-
tions and UCM, and significantly different relative ratios
of isoprenoids to normal alkanes. Fig. 3 shows GC-FID
chromatograms for six different oils. Clearly, these six
oils are very different, as not only are there large dif-
ferences in the n-alkane distributions and UCMs, but
also in relative ratios of isoprenoids to normal alkanes.
Note that the Orimulsion sample, has nearly no n-alk-
anes in its GC-FID chromatogram.
3.2. General chemical composition features of refined
products
Refined petroleum products are obtained from crude
oil through a variety of distillation, cracking, catalytic
reforming, isomerization, alkylation, and blending pro-
cesses:
(1) Light distillates are typically products in the C3 –C12
carbon range. They include aviation gas, naphtha,
and automotive gasoline. The GC trace of fresh light
distillates are featured with dominance of light-end,
resolved hydrocarbons and a minimal UCM. The
most common light distillate, gasoline, has consider-
able BTEX and alkylated benzene compounds.
Other compound classes found in abundance in gas-
oline includes branched-chain alkanes and olefin
hydrocarbons with double bonds.
(2) Mid-range distillates are typically products in a rel-
ative broad carbon range (C6 –C26 ) and include kero-
sene, jet fuel, and diesel products. Jet fuels are
similar in gross composition, with many of the dif-
ferences in them attributable to additives designed
to control some fuel parameters such as freeze and
pour point characteristics. For example (Fig. 4),
Jet B fuel from Alaska is dominated by GC-resolved
n-alkanes in a narrow range of n-C8 to n-C18 with
maximum being around n-C12 . The UCM is well

Fig. 3. GC-FID chromatograms for six oils. These six oils are different, as not only are there large differences in the n-alkane distributions and UCMs,
but also in relative ratios of isoprenoids to normal alkanes. Note that the Orimulsion sample, has nearly no n-alkanes on its GC-FID chromatogram.
432 Z. Wang, M.F. Fingas / Marine Pollution Bulletin 47 (2003) 423–452
Fig. 4. GC-MS (m=z 85) chromatograms of four petroleum products, illustrating distinguishing features of n-alkane distribution patterns between
these oil products.
defined. As for Diesel No. 2, characteristic wider-re-
solved hydrocarbons (in the carbon-range of C6 –C23
with maxima being around C12 –C14 ) and a central
UCM ‘‘hump’’ are obvious. The properties of a
given diesel are largely a function of the crude oil
feedstock.
(3) Classic heavy fuel types include fuel Nos. 5 and 6
(also known as Bunker C) or residual. The heavy
residual fuels are largely used in marine diesel and
industrial power generation. The chemical compo-
sition of Bunker C can vary widely and remarkably,
depending on production oilfields, production
years, and processes it has undergone. Currently,
many Bunker type fuels are produced by blending
residual oils with diesel fuels or other lighter
fuels in various ratios for marine or power plant
use. A case study in which biomarkers and PAHs
were used to correlate a spilled Bunker C to its sus-
pected sources was recently reported (Stout et al.,
2001).
(4) Lubricating oils are specialty products that have a
broad profile in the C18 –C40 with nearly no resolved
alkanes being present. Common type of lubricating
oils include crackcase oil, transmission fluid, hy-
draulic fluid, and cutting oil. In some hydraulic flu-
ids, for example, the PAH concentrations can be
very low, while the biomarker concentrations could
be very high, in comparison with most other refined
products. These features in chemical compositions
can be used to distinguish refined products.
3.3. Source identification by comprehensive two-dimen-
sional GC
Gains et al. (1999) recently described application of
two dimensional GC–GC with FID detection for spill
source identification. In this method, each analyte in oil
is subject to two different separations achieved using two
GC columns connected serially by a thermal modulator.
Compounds of similar chemical structure were grouped
 Z. Wang, M.F. Fingas / Marine Pollution Bulletin 47 (2003) 423–452
together in ordered two-dimensional chromatograms.
The GC–GC analysis resulted in a match between the
spill samples and one of the source samples. This result
was consistent with the results obtained by GC–MS.
4. Effects of weathering on oil hydrocarbon fingerprinting
When crude oil or petroleum products are acciden-
tally released to the environment, they are immediately
subject to a wide variety of weathering process (Jordan
and Payne, 1980). These weathering processes can in-
clude: (1) evaporation, (2) dissolution, (3) microbial
degradation, (4) other processes such as dispersion and
water–oil emulsification, photooxidation, adsorption
onto suspended particulate materials, and oil–mineral
aggregation.
Evaporation. In the short term after a spill (hours to
days), evaporation is the single most important and
dominant weathering process, in particular for the light
petroleum products. In the first few days following a
spill, the loss can be up to 70% and 40% of the volume of
light crudes and petroleum products. For heavy or re-
sidual oils the losses are only about 5–10% of volume
(Fingas, 1995).
Dissolution. The amount of the oil hydrocarbons
dissolving in water phase from oil slick largely depend
on the molecular structure and polarity of a given oil
component, and the relative solubility of the oil com-
ponent in water phase versus its solubility in the oil
phase. In general, (1) the aromatic hydrocarbons are
more soluble than aliphatic hydrocarbons, (2) solubili-
ties increase as the alkylation degrees of alkylated ben-
zene or PAHs decrease, (3) the lower molecular weight
hydrocarbons are more soluble than the high molecular
weight hydrocarbons in that class. Therefore, it can be
readily understood why the BTEX and lighter alkyl-
benzene compounds and some smaller PAH compounds
such as naphthalene are particularly susceptible to dis-
solution or ‘‘water-washing’’.
Biodegradation. Biodegradation of hydrocarbons by
natural populations of microorganisms represents one
of the primary mechanisms by which petroleum and
other hydrocarbon pollutants are eliminated from the
environment (Prince, 1993; Leahy and Colwell, 1990).
The biodegradation of petroleum and other hydrocar-
bons in the environment is a complex process, whose
quantitative and qualitative aspects depend on the type,
nature and amount of the oil or hydrocarbon present,
the ambient and seasonal environmental conditions
(such as temperature, oxygen, nutrients, water activity,
salinity, and pH), and the composition of the auto-
chthonous microbial community. Hydrocarbons differ
in their susceptibility to microbial attack. In general, the
degradation of hydrocarbons is ranked in the following
order of decreasing susceptibility: n-alkanes > branched
433
alkanes > low-molecular-weight aromatics > high-mole-
cular-weight aromatics and cyclic alkanes.
Photooxidation. Photooxidation is considered to be
another most important factor involved in the trans-
formation of crude oil or its products released into the
marine environment (Garrett et al., 1998). The photo-
chemical degradation yields a great variety of oxidized
compounds which are highly soluble in water.
Aggregation. Following the Exxon Valdez oil spill
in Prince William Sound, Alaska in March 1989, the
process of oil–mineral aggregates (OMA, also called
clay–oil flocs or clay–oil aggregates in the past) was dis-
covered as a mechanism affecting the rate of natural
cleansing of oil residues from shorelines (Bragg and
Owens, 1994). Oil-mineral aggregates was found to re-
sult from interactions among the oil residues, fine min-
eral particle, and seawater. Since then, a number of lab
studies, field trials, and spill site investigations have
been conducted. OMA formation has now been identi-
fied as an important process that facilitates the natural
removal of oil stranded in coastal sediments. OMA
formation is enhanced by physical processes such as
wave, energy, tides or currents. It has recently been
noted that oil biodegradation may be enhanced by
OMA formation.
4.1. Chemical composition changes due to weathering
Weathering causes considerable changes in the chem-
ical and physical properties of spilled oils. The degree
(lightly, moderately, or highly weathered) and rate of
weathering is different for each spill and is controlled by
a number of spill conditions and natural processes such
as type of the spilled oil, spill site and environmental
conditions, and microbiological activities. Major chem-
ical compositional changes due to weathering can be
summarized as the following (Page et al., 1995; Wang
et al., 1999a):
• For lightly weathered oils, significant losses occur
in the low-molecular-weight n-alkanes, however the
ratios of n-C17 /pristane and n-C18 /phytane have been
found to be virtually unaltered from those measured
for the source oil. Therefore, for fresh or mildly
weathered oil products, alkane and isoprenoid ana-
lysis may be used for oil source identification. In
heavily weathered oils, the n-alkanes, and even the
isoprenoids in some cases, may be completely lost.
Under such circumstances, GC-FID analysis is of lit-
tle value for suspect source identification.
• Rapid loss of volatile aromatic compounds including
BTEX (benzene, toluene, ethylbenzene, and xylenes)
and C3 -benzenes. When oils are weathered to a cer-
tain degree (approximately in the range of 20–25%
weathering), the BTEX and C3 -benzenes are com-
pletely lost.
434 Z. Wang, M.F. Fingas / Marine Pollution Bulletin 47 (2003) 423–452
• Pronounced decrease in the naphthalenes relative to
other alkylated PAH series.
• Development of a profile in each alkylated PAH fam-
ily showing the distribution of C0 < C1 < C2 < C3 .
• Enhancement of the chrysenes relative to other PAH
series and significant decrease in the relative ratios
of the sum of naphthalenes, phenanthrenes, dibenzo-
thiophenes, and fluorenes to chrysenes.
• Gradual concentration in the relative abundances of
biomarker compounds (terpanes and steranes) be-
cause of their refractory nature and high resistance
to biodegradation. Also, the relative ratios of paired
terpane compounds including Ts=Tm, C23 /C24 , C29 /
C30 , C31 22S/(22S + 22R), C32 22S/(22S + 22R), C33
22S/(22S + 22R) are almost not altered by weathering.
4.2. Degradation rate
The early effect of microbial degradation is moni-
tored by the ratios of biodegradable to less degradable
compounds such as the n-C17 /pristane and n-C18 /phy-
tane ratios. It has been demonstrated, however, that
changes in these ratios may substantially underesti-
mate the extent of biodegradation because isoprenoids
also biodegrade to a significant degree. Later, highly
degradation-resistant components such as C30 17a(H),
21b(H)-hopane are selected to serve as conserved ‘‘inter-
nal standards’’ for determining rate and extent of
weathering for the spilled residual oil (Butler et al., 1991;
Prince et al., 1994). For distilled oil products, such as
diesel and jet fuel samples, which may not contain sig-
nificant quantities of biomarker compounds and chry-
senes, less ‘‘conservative’’ PAHs with a high degree of
alkylation such as C4 or C3 -phenanthrenes can be se-
lected and used as alternative internal standards.
As an example, Fig. 5A and 5B show the GC chro-
matograms for TPH and n-alkane analysis and GC–
SIM–MS chromatograms for alkylated benzene and
alkylated PAH distribution analysis for 25-year-old
Nipisi spilled oil samples (Wang et al., 1998a), illus-
trating the effect of field weathering conditions and
sample depths on chemical composition changes of the
spilled oil during the 25 year period. Fig. 5 clearly
demonstrates that 25 years after the spill, the remaining
underground oil is still relatively ‘‘fresh’’ in comparison
to the reference oil and the surface residual oil. Sub-
surface oil degradation has been demonstrated to be
slow and will proceed at a very slow rate because the
peat in this wetland habitat system is acidic, and water
saturated, i.e., largely anaerobic. Also, the average an-
nual temperature is only 1.7 C, based on 22 years of
weather records.
Sasaki et al. (1998) found similar to 17a, 21b-hopane,
vanadium, the most abundant heavy metal in crude oils,
was not significantly reduced even after an intensive
biodegradation of crude oil. Thus, they used vanadium
as an internal marker for evaluation of the biodegra-
dation and weathering of crude oil.
4.3. Kinetic model to evaluate PAH weathering
Short and Heintz (Short and Heintz, 1997) have de-
veloped a first-order loss-rate (FOLR) kinetic model of
PAH weathering to evaluate 7767 environmental samples
collected for the Exxon Valdez oil spill for the presence of
spilled oil. The modelled PAHs included the 14 most
persistent compounds of 31 analyzed by GC-MS. Pa-
rameters include loss-rate constants related to energy
required for PAHs to escape from petroleum and a
quantitative index of weathering. The model accounts for
91% of the temporal variability of modelled PAH con-
centrations. Short (Short, 2002) has applied this model to
four independent case studies. The approach used in these
case studies evaluates a goodness-of-fit metric between
the measured hydrocarbon composition of an environ-
mental sample and a suspected source after correcting for
PAH weathering loss based on FOLR kinetics.
4.4. Estimation of weathering age of refined products
As discussed above, oil weathering is a very complex
process, and the chemical composition changes due to
weathering, the weathering degree and weathering rate
are determined by many factors. Estimation of weath-
ering age of a spill is, therefore, a very complex issue and
difficult task, and it should be dealt case by case in most
situations. For example, we found during the 25-year
old Nipisi spill study (Wang et al., 1998a) that the
weathering degrees of the residual oil were dramatically
different from sample to sample: some samples were
highly weathered with all n-alkanes and isoprenoids
being completely lost, while some samples were only
very lightly weathered (indicated by existence of large
quantities of BTEX and alkylbenzene compounds, and
the n-alkane distribution being almost not changed in
comparison with the reference oil).
Christensenand and Larsen (1993) assembled data
from 12 diesel spill sites with known spill time for each
spill in northern Europe. The data from these sites ul-
timately yielded a linear correlation between the ‘‘time
since the release in years’’ and ‘‘average n-C17 /pristane
ratio’’. Kaplan et al. (1995) extracted the plotted data
points from Christensen and Larsen and published a
linear equation used for weathering age determination
of diesel. However, it should be noted that their cali-
bration chart was developed for particular spill sites
under a unique set of environmental conditions. Bacte-
rial activity could be greatly different from site to site,
resulting in very different rate of biodegradation. Other
environmental factors such as temperature, water level,
salinity, and many others will also play key roles in
determining the rate of biodegradation. Stout et al.
 Z. Wang, M.F. Fingas / Marine Pollution Bulletin 47 (2003) 423–452 435

Fig. 5. GC-FID (Fig. 5A, left panel) and GC–SIM–MS (Fig. 5B, right panel) chromatograms of saturated and aromatic fractions for the Nipisi
reference source oil PL-B, and samples N2-1A (0–2 cm), N2-1B (12–16 cm), and N2-1C (30–40 cm), illustrating the effects of field weathering
conditions and sample depths on chemical composition changes of aliphatic (in particular n-alkanes) and alkylbenzenes and alkylated PAHs, re-
spectively. Sur. and IS represent surrogate and internal standard. B and N represent benzene and naphthalene respectively; n, 0, 1, 2, and 3 represent
carbon numbers of alkyl groups in alkylbenzenes and alkylated naphthalene homologues.

(2002) and Philp (2002a) have discussed in detail the
numerous caveats that must considered in this age-dat-
ing method that otherwise might lead to oversimplica-
tion of the very complex issue of age dating diesel or
other oil product contamination.
5. Oil correlation and source identification by PAH
fingerprinting analysis
In some instances, qualitative chemical analysis and
visual comparison of chromatograms of spilled oil,
suspected candidate sources, and background materials
may sufficiently meet the needs of a forensic investiga-
tion. However, when the chemical similarity/difference
between spilled oil and the suspected source(s) is not
obvious, or a large number of candidate sources are
involved, or spilled oil has undergone heavy weathering
and significant alteration in its chemical compositions,
the qualitative approach would be difficult to defend,
and therefore the quantitative fingerprinting analysis of
degradation-resistant PAH and biomarker compounds
must be performed.
436 Z. Wang, M.F. Fingas / Marine Pollution Bulletin 47 (2003) 423–452

5.1. PAH distribution pattern recognition
Crude oils and refined products from different sources
can have very different PAH distributions. Also, many
PAH compounds are more resistant to weathering than
their saturated hydrocarbon counterparts (n-alkanes
and isoprenoids) and volatile alkylbenzene compounds,
thus making PAHs one of the most valuable finger-
printing classes of hydrocarbons for oil identification.
Even differences between the same types of products are
discernible through examination of the PAH distribu-
tion. Examples of PAH distribution of some oil and
petroleum product types are illustrated in Fig. 6. The oil
products differ significantly in the PAH distribution

Fig. 6. Alkylated homologous PAH and other EPA priority PAH distributions for the Federated crude, Jet B, Diesel, and Orimulsion, illustrating
differences in PAH distribution features between different oil and oil products. Note that for clarity, different scales are used for Y-axis. N, P, D, F,
and C represent naphthalene, phenanthrene, dibenzothiophene, fluorene, and chrysene, respectively; 0–4 represent carbon numbers of alkyl groups in
alkylated PAH homologues. See Table 2 for abbreviations for other EPA priority PAHs.
 Z. Wang, M.F. Fingas / Marine Pollution Bulletin 47 (2003) 423–452 437

from the crude oils and from each other. Jet B fuel has
extremely high content of the naphthalene series (99%)
with the other four alkylated PAH series being only 1%
in total. In addition, no 4- to 6-ring PAHs were detected
of the other 15 EPA priority PAHs. Diesel No. 2 has a
high naphthalene content (86%), a low phenanthrene
content (5%), and no chrysenes. In the Orimulsion 400,
the unusually high contents of the alkyl phenanthrenes
and dibenzothiophenes were pronounced, accounts for
approximately 38% and 22%, respectively, of the total
PAHs. In addition, a profile in each alkylated PAH
family showing the distribution of C0 < C1 < C2 < C3 is
very apparent, similar to the severely weathered oil.
5.2. Diagnostic ratios of PAH compounds
A number of diagnostic ratios of target alkylated
PAH species have been successfully used as indicators
for oil spill identification. These are briefly summarized
in Table 4. A benefit of comparing diagnostic ratios of
spilled oil and suspected source oils is that any con-
centration effects are minimized. In addition, the use of
diagnostic ratios to correlate and differentiate oils tends
to induce a self-normalizing effects on the data since
variations due to instrument operating conditions, op-
erators, or matrix effects are minimized.
A method using the double ratio plots of alkylated
PAH homologues, C2 D/C2 P versus C3 D/C3 P, for iden-
tification and differentiation of petroleum product sour-
ces has been developed and extensively used in the studies
of the Gulf War oil spill (Sauer et al., 1993, 1998) and of
the 1989 Exxon Valdez oil spill to distinguish Alaska
North Slope (ANS) crude, its weathering products, and
diesel refined from ANS feed stock from other petrogenic
hydrocarbons (Bence and Burns, 1995; Bence et al., 1996;
Page et al., 1995; Brown and Boehm, 1993). Further-
more, Douglas et al. (1996) have defined the C3 D/C3 P
and C3 D/C3 C as ‘‘source ratios (the ratios that be almost
constant because the compounds degraded at the same
rate)’’ and ‘‘weathering ratios (the ratios that change
substantially with weathering and biodegradation)’’, re-
spectively. They were applied to described oil depletion
and to identify sources in subtidal sediment data from the
Exxon Valdez spill and a North Sea oil spill.
Hostettler et al. (1999) reported a method using the
PAH refractory index, ratio of two of the most refractory
constituents of most oils (triaromatic steranes and methyl-
chrysenes), as a source discriminant of hydrocarbon input
for differentiation of three different oils (Exxon Valdez oil,
Katalla oil, and PWS sediment hydrocarbons).
In the studies of characterization of spilled oil resi-
dues from the Arctic environments and northern inland,

Table 4
Diagnostic ratios of ‘‘source-specific’’ PAH compounds used for oil spill studies
Diagnostic ratios Application References
Double ratio plots (C2D/C2P vs. ––Distinguishing between sources with similar chemical compositions Bence et al. (1996);
C3D/C3P) ––Useful in establishing statistical models for source allocation Boehm et al. (1997);
––Examples: Exxon Valdez oil spill study; Gulf War oil spill study Page et al. (1995, 1996)
Double ratio plots (C3D/C3P vs. ––Distinguishing among weathered crude oils Douglas et al. (1996);
C3D/C3C) ––Distinguishing spilled oil from other sources Sauer and Boehm (1995)
––Examples; to describe oil depletion and to identify in subtidal data
from the M/C Haven spill in Italy, Exxon Valdez spill, and a North
Sea oil spill
P
4- to 6-ring non-alkylated PAH/ ––Used for multi-source hydrocarbons identification in the study Kennicutt (1998);
PPAH P hydrocarbon contamination on the Antartic Peninsula Kvenvolden et al. (1995);
Naphs/ PAH Sauer and Boehm (1995)
P P
P Phens/P dibens
Phen/ phens

Ratios of 3 m-DBT isomers ––Used for source identification of unknown spilled oils Fayad and Overton (1995);
––Distinguishing between oils with a similar chemical compositions Wang and Fingas (1995b, 1999a)
––Differentiation between oils due to physical weathering and biode-
gradation
––Marker of biodegradation
C0 C; C1 C: C2 C: C3 C ––Used for source identification in the Arrow and BIOS spill studies Boehm et al. (1997);
P P
P chrys/P phens ––Weathering indicator Sauer et al. (1998);
chrys/ dibens ––Differentiation between compositioin changes due to physical Wang et al. (1994b, 1999a)
Relative distribution of PAH in weathering and biodegradation
each homologous family
P
PAH: the sum of total PAH including five target alkylated PAH homologue and the other EPA priority PAH; m-DBT: methyl-dibenzothiophene;
4- to 6-ring non-alkylated PAH include fluoranthene, pyrene, benzofluoranthenes, benzopyrenes, indenopyrene dibenzoanthracene and benzo-
peryene.
438 Z. Wang, M.F. Fingas / Marine Pollution Bulletin 47 (2003) 423–452
Wang et al. (1994b, 1998a,c), utilized a number of di-
agnostic ratios of selected source-specific alkylated
PAHs in combination with determination of ratios of
selected paired biomarkers for source identification and
differentiation, determination of weathering extent and
degree of surface and subsurface samples, and distin-
guishing between composition changes due to physical
weathering and biodegradation.
5.3. PAH isomer analysis
The use of the sum of the alkylated PAHs as multi-
component analytes in deriving diagnostic ratios for oil
characterization and spill assessment have been made
considerable advances as described above. Recently,
research has been further expanded to use individual
source-specific isomers within the same alkylation level
and to determine the relative isomer-to-isomer distribu-
tion for source identification of spilled oil. For example,
chromatographically well-separated C1 -dibenzothio-
phene isomers (Fayad and Overton, 1995; Wang and
Fingas, 1995b) present in all oils at relatively high con-
centrations and their relative abundance distributions
vary significantly from different sources. As the alkyla-
tion levels increase, more isomers will be detected (for
example, the C3 -dibenzothiophenes as a group, contain
more than 20 individual isomers with different relative
abundances). The differences between the isomer dis-
tributions reflect the differences of the depositional
environment during oil formation. Compared to PAH
homologous groups at different alkylation levels, higher
analytical accuracy and precision may be achieved due
to the close match of physical/chemical properties of the
isomers. Also, the relative distribution of isomers are
subject to little interference from weathering in short-
term or lightly weathered oils. Hence this approach can
be positively used for oil spill identification. On the
other hand, it has been demonstrated that the position
of the alkylation on the PAHs can influence the biode-
gradation rate of the isomers within an isomer group.
This information can be used to sort out environmental
factors such as the impact of biodegradation on the
PAH distribution and to differentiate oil compositional
changes due to physical weathering from those due to
biodegradation.
GC–MS method has been developed for the differen-
tiation and source identification of crude, weathered and
biodegraded oils using the relative abundances of three
isomeric methyldibenzothiophene (4-:2-/3-:1-m-DBT)
compounds (Wang and Fingas, 1995b). A database of
the ratios of the C1 –DBT isomers for several hundred
crude, weathered and biodegraded oils, and petroleum
products has been established. Fig. 7 plots 2-/3-methyl-
dibenzothiophene versus 1-methyldibenzothiophene
(both isomers are normalized relative to 4-methyldi-
benzothiophene) using data from the database. Fig. 7
Fig. 7. Plot of the relative ratios of 2-/3-methyldibenzothiophene to 4-
methyldibenzothiophene versus the relative ratios of 1-methyl-
dibenzothiophene to 4-methyldibenzothiophene for 49 different oils
and oil products. The circles 1 and 2 indicate related samples from
origins of North Slope and Terra Nova, respectively.
shows how scattered the data points representing the
various oils are. Another pronounced feature observed
from Fig. 7 is that related oils produce tight clusters on
the plot. The use of these ratios complements existing
methods of oil characterization, but has its own distinct
advantages. The ratios of the C1 –DBT compounds, in
combination with other fingerprinting data, have been
used to successfully discriminate different oil samples
(Wang et al., 1999c) and to identify the source of oil on
contaminated birds (Wang et al., 1997b).
During January and February 1996, a significant
number of tarball/patty incidents occurred along the
coast of Vancouver Island (British Columbia), Wash-
ington, Oregon, and California (Wang et al., 1998b). In
addition of determination of conventional diagnostic
PAH and biomarker ratios, a number of ‘‘source-spe-
cific’’ isomeric PAHs within the same alkylation levels
were quantified, and their relative abundance ratios were
computed in order to definitively identify and differen-
tiate the sources of the tarballs. The selected isomers
include three isomers each within C3 -naphthalenes and
C4 -naphthalenes, four isomers each within C1 -phen-
athrenes and C2 -phenathrenes, two isomers within
C4 -phenathrenes, and three isomers each within C1 -flu-
orenes and C1 -dibenzothiophenes. Comprehensive ana-
lysis results revealed that California/Oregon tarball
samples were chemically similar to the British Columbia/
Washington tarball samples, but they originated from
two different Bunker type fuels.
6. Oil correlation and source identification by biomarker
fingerprinting analysis
Biomarker fingerprinting has historically been used
by petroleum geochemists in characterization of marine
 Z. Wang, M.F. Fingas / Marine Pollution Bulletin 47 (2003) 423–452 439

oils in terms of source rock, genetic family, migration

and maturation properties, and in identification of pe-
troleum deposits. Chemical analysis of source-charac-
teristic and environmentally persistent biomarkers
generates information of great importance in determin-
ing the source of spilled oil, differentiating oils, moni-
toring the degradation process and weathering state of
oils under a wide variety of conditions. In the past de-
cade, use of biomarker fingerprinting techniques to
study spilled oils has greatly increased, and biomarker
parameters have been playing a prominent role in al-
most all oil spill work.

6.1. Biomarker distributions

Much of the knowledge of biomarkers and their di-

agnostic ratios comes from the oil geochemistry (Peters
and Moldowan, 1993). A wide variety of biomarkers
have been identified as being of use in characterization
of crude oils and oil fractions, including tricyclic, tetra-
cyclic and pentacyclic terpanes (m=z 191), methyl-
hopanes (m=z 205), steranes (m=z 217/218), methylsteranes Fig. 8. GC–MS chromatograms of biomarker terpanes at m=z 191 for
North Slope, Cook Inlet, Diesel No. 2, and Jet B fuel from Alaska. The
(m=z 217/231), and diasteranes (m=z 217/259). The dis-
Cook inlet oil showed significantly different biomarker distribution
tribution patterns are, in general, different from oil to from the North Slope oil with much lower total concentration of ter-
oil. As for refined products, no biomarker compounds panes and with only C30 ab-hopane being prominent. No biomarker
are detected in jet fuel and only trace C20 –C24 terpanes compounds were detected in Jet B fuel and only trace C20 –C24 terpanes
were present in the diesel, while most lube oils and hy- present in the diesel. Obviously, refinery processes have removed most
high molecular weight biomarkers from the corresponding crude oil
draulic fluids contain very high quantity of biomarkers.
feed stocks.
Obviously, refining processes have removed or concen-
trated most high molecular mass biomarkers from the
corresponding crude oil feed stocks.
an interpretational advantage in fingerprinting sources
Based on analysis of triterpane distribution patterns
of spilled oils and to provide additional diagnostic in-
and determination of two pentacyclic C27 triterpanes,
formation on the types of organic matter that give rise to
Shen (1984) distinguished four Arabian crudes, which in
the crude oil. For example, the geologically rare acyclic
their weathered forms were extremely similar to one
alkane botrycoccane (C34 H70 ) was used to identify a new
another. A study by Bieger et al. (1996) demonstrated
class of Australian non-marine crude oils (McKirdy et al.,
the use of tricyclic and pentacyclic terpanes as indicators
1986). The biomarkers 18a(H)-oleanane and 17a(H),
of the origin of diffuse lubricating oil contamination in
18a(H), 21b(H)-28, 30-bisnorhopane have been of spe-
plankton and sediments around St. JohnÕs, Newfound-
cial interest. The presence of biomarker 18a(H)-olean-
land, Canada. In this study, variable inputs of auto-
ane in benthic sediments in PWS, coupled with its
motive and outboard motor oils in different areas were
absence in Alaska North Slope crude and specifically in
clearly recognized and identified.
Exxon Valdez oil and its residues, confirmed another
As an example, Fig. 8 shows GC–MS chromatograms
petrogenic source (Bence et al., 1996; Page et al., 1996).
at m=z 191 for North Slope, Cook Inlet, Diesel No. 2,
Other ‘‘specific’’ pentacyclic terpanes include gammace-
and Jet B fuel from Alaska. Fig. 8 clearly demonstrates
rane, moretanes, lupanes, and bicadinanes.
that the biomarker distributions are significantly differ-
ent from oil to oil, and from oil to petroleum products.
6.3. Sesquiterpane and diamondoid biomarkers for corre-
lation of oil and refined products
6.2. Unique biomarker compounds
Various bicyclic sesquiterpanes and diamondoid com-
Biomarker terpanes and steranes are common con- pounds boiling within diesel range have been identified
stituents of crude oils. However, a few ‘‘specific’’ bio- in a number of crude oils. Diamondoid hydrocarbons
marker compounds including several geologically rare (such as adamantane, C10 , and diamantane, C14 , and their
acyclic alkanes are found to exist only in certain oils alkyl homologues) are rigid, three-dimensionally fused-
and, therefore, can be used as unique markers to provide cyclohexane-ring alkanes that have a diamond-like
440 Z. Wang, M.F. Fingas / Marine Pollution Bulletin 47 (2003) 423–452
structure. These biomarker compounds are thermally
stable and highly resistant to biodegradation.
In a series cracking experiments in the laboratory,
Dahl et al. (1999) found that the increase in methyl-
diamantane (C15 ) concentration is directly proportional
to the extent of cracking, indicating that under the
conditions of their experiments, diamondoids are nei-
ther destroyed nor created. Instead, they are conserved
and concentrated, and hence can be considered to be a
naturally occurring ‘‘internal standard’’ by which the
extent of oil destruction can be determined. Chen et al.
(1996) identified 26 diamondoid hydrocarbons in oil
and source rock samples from the Tarim, Yinggehai,
Qiongdongnan and other Chinese basins. Two dia-
mondoid hydrocarbon ratios have been developed and
used as novel high maturity indices to evaluate the
maturation and evolution of crude oils and condensates
in these Chinese basins. Noble et al. (1986) compared
the chromatographic distributions of bicyclic sesquiter-
panes (m=z 123) of two weathered diesel fuel #2 samples
from two adjacent petroleum terminal properties. The
samples have been highly weathered with n-alkanes
being completely lost. However, GC/MS (m=z 123) ana-
lysis results showed very different distribution profiles
of sesquiterpane compounds between two samples,
strongly indicating that two sources of diesel existed in
the study area.
Clearly, the smaller and lower boiling sesquiterpane
and diamondoid biomarkers are useful and promising
for source correlation and differentiation of refined
products, in particular for the weathered refined pro-
ducts, because of their stability and resistance to bio-
degradation. It can be anticipated that more work will
be published in this fertile area of research (Stout et al.,
2002; Philp, 2002a).
6.4. Diagnostic ratios of biomarkers
A number of ratios of selected terpanes and steranes
has been defined and increasingly used for tracking
spilled oils and identifying spill sources. The diagnostic
ratios of biomarkers most used include the following:
• Tm=Ts: 17a(H), 21b(H)-22,29,30-trisnorhopane/18a(H),
21b(H)-22,29,30-trisnorhopane.
• Triplet ratio: [C26 -tricyclic terpane (S?) + C26 -tricyclic
terpane (R?)]/C24 -tetracyclic terpane.
• C23 /C24 : C23 -tricyclic terpane/C24 -tricyclic terpane.
• C29 /C30 : 17a(H), 21b(H)-norhopane/17a(H), 21b(H)-
hopane.
• C23 /C30 and C24 /C30 . These ratios are used as source
parameters in biodegradation assessments.
• C31 S/(S + R), C32 S/(S + R), C33 S/(S + R): These al-
kylhopane epimer ratios is typical terpane-maturity
parameter used extensively in petroleum geochemis-
try.
• BTO: 17a(H), 18a(H), 21b(H)-28,30-bisnorhopane (B),
17a(H), 18a(H), 21b(H)-25,28,30-trisnorhopane (T)
and oleanane (O).
• steranes C27 abb/C29 abb, C28 abb=ðabb þ aaaÞ, and
C29 abb=ðabb þ aaaÞ.
The triplet ratio, in general, varies in oils from dif-
ferent sources and is dependent upon sources, deposi-
tional environment and maturity. The triplet ratio was
first used in a chemistry study of North Slope crude by
Kvenvolden et al. (1985), in which the ratio is
2. Exxon
Valdez oil (an Alaska North Slope crude) and its resi-
dues also have triplet ratios of
2; in contrast, many
tarballs collected from the shorelines of the Sound have
triplet ratios of
5.
During the Arrow oil spill work, the ratio of the most
abundant C29 –C30 hopane was defined and used as a
reliable source indicator (Wang et al., 1994b). Recently,
Zakaria et al. (2000) studied oil pollution in the Straits
of Malacca. Various samples including Malaysia oil,
Middle East crude oils, South East Asian crude oils,
tarballs, sediments, and mussels were collected and an-
alyzed. The analytical results in
Pthis study demonstrated
the utility of C29 /C30 ratio, (C31 –C35 )/C30 , and ho-
mohopane index as molecular tools to distinguish the
source of petroleum in the Straits of Malacca. Barakat
et al. (1997) studied biomarker properties of five crude
oils from the Gulf of Suez, Egypt. The results reveal
significant difference in biomarker distribution within
the oils that suggest two oil types and one mixed type.
Type 1 oils show a high relative abundance of gam-
macerane indicating a marine saline-source depositional
environment. Another related feature of these oils is the
predominance of C35 over C34 17a(H)-homohopanes.
Type 2 oils show oleanane indices over 20%, indicating
they originated from an angiosperm-rich, Tertiary
source rock. Type 3 oil has geochemical characteristics
intermediate between type 1 and 2 oils. Barakat et al.
(2002) recently also reported a study results using mo-
lecular ratios of triaromatic sterane compounds (ratios
of C28 20R/C28 20S, C27 20R/C28 20R, and C28 20s/[C26
20R + C27 20S] triaromatic steranes) for oil weathering
monitoring and source correlation.
6.5. Effect of biodegradation on biomarker distribution
The effects of biodegradation on biomarkers have
been investigated by many authors. Several in vitro and
in situ studies have shown that hopane and sterane
compounds are very resistant to biodegradation. In
laboratory studies of biodegradation of nine Alaska oils
and oil products (Wang et al., 1997a) and eight Cana-
dian oils (Wang et al., 1998c) by a defined bacterial
consortium incubated under freshwater and cold/marine
conditions, it is found that the fingerprint patterns of
triterpanes and steranes showed no changes after incu-
 Z. Wang, M.F. Fingas / Marine Pollution Bulletin 47 (2003) 423–452
bation, despite extensive saturate and aromatic losses,
and the ratios of selected paired biomarkers also re-
mained constant. Therefore, biomarkers can, in many
cases, be and have been used as conserved internal ref-
erences (Butler et al., 1991; Prince et al., 1994) for oil
weathering and biodegradation studies, in particular for
those highly degraded or long-term weathered residual
oils and complex petroleum-contaminated environmen-
tal samples.
However, it should be noted that in severely weath-
ered or long-term weathered oil, degradation of some
biomarkers was observed (Williams et al., 1986; Seifert
et al., 1984). Munoz et al. (1997) found that isoprenoids
were severely degraded and biomarkers were more or
less altered eight years after an oil spill in a peaty
mangrove in a tropical ecosystem. They also found that
norhopanes were the most biodegradation-resistant
among the studied terpane and sterane groups and the
C30 ab-hopane appeared more sensitive to weathering
than its higher homologues. Because of the differential
resistance of biomarkers to biodegradation, compari-
sons of their relative ratios can be used to rank oils as to
the extent of biodegradation. In a very recent study on
long-term fate and persistence of the spilled Metula oil
in a marine marsh environment, Wang et al. (2001)
found that in highly degraded asphalt pavement sam-
ples, even the most refractory biomarker compounds
showed some degree of biodegradation, and that the
biomarkers were generally degraded in the declining
order of importance of diasterane > C27steranes > tri-
cyclic terpanes > pentacyclic terpanes > norhopanes

C29 abb-steranes. Peters and Moldowan (1993) have
created a ‘‘quasi-stepwise’’ sequence for assessing the
extent to which an oil has been biodegraded, based on
the relative abundances of the various biomarker hydro-
carbon classes.
7. Characterization of additives for source identification
of refined products
Refined products often contain additives that can be
used for source identification, such as the alkyl lead
added to automotive gasolines in the US in the pre-1996
time (Stout et al., 2002).
Recently, Wang et al. (2002) identified major unknown
compounds with remarkable abundances in three un-
known oil samples with very similar bulk chemical com-
positions and nearly identical GC-FID chromatograms.
They are identified as 2,6-bis(1,1-dimethylethyl)-phenol,
butylated hydroxytoluene or 2,6-di-tert-butyl-4-methyl-
phenol, and N-phenyl-1-naphthalenamine. Samples 2996
and 2997 contained these three compounds with nearly
equal concentrations. However, butylated hydroxytolu-
ene (BHT) was not detected in the sample 2998. The
sample 2998 only contained the first and the last
441
compounds with the abundance of 2,6-bis(1,1-dimethyl-
ethyl)-phenol being largely higher than N-phenyl-1-
naphthalenamine.
All these three compounds identified are antioxidant
compounds, also called inhibitors. They are added to
oxidizable organic materials (such as lubricants and
gasoline) to retard autooxidation and, in general, to
prolong the useful life of the substrates. The identifica-
tion and differentiation of these additives clearly sup-
ports the general conclusion obtained from PAH and
biomarker characterization, that is, Samples 2996 and
2997 are identical and come from the same source, and
the sample 2998 is different from samples 2996 and 2997
and does not come from the same source as samples
2996 and 2997 do.
8. Using the isotopic composition of oil hydrocarbons for
oil correlation and source identification
The stable carbon composition of oils and their re-
fined products is essentially a manifestation of the
myriad physical and biological processes that influence
oil formation and refining (Whittaker et al., 1995; Philp,
2002a; Philp et al., 2002b). The complex isotopic frac-
tionation patterns induced by these processes result in
characteristic 13 C/12 C ratios that can be used to classify
crude oils, petroleum products and tars and can be in-
terpreted to elucidate oil depositional environment,
maturity, migration and biodegradation. In many cases,
the absence or low concentrations of biomarkers and
high molecular weight PAHs in refined products pre-
clude their successful use for making unique correlation.
An alternative and, sometimes, complimentary tech-
nique for correlation of such products is evolving
through the use of combined GC-isotope ratio MS
(GC–IRMS).
The isotopic analysis technique involves combustion
of samples to CO2 and H2 O at high temperature fol-
lowed by analysis of the isotopic composition of purified
CO2 using isotope ratio mass spectrometer (IRMS). The
ratio of 13 C/12 C is reported in the usual delta-notation
(d13 C) in parts per thousand (‰) relative to the PeeDee
belemnite (PDB) standard. In a review Whittaker et al.
(1995), placed particular emphasis on a critical evalua-
tion of the potential use of bulk and compound specific
carbon isotope ratio mass spectrometry in the elucida-
tion of waste source terms and extent of weathering.
8.1. Stable isotope of bulk hydrocarbons
The primary advantage of using the carbon-isotopic
technique lies in the analysis of samples that have un-
dergone extensive weathering, since the isotopic com-
positions of the whole oil remains largely unaffected and
can therefore can be used as a correlation parameter.
442 Z. Wang, M.F. Fingas / Marine Pollution Bulletin 47 (2003) 423–452
This was demonstrated by Kvenvolden et al. (1985,
1993), who used similarity and dissimilarity in isotopic
composition as further evidence of correlation between
weathered shoreline Exxon Valdez oils (d13 C ¼ 29:4 
0:1‰) and North Slope oil (d13 C ¼ 29:2 to )29.5‰),
and differentiation between Exxon Valdez oils, the pre-
spill petroleum hydrocarbon background Katalla seep
oil (d13 C ¼ 25:7‰), and Monterey-type (California-
source) shoreline tars (d13 C ¼ 23:7  0:2‰), respec-
tively.
Isotopic fingerprinting may be particularly useful for
characterization of heavy oil contaminated land since it
does not rely upon GC resolution of waste components
and therefore avoids the primary analytical constraint
associated with refractory wastes. Whittaker et al.
(1996) have reported utility of the IRMS technique as a
screening tool for identifying a predominance of polar
and asphaltenic material in heavy oils and for providing
an additional source correlation parameter for unde-
graded oily contaminants.
While most emphasis has been placed on the use of
bulk carbon isotopes for correlation purposes, there are
a number of forensic applications that have used other
stable isotopes. Kaplan et al. (1997) applied deuterium
values against carbon isotope values as a viable tool for
correlation of ground-water extracts and suspected
gasoline.
8.2. Compound-specific stable isotope analysis
One of the most significant advances in geochemistry
in the past few years has undoubtedly been the devel-
opment of individual hydrocarbon compound-specific
stable isotope analysis. Several studies that describe the
use of this technique to elucidate the origin of various
hydrocarbon products found in the aquatic environment
have been published (Hayes et al., 1990; OÕMalley et al.,
1994, 1996; Dowling et al., 1995). In conjunction with
the existing tools, Mansuy et al. (1997) utilized GC–
IRMS as a correlation tool for hydrocarbons spilled in
aquatic environments with their suspected source(s)
based on comparison of the isotopic composition of the
bulk saturates and aromatics and individual n-alkanes.
Differences in the isotope composition of n-alkanes are
immediately apparent and reflect their different origins.
In this work, a method for the correlation of severely
biodegraded oils based on the isotopic characterization
of asphaltene pyrolysates was also discussed. OÕMalley
et al. (1994) performed compound-specific carbon iso-
tope analysis on individual PAH compounds isolated
from environmental samples and concluded that the
dominant signatures identified in the surface sediments
of St. JohnÕs Harbour and Conception Bay were at-
tributed to crankcase oil.
After the Erika spill, Mazeas and Budzinski (2002)
performed both bulk and individual compound isotopic
analyses on oil residues and oiled bird feathers sampled
along the Atlantic Coast of France. Bulk stable carbon
isotopic composition has been shown to be a valuable
screening correlation tool as it confirms the link of
samples collected in the north part of Atlantic Coast
with the Erika oil spill. Molecular isotopic composition
of saturated hydrocarbons and of phenanthrene com-
pounds also allows unambiguous differentiation of
samples related to the Erika oil spill from those due to
tar ball incidents.
The hydrogen isotope ratio is interesting. In com-
parison with the carbon isotopes, the hydrocarbon iso-
topes are commonly fractionated to a much greater
extent and as a result display large variation in d values.
Pond et al. (2002) recently studied the effect of in vitro
aerobic biodegradation on the hydrogen isotopic com-
position of individual n-alkanes from crude oil. They
found that the n-alkanes that were degraded at the fast
rates also showed the largest overall isotopic fractiona-
tion (12–15& deuterium enrichment), suggesting that
the lower molecular weight n-alkanes can be used to
monitor in situ bioremediation of crude oil contamina-
tion.
9. Oil spill identification by statistical and numerical
analysis
The quantitative oil analysis data, when used in
conjunction with multivariate statistical analyses, can
increase the precision of analytical data and provide an
unbiased and defensible means to differentiate among
qualitatively similar oils. In modern oil forensic inves-
tigations, various statistical and numerical analysis
techniques have been developed and applied to the data
interpretation (Burns et al., 1997; Stout et al., 1998).
These powerful tools include principal components
analysis, discriminant analysis and cluster analysis.
Among them, principal components analysis (PCA) is
the most widely used and powerful multivariate analysis
technique. It is used to transform original sample com-
position data into new, smaller and uncorrelated vari-
ables called principle components. For data sets with
large number of interrelated variables, PCA is a pow-
erful tool for analyzing the structure of the data and
reducing the dimensionality of the pattern vectors. By
using the pattern recognition and PCA techniques,
spilled jet fuels which had undergone weathering in
subsurface environment were characterized chromato-
graphically and then successfully classified (Lavine et al.,
1995) as different jet fuel types (JP-4, Jet-4, JP-5, JP-8, or
JPTS).
Aboul-Kassim and Simoneit (1995a,b) have used a
variety of statistical techniques for source oil identifi-
cation. In their analysis of the aliphatic and aromatic
compositions in particulate fallout samples (PFS) in
 Z. Wang, M.F. Fingas / Marine Pollution Bulletin 47 (2003) 423–452
Alexandria (Aboul-Kassim and Simoneit, 1995a), mul-
tivariate statistical analyses, including extended Q-mode
factor analysis and linear programming, were performed
in order to reduce the hydrocarbon data set into a
meaningful number of end members (sources). Their
analysis indicated that there are two significant end
members explaining 90% of the total variation among
the samples and confirming petrochemical (79.6%) and
thermogenic/pyrolytic (10.4%) sources in the PFS model.
In a study of sediment samples in the Eastern Har-
bour (EH) of Alexandria (Aboul-Kassim and Simoneit,
1995b), a similar multivariate statistical approach, in-
cluding both factor analysis and linear programming
techniques, was used to determine the end member com-
positions and evaluate sediment partitioning and trans-
port in the EH area. In this study, Aboul-Kassim and
Simoneit determined that the untreated sewage was
the main source of petroleum hydrocarbons in the EH
area rather than direct inputs from boating activities or
urban run-off.
In a case study, Stout et al. (2001) reported a strategy
and methodology for defensibly correlating spilled oil to
source candidates. By using principle component anal-
ysis method (PCA), only six of the 29 vessels containing
oils were positively identified to be correlated to the
spilled oil.
The application of sophisticated statistical analysis
techniques to oil analysis is a relatively new and dy-
namic area of research which enhances the interpretive
power of petroleum hydrocarbon fingerprinting and
promises to greatly improve the identification of oil spill
sources.
10. Oil spill identification by petroporphyrins analysis and
by characterization of UCM
Porphyrins are naturally occurring pigments that are
composed of four pyrrole rings. These near-planar
structures are usually found in nature in the form of
metal complexes. The metalloporphyrins, also known as
petroporphyrins, found in crude oil are the product of
the metabolism of chlorophyll by microorganisms and
are usually complexed with metals they have scavenged
from the environment, predominately nickel and vana-
dium. The chemical identity of petroporphyrins varies
between sources, depending upon the biological condi-
tions inherent to each site. Using HPLC (Xu and Lesage,
1992), these various compounds can be differentiated
based on the different alkyl substituents attached to each
porphyrin ring. Each oil sample produces a petro-
porphyrin ‘‘fingerprint’’ which links the sample to its
geographic origins. By comparing these fingerprints, oils
from different origins can then be distinguished. Similar
to biomarker compounds, petroporphyrins break down
very slowly in the environment. This means that oil spills
443
can be matched to their sources even years after the spill
occurred by the use of petroporphyrin analysis. Appli-
cation of petroporphyrins (Xu et al., 1994) as chemical
indicators of soil contamination by crude oils has been
also reported.
Unresolved Complex Mixture (UCM), or ‘‘hump’’ of
hydrocarbons, are a common feature of the gas chro-
matograms of crude oils and certain refined products
such as lubricating oils, and it is especially pronounced
for weathered and biodegraded oils and oil-polluted
sediment extracts. It is perhaps surprising that virtually
little is known about UCM compositions and molecular
structures, even though the concentrations of these
components in oils are significant. Work by several au-
thors (Gough and Rowland, 1990, 1991; Killops et al.,
1990) have shown that oxidative degradation of UCM
yields some gas chromatographically resolved products.
It has been suggested that these products, which were
identified to be acids, lactones and ketones, may be
useful for ‘‘fingerprinting’’ UCM. The oxidation prod-
ucts of UCM isolated from sediments known to be
contaminated with a tank oil (Howells et al., 1986) have
been successfully used to identify the source oils. There
is much to be learned about UCM and the subject
should provide a fruitful area for further research.
11. Distinguishing biogenic hydrocarbons from petrogenic
hydrocarbons
Characterization and differentiation of hydrocarbons
from different sources is an essential part of any objec-
tive oil spill study. After oil spills, oil hydrocarbons of-
ten mix with other background hydrocarbon sources in
the impacted area. One of the potential sources of hy-
drocarbons contributing to the background is biogenic
hydrocarbons. Hydrocarbons from both anthropogenic
and natural sources including biogenic source are very
common in the marine and inland environments.
Biogenic hydrocarbons are generated either by bio-
logical processes or in the early stages of diagenesis in
recent marine sediments. Biological sources include land
plants, phytoplankton, animals, bacteria, macroalgae
and microalgae.
It has been recognized (Venkatesan, 1988; Cretney
et al., 1987; Kolattukudy, 1976; Blumer and Young-
blood, 1975; Page et al., 1995; Bence et al., 1996) that
the biogenic hydrocarbons have the following chemical
composition characteristics:
• n-alkanes show a distribution pattern of odd carbon-
numbered alkanes being much abundant than even
carbon-numbered alkanes in the range of n-C21 to
n-C33 , resulting in unusually high carbon preference
index (CPI) values, which is defined as the sum of
the odd carbon-numbered alkanes to the sum of the
444 Z. Wang, M.F. Fingas / Marine Pollution Bulletin 47 (2003) 423–452
even carbon-numbered alkanes (oils characteristically
have CPI values around 1.0);
• notable absence of the ‘‘unresolved complex mixture
(UCM)’’ hump in the chromatograms;
• pristane is often more abundant than phytane, sug-
gesting a phytoplankton input and resulting in abnor-
mally high pristane/phytane ratio values;
• presence of ‘‘biogenic cluster’’(identified as olefinic
hydrocarbons of biogenic origin) in the gas chroma-
tograms of the aromatic fractions; and
• wide distribution of the biogenic PAH perylene, an
unsubstituted PAH produced in subtidal sediments
by a process known as early diagenesis.
In a study of hydrocarbon biogeochemical setting of
the Baffin Island oil spill (BIOS) experimental site,
Cretney et al. (1987) found that the BIOS subtidal
samples showed very high pristane/phytane ratios (5–15)
and CPI values (3–11). High concentrations of pristane
relative to phytane in most of beach and subtidal sedi-
ments indicate biological hydrocarbon input from a
marine biological source. In addition, the GC chroma-
tograms of the aromatic fractions were typified by the
olefinic hydrocarbon clusters. This cluster is a common
feature of coastal marine subtidal sediments and is be-
lieved to be of marine biological (planktonic or bacte-
rial) origin. The possibility of in situ genesis of PAHs is
indicated by the presence of perylene as a major PAH in
almost all the beach and subtidal sediments, however, it
should be noted that it cannot be used alone as a de-
finitive source identification criterion because perylene is
also produced in combustion processes. In a recent
study of chemical characterization of oil residues in the
Baffin Island intertidal sediment samples, Wang et al.
(1995a) noted that the BIOS sample S-3 demonstrated
some distinct characteristics of biogenic hydrocarbons
including much higher abundance of odd n-alkanes than
even n-alkanes in the range of n-C21 –n-C33 and high CPI
and pristane/phytane values. However, the presence of
petrogenic hydrocarbons were also obvious, indicated
by the distribution of n-alkanes in a wide range from C15
to C40 and the notable presence of the chromatographic
UCM. This conclusion was further confirmed by the
presence of petrogenic PAH and biomarker compounds,
which showed similar distribution pattern to other oil
residue samples. Page et al., 1995, 1996 found that the
background alkane distribution in the PWS benthic
sediments is dominated by biogenic components.
During the years 1970–1972 the Nipisi, Rainbow and
Old Peace River pipeline spills occurred in the Lesser
Slave Lake area of northern Alberta. The Nipisi spill
was by far the largest of the three spills and is also one of
the largest land spills in Canadian history. The most
recent field survey was conducted in 1995 in order to
determine which cleanup methods were most successful,
and to provide up-to-date information about any
changes in residual oil and vegetative recovery 25 years
after the spills. The comprehensive chemical data (Wang
et al., 1998a) from analysis of the Nipisi samples indi-
cate the following:
• The Nipisi samples can be categorized into three
groups plus the background group, according to the
contamination level and degradation degree of the
samples.
• The background samples showed typical biogenic n-
alkane distribution in the range of C21 –C33 with abun-
dances of odd-carbon-number n-alkanes being much
higher than that of even-carbon-number n-alkanes.
The biogenic cluster was also obvious and no UCM
was observed (see Fig. 9). No petrogenic hydrocar-
bons, in particular no alkylated PAH homologues
and petroleum-characteristic biomarker compounds
such as pentacyclic hopanes and C27 –C29 steranes
were detected. In addition, three vegetation biomar-
ker compounds with remarkable abundances were de-
tected and identified.
• Hydrocarbons in the Group 3 samples taken from a
depth of 40–100 cm were identified to be mixtures
of vegetation hydrocarbons and lightly contaminated
oil hydrocarbons. Fig. 9 presents the GC chromato-
grams of two representative background and Group
3 samples, illustrating the differences between bio-
genic hydrocarbons from petrogenic hydrocarbons.
12. Distinguishing pyrogenic hydrocarbons from petro-
genic hydrocarbons
PAH distributions are the most useful tool in distin-
guishing pyrogenic hydrocarbons from petrogenic hy-
drocarbons. It has been recognized that in general,
pyrogenic PAHs are characterized by:
• the dominance of the unsubstituted compounds over
their corresponding alkylated homologues (i.e.,
skewed or sloped PAH distribution profile of C0 
C1 > C2 > C3 > C4),
• the dominance of the high molecular mass 4–6 ring
PAHs over the low molecular mass 2–3 ring PAHs,
and
• on the gross level PAH can comprise a much higher
mass percentage in most pyrogenic source materials
than in most petrogenic source materials (Bjøeseth,
1985; Benlahcen et al., 1997; Blumer and Young-
blood, 1975). In contrast, petrogenic PAHs exhibit
the characteristic bell-shaped distribution profiles,
which are readily modified to the distribution profile
of C0 < C1 < C2 < C3 by weathering or degradation.
As an example, Fig. 10 compares PAH fingerprints
for the 1994 Mobile Burn starting oil, burn residue, and
 Z. Wang, M.F. Fingas / Marine Pollution Bulletin 47 (2003) 423–452 445

Fig. 9. GC chromatograms of two representative Nipisi samples: background sample N3-1 (left, biologic hydrocarbons) and Group 3 sample R7-1
(right, mixture of vegetation hydrocarbons and lightly contaminated oil hydrocarbons), illustrating differences between petrogenic and biogenic
hydrocarbon distributions. Top panel (A) and (D): GC-FID chromatograms for total petroleum hydrocarbon (saturates and aromatics) analysis.
Sample R7-1 showed distribution of mixed petrogenic and biogenic n-alkanes, while Sample N3-1 showed only typical biogenic n-alkane distribution
in the range C21 –C33 . The biogenic cluster was also obvious and no UCM was observed. Middle panel (B) and (E): total ion GC–MS chromatograms
of aromatic fractions. Surrogate: o-terphenyl; internal standard (IS): d14 -terphenyl. Bottom panel (C) and (F): GC–MS chromatograms (m=z 191) of
saturated fractions. Petrogenic alkylated PAH homologues and biomarkers were detected in Sample R7-1. In contrast, No petrogenic PAHs and
biomarkers were detected in sample N3-1. However, three vegetation biomarkers with remarkable abundances were detected.

soot sample, illustrating the distinguishing features of
pyrogenic PAH distribution from the petrogenic PAH
distribution (Wang et al., 1999b). Fig. 11 compares ex-
tracted ion chromatograms at m=z 178, 228, 252, and
276 for the 1994 Mobile diesel, residue sample MB-16
and soot sample TSP-B3. The changes in relative dis-
tribution patterns of selected PAHs clearly demonstrate
the formation of pyrogenic PAH from 3-ring anthracene
to 6-ring indeno[1,2,3-cd]pyrene and benzo[ghi]perylene
due to combustion. The concentrations of PAHs with
five or more rings were many times greater in the smoke
than in oil.
In order to obtain an approximation of the hydro-
carbon input by the river Elbe into the North sea,
Theobald et al. (1995) performed UV–VIS, GC and
GC–MS measurements for over 2.5 years at a fixed
station at the freshwater edge of the Elbe to determine
the composition and concentration of hydrocarbons in
its water. The characterization results indicate three
types of hydrocarbons: some of them originate from
natural sources (plant waxes with predominance of odd-
chain n-alkanes); some originate from petroleum sources
(unresolved complex mixture), and some originate from
the incomplete combustion of fossil fuel (unsubstituted
PAHs). Gonzalez-Vila et al. (1991) investigated the in-
fluence of different burning conditions upon the PAH
patterns generated from combustion of pine biomass
and found that when burned at moderate temperature
for a long period of time, the most abundant homo-
logues generated were alkylated derivatives of naph-
thalene, whereas phenanthrene alkyl derivatives were
predominant after a forest wildfire, where higher tem-
peratures were reached in less time. More condensed
PAHs were detected only in minor amounts. Page et al.
(1999) and Bence et al. (1996) identified combustion
products throughout the marine environment in Prince
William Sound and Gulf of Alaska. Two components
of pyrogenic PAHs occur in the benthic sediments: a
446 Z. Wang, M.F. Fingas / Marine Pollution Bulletin 47 (2003) 423–452

94-MB Diesel Other 3-6 ring PAHs

3-ring
Naph
7000 100
Concentration (µg/g oil) 6000
80
60 4-ring
40
5- & 6-ring
5000
20
4000 0

Acl

Ace

An

Py

BaA

BbF

BkF

BeP

BaP

Pe

IP

DA

BP
Fl
3000 Dibenz
Fluo
2000 Phen 2-ring 3-6 ring PAHs
Chry
1000
0
C0-N
C1-N
C2-N
C3-N
C4-N
C0-P
C1-P
C2-P
C3-P
C4-P
C0-D
C1-D
C2-D
C3-D
C0-F
C1-F
C2-F
C3-F
C0-C
C1-C
C2-C
C3-C
Bph
Acl
Ace
An

Py
BaA
BbF
BkF
BeP
BaP
Pe

DA
BP
Fl

lP
94-MB Residue Other 3-6 ring PAHs
3-ring
4-ring
7000 100
5- & 6-ring
Concentration (µg/g oil)

80
6000 60
5000 40
20
4000 Dibenz 0
Phen

Fl
Acl

Ace

An

Py

BaA

BbF

BkF

BeP

BaP

Pe

IP

DA

BP
3000 Naph
2000 Fluo 3-6 ring PAHs
Chry
1000
0
C0-N
C1-N
C2-N
C3-N
C4-N
C0-P
C1-P
C2-P
C3-P
C4-P
C0-D
C1-D
C2-D
C3-D
C0-F
C1-F
C2-F
C3-F
C0-C
C1-C
C2-C
C3-C
Bph
Acl
Ace
An
Fl
Py
BaA
BbF
BkF
BeP
BaP
Pe
IP
DA
BP
94-MB Soot (PM10-B1) Other 3-6 ring PAHs
5- & 6-ring
400 160
3-ring
Concentration (µg/g soot)

350 120 4-ring

300 80

40
250
0
200

IP
FL
Acl

Ace

An

Py

BaA

BbF

BkF

BeP

BaP

Pe

BP
DA
Naph
150 3-6 ring PAHs
Phen
Dibenz Fluo Chry
100
50
0
C0-N

C2-N

C4-N

C1-P

C3-P

C0-D

C2-D

C0-F

C2-F

C0-C

C2-C

Bph

Ace

FL

BaA

BkF

BaP

IP

BP

94-MB Soot (TSP-B1) Other 3-6 ring PAHs

5- & 6-ring
400 160
3-ring 4-ring
Concentration (µg/g soot)

350 120
80
300
40
250 0
IP
FL
Acl

Ace

An

Py

BaA

BbF

BkF

BeP

BaP

Pe

BP
DA

200
150 Naph 3-6 ring PAHs
100 Phen Chry
Dibenz Fluo
50
0
C0-N
C1-N
C2-N
C3-N
C4-N
C0-P
C1-P
C2-P
C3-P
C4-P
C0-D
C1-D
C2-D
C3-D
C0-F
C1-F
C2-F
C3-F
C0-C
C1-C
C2-C
C3-C
Bph
Acl
Ace
An
Fl
Py
BaA
BbF
BkF
BeP
BaP
Pe
IP
DA
BP

Fig. 10. PAH fingerprints and distinguishing features of distribution patterns between petrogenic and pyrogenic PAHs for the starting oil, burn
residue, and soot samples from 1994 Mobile burn study. N, P, D, F, and C represent naphthalene, phenanthrene, dibenzothiophene, fluorene, and
chrysene, respectively; 0–4 represent carbon number of alkyl groups in the alkylated PAH homologous series. The abbreviations from Acl to BgP
represent the other EPA priority unsubstituted PAHs (please refer Table 2 for the full names of these PAHs). For comparison, the fingerprints of the
other 3–6 ring PAHs have been enlarged and shown in the left insets. Note that for clarity, different Y -axis scales are used for soot samples.

relatively uniform, low level, regional pre-spill back- local relatively high background, at some nearshore lo-
ground believed to be due to atmospheric input, and a cations, that is a consequence of current or historical
 Z. Wang, M.F. Fingas / Marine Pollution Bulletin 47 (2003) 423–452 447

Fig. 11. Comparison of representative extracted ion chromatograms at m=z 178, 228, 252, and 276 for the starting oil, burn residue MB-16, and soot
sample TSP-B3, illustrating changes in the relative distribution of unsubstituted PAH isomers and demonstrating the formation of pyrogenic PAHs
from 3-ring anthracene (An) to 6-ring indeno[1,2,3-cd]pyrene (IP) and benzo[ghi]perylene (BP) due to combustion. Refer Table 2 for the full names of
the remaining EPA priority unsubstituted PAHs shown in Fig. 2.

human activities. Probable local sources include the
burning of coal, diesel fuel, and wood at communities,
fish camps, and campsites, and creosote from marine
installations. Identification of pyrogenic components in
subtidal sediments is based entirely upon the PAH
fraction. The dominance of the 4–6-ring unsubstituted
PAHs was very distinct in the local source samples.
In field studies, it is often difficult to identify which
PAHs have been introduced from petrogenic or pyro-
genic sources. This is because there are many ways in
which PAHs are introduced into the environment that
the PAH signature from one source could be obscured
by PAHs from another source(s). In addition, under the
comparable combustion conditions, the same amount of
organic materials can yield largely different amount of
PAHs at different temperatures. Therefore, in addition to
qualitative criteria, quantitative criteria should be de-
fined to recognize sources of PAHs. Numerous quanti-
tative diagnostic ratios have been defined to differentiate
pyrogenic PAHs from other hydrocarbon sources
(Benlahcen et al., 1997; Blumer and Youngblood, 1975;
Lake et al., 1979; Sicre et al., 1987), including phe-
nanthrene/anthracene (Ph/An), phenanthrene/methyl-
phenanthrene (Ph/m-Ph), fluoranthene/pyrene (Fl/Py),
benz[a]anthracene/chrysene (BaA/Ch), Ph/(Ph + An),
benzo[e]pyrene/(benzo[e]pyrene + benzo[a]pyrene), and
indeno[1,2,3-cd]pyrene/(indeno[1,2,3-cd]pyrene + benzo-
[ghi]perylene). Benlahcen et al. (1997) reported a method
using the ratio phenanthrene/anthracene < 10 and fluo-
ranthene/pyrene > 1 to identify contamination sources of
combustion processes. By determination of characteris-
tic ratios of three pairs of unsubstituted PAHs, Bauza de
Mirabo et al. (1997) identified five pyrogenic hydrocar-
bon sources which might be potential sources of PAHs
in aerosol samples collected from semi-rural stations in
the island of Majorca (Spain). Zeng and Vista (1997)
applied several compositional indices of PAHs to iden-
tify the sources of PAHs in the coastal environment off
448 Z. Wang, M.F. Fingas / Marine Pollution Bulletin 47 (2003) 423–452
San Diego, California and concluded that PAHs de-
tected in the microlayer and sediments collected in 1994
in San Diego Bay were mainly derived from combustion
sources rather than oil spills, despite the heavy shipping
activities in the area.
In the 1994 Mobile burn study (Wang et al., 1999b),
we found that the Pyrogenic Index (which was defined as
the ratios of the total of the other EPA priority un-
substituted 3–6 ring PAHs toPthe total of five target
alkylated PAH homologues), (other 3–6 ring PAHs)/
P multiple sources
(5 alkylated PAHs), in the soot samples were signifi-
cantly different from that for crude oils and petroleum
products and can be positively used to differentiate the
pyrogenic and petrogenic PAHs. P For comparison, Fig.
12
P depicts the relative ratios of (other 3–6 ring PAHs)/
(5 alkylated PAHs) versus the relative ratios of phe-
nanthrene to anthracene determined from 1994 soot
samples and over 60 oils and petroleum products in-
cluding jet fuel, diesel, lube oil, Bunker C, Pand heavy
fuel. Fig. 12 Pdepicts the relative ratios of (other 3–6
ring PAHs)/ (5 alkylated PAHs) versus the relative
ratios of phenanthrene to anthracene using the data
obtained from this study. It can be clearly seen from Fig.
12 that the
P jet fuel, diesel, and most
P crudes show the
ratios of (other 3–6 ring PAHs)/ (5 alkylated PAHs)
to be smaller than 0.01 versus very scattered ratios of
phenanthrene/anthracene. Heavy oils (such as Cold
Lake Bitumen and Orimulsion) and heavy fuels (such as
IFO-180, A-02, IF-30, and Bunker C type oils) show
significantly higher ratios falling in the range of 0.01–
0.05 (clusters 1 and 2). In sharp contrast, the average
ratio for the six soot samples of 1994 Mobile Burns is as
high as 1.13 (in a range of 0.8–2.0). Obviously, this
P
Fig. 12. Plot of the relative ratios of ðother 3–6 ring PAHsÞ=
P
ð5-alkylated PAHsÞ over the relative ratios of phenanthrene/an-
thracene for over 60 oils and petroleum products. Lighter petroleum
P
products and P most crudes show the ratios of ðother 3–6
ring PAHsÞ= ð5-alkylated PAHsÞ fall into a range of 0–0.01, while
heavy oils and heavy fuels show significantly higher ratios in the range
of 0.01–0.05. The soot samples show the most striking increase in the
ratio, indicated by the right circle.
quantitative ratio, combined with other qualitative cri-
teria, can be used to unambiguously differentiate sources
of PAHs.
13. Allocation of complex hydrocarbons to multiple
sources
13.1. Quantitative allocation of complex hydrocarbons to
Chemical fingerprinting techniques to identify the
sources of environmental pollutants have been in use for
the last two decades and major advances have been
made in recent years to address difficult oil spill issues on
source identification and, in particular, quantitative al-
location of complex hydrocarbons to multiple sources.
The major approach used in source identification and
allocation in complex mixtures include pattern recog-
nition, source-specific diagnostic ratios of target ana-
lytes, and principal component analysis.
After the 1989 Exxon Valdez oil spill, contract re-
search organizations and university scientists collected
and analyzed thousands of sediment samples from the
spill area. These samples were found to contain hydro-
carbons from spill oil, diesel fuel, coal, combustion
products, creosote, products of natural biological pro-
cesses, and oil from natural oil seeps. Page et al. (1995,
1996, 1999) and Boehm et al. (1998, 2001) used these
advanced fingerprinting techniques, in particular distri-
butions of PAHs and double ratios of C2D/C2P to C3D/
C3P, to identify and allocate four major PAH sources in
the sediment samples: biological PAHs; combustion
product PAHs; natural petrogenic background PAHs
derived from oil seeps outside of the Sound; and pe-
troleum PAHs from ANS sources (i.e., either spilled oil
or diesel oil refined from ANS oil). Carbon isotopes and
terpane distribution distinguished Exxon Valdez resi-
dues found on shorelines from tars from other sources.
Diesel and diesel soot were identified by the absence of
alkylated chrysenes and a narrow distribution of n-alk-
anes, whereas pyrogenic products were distinguished by
the dominance of 4- to 6-ring PAHs over 2-to 3-ring
PAHs and by the dominance of non-alkylated over al-
kylated homologues of each PAH series. The back-
ground hydrocarbons present within Prince William
Sound and the Gulf of Alaska were identified to origi-
nate from natural oil seeps and eroding source rocks in
the same regions. Burns et al. (1997) developed a more
detailed method to more precisely allocate PAHs in
sediment samples to the PAH sources from which they
came. This new approach uses principal component
analysis to identify possible sources and a least-squares
model to find the source mix that gives the best fit of 36
PAH analytes (including chrysenes) in each sample. The
method identified 18 possible PAH sources within PWS
 Z. Wang, M.F. Fingas / Marine Pollution Bulletin 47 (2003) 423–452
of Alaska, including diesel oil, diesel soot, spilled crude
oil in various weathering states, natural background,
creosote, and combustion products from human activi-
ties and forest fires. The PCA and least-squares model-
ling procedures can be generalized to allocate PAHs or
other complex hydrocarbons to multiple sources in
other situations, including other spills.
Short and co-worker from the NOAA Auke Bay
Laboratory cited evidence based on the presence of coal
nearby beaches and the extensive coal measures between
Bering River and Ice Bay and agued that the back-
ground hydrocarbons come from such deposit (Short
et al., 1999).
Multivariate statistical techniques have become
available in recent years which allow signature to be
determined from source samples which can then be
quantitatively extracted from environmental samples. In
an attempt to resolve the issue of origin of background
hydrocarbons in the benthic sediments of PWS and the
Gulf of Alaska, Mudge (Mudge, 2002) uses this pow-
erful technique to reassess the percentage contribution
of coal, seep oil, shales and rivers to the hydrocarbon
loading in the Gulf of Alaska. The data analysis results
suggests mixed sources whose contributions vary sig-
nificantly across the sampling area.
13.2. Identification and allocation of multiple hydrocarbon
sources using the holistic approach and TOC
Total organic carbon, (TOC) is one important tool in
holistic approach to hydrocarbon source fingerprinting
(Boehm et al., 2002; Page et al., 2002). It can constrain
the contributions of specific sources and rule out in-
correct source allocation in cases where inputs are
dominated by fossil organic carbon. In a study of a
benthic sediments from Prince William Sound (PWS)
and the Gulf of Alaska (GOA), Boehm et al. found
excellent agreement between measured TOC and TOC
calculated from hydrocarbon fingerprinting matches of
PAH and biomarkers. Confirmation by two indepen-
dent source indicators (TOC and fingerprint matches)
provides evidence that source allocation determined by
fingerprint matches are robust and that the major TOC
sources have been correctly identified. They concluded
that the natural petrogenic hydrocarbon background in
sediments this area comes from eroding Tertiary shales
and associated oils seeps along the northern GOA coast.
14. Conclusions
The advances in petroleum hydrocarbon fingerprint-
ing and data interpretation methods and approaches in
the last two decades have now allowed for detailed
qualitative and quantitative characterization of spilled
oils. Chemical fingerprinting is a powerful ‘‘tool’’ for
449
hydrocarbon source identification and differentiation,
when it is applied properly. However, in many cases,
particularly for complex hydrocarbon mixtures or ex-
tensively weathered and degraded oil residues, there is
no single fingerprinting technique which can meet the
objectives of forensic investigation and quantitatively
allocate hydrocarbons to their respective sources.
Combined and integrated multiple ‘‘tools’’ are often
necessary under such situations.
Development in hydrocarbon fingerprinting tech-
niques will continue as analytical and statistical methods
evolve. It can be anticipated that these developments
will further enhance the utility and defensibility of oil
hydrocarbon fingerprinting.
References
Aboul-Kassim, T.A.T., Simoneit, B.R.T., 1995a. Aliphatic and
aromatic hydrocarbons in particulate fallout of Alexandria, Egypt:
sources and implications. Environ. Sci. Technol. 29, 2473–2483.
Aboul-Kassim, T.A.T., Simoneit, B.R.T., 1995b. Petroleum hydrocar-
bon fingerprinting and sediment transport assessed by molecular
biomarker and multivariate statistical analyses in the Eastern
Harbour of Alexandria, Egypt. Mar. Pollut. Bull. 30, 63–73.
ASTM Method 3328-90 1997a. In: Annual Book of ASTM Standards,
Water (II), vol. 11.02. American Society for Testing and Materials,
Philadelphia, PA.
ASTM Method 5037-90 1997b. In: Annual Book of ASTM Standards,
Water (II), vol. 11.02. American Society for Testing and Materials,
Philadelphia, PA.
ASTM Method 5739-95 1997c. In: Annual Book of ASTM Standards,
Water (II), vol. 11.02. American Society for Testing and Materials,
Philadelphia, PA.
Barakat, A.O., Mostafa, A., El-Gayar, M.S., Rullkotter, J., 1997.
Source-dependent biomarker properties of five crude oils from the
Gulf of Suez. Egypt Org. Geochem. 26, 441–450.
Barakat, A.O., Qian, Y., Kim, M., Kennicutt M.C., II. 2002.
Compositional changes of aromatic steroid hydrocarbons in
naturally weathered oil residues in the Egyptian Western Desert.
In: Proceedings of the 25th Arctic and Marine Oil Spill Program
(AMOP) Technical Seminar. Environment Canada, Ottawa. pp.
477–488.
Bauza de Mirabo, F., Mateu, J., Forteza, R., Cerda, V., Colom, M.,
Oms, M., 1997. Determination of aliphatic and aromatic com-
pounds in aerosols collected at two semi-rural stations in Majorca
(Spain). J. Environ. Sci. Health. A 32, 1415–1433.
Bence, A.E., Kvenvolden, K.A., Kennicutt II, M.C., 1996. Organic
geochemistry applied to environmental assessments of Prince
William Sound, Alaska, after the Exxon Valdez oil spill––a review.
Org. Geochem. 24, 7–42.
Bence, A.E., Burns, W.A., 1995. Fingerprinting hydrocarbons in the
biological resources of the Exxon Valdez spill area. In: Wells, P.G.,
Butler, J.N., Hughes, J.S. (Eds.), Exxon Valdez Oil Spill: Fate and
Effects in Alaska Waters. ASTM STP 1219. ASTM, Philadelphia,
PA, pp. 84–140.
Benlahcen, K.T., Chaoui, A., Budzinski, H., Bellocq, J., Garrigues, P.,
1997. Distribution and sources of polycylic aromatic hydrocarbons
in some Mediterranean coastal sediments. Mar. Pollut. Bull. 34,
298–305.
Bieger, T., Hello, J., Abrajano Jr., T.A., 1996. Petroleum biomarkers
as tracers of lubricating oil contamination. Mar. Pollut. Bull. 32,
270–274.
450 Z. Wang, M.F. Fingas / Marine Pollution Bulletin 47 (2003) 423–452
Bjøeseth, A., 1985. Sources of emissions of PAH. In: Bjøeseth, A.,
Ramdahl, T. (Eds.), Handbook of Polycyclic Aromatic Hydrocar-
bons. Marcel Dekker, New York, pp. 1–20.
Blumer, M., Youngblood, W.W., 1975. Polycyclic aromatic hydrocar-
bons in soils and recent sediments. Science 188, 53–55.
Boehm, P.D., Douglas, G.S., Burns, W.A., Mankiewicz, P.J., Page,
D.S., Bence, A.E., 1997. Application of petroleum hydrocarbon
chemical fingerprinting and allocation techniques after the Exxon
Valdez oil spill. Mar. Pollut. Bull. 34, 599–613.
Boehm, P.D., Page, D.S., Gilfillan, E.S., Bence, A.E., Burns, W.A.,
Mankiewicz, P.J., 1998. Study of the fate and effects of the Exxon
Valdez oil spill on benthic sediments in two bays in Prince William
Sound, Alaska. 1. Study design, chemistry and source fingerprint-
ing. Environ. Sci. Technol. 32, 567–576.
Boehm, P.D., Page, D.S., Burns, W.A., Bence, A.E., Mankiewicz, P.J.,
Brown, J.S., 2001. Resolving the origin of the petrogenic hydro-
carbon background in Prince William Sound. Alaska Environ. Sci.
Technol. 35, 471–479.
Boehm, P.D., Burns, W.A., Page, D.S., Bence, A.E., Mankiewicz, P.J.,
Brown, J.S., Douglas. G.S., 2002. Total organic carbon, an
important tool in holistic approach to hydrocarbon source finger-
printing. In: Proceedings of the 25th Arctic and Marine Oil Spill
Program (AMOP) Technical Seminar, Environment Canada,
Ottawa, pp. 413–428.
Bragg, J.R., Owens, E.H., 1994. Clay-oil flocculation as a natural
cleansing process following oil spill: Part 1––studies of shoreline
sediments and residues from past spills. In: Proceedings of the 17th
Arctic and Marine Oil Spill Program (AMOP) Technical Seminar.
Environment Canada, Ottawa, Ontario, pp. 1–25.
Brown, J.S., Boehm, P.D., 1993. The use of double ratio plots of
polynuclear aromatic hydrocarbon (PAH) alkyl homologues for
petroleum source identification. In: Proceedings of the 1993
International Oil Spill Conference, American Petroleum Institute,
Washington, DC, pp. 799–801.
Burns, W.A., Mankiewicz, P.J., Bence, A.E., Page, D.S., Parker, K.R.,
1997. A principal-component and least-squares method for allo-
cating sediment hydrocarbons to multiple sources. Environ.
Toxicol. Chem. 16, 1119–1131.
Butler, E.L., Douglas, G.S., Steinhauter, W.S., Prince, R.C., Axcel, T.,
Tsu, C.S., Bronson, M.T., Clark, J.R., Lindstrom, J.E., 1991.
Hopane, a new chemical tool for measuring oil biodegradation. In:
Hinchee, R.E., Olfenbuttel, R.F. (Eds.), On-site Reclamation.
Butterworth-Heinemann, Boston, MA, pp. 515–521.
Chen, J., Fu, J., Sheng, G., Liu, D., Zhang, J., 1996. Diamondoid
hydrocarbon ratios: novel maturity indices from highly mature
crude oils. Org. Geochem. 25, 179–190.
Christensenand, L.B., Larsen, T.H., 1993. Method for determining the
age of diesel oil spills in the soil. Ground Water Monitor.
Remediat. Fall, 142–149.
Cretney, W.J., Green, D.R., Fowler, B.R., Humphrey, B., Fiest, D.L.,
Boehm, P.D., 1987. Hydrocarbon biogeochemical setting of the Baffin
Island oil spill experimental site, I, Sediments. Arctic 40, 51–55.
Dahl, J.E., Moldowan, J.M., Peters, K.E., Claypool, G.E., Rooney,
M.A., Michael, G.E., Mello, M.R., Kohnen, M.L., 1999. Dia-
mondoid hydrocarbons as indicators of natural oil cracking.
Nature 399, 54–57.
Daling, P.S., Faksness, L.G., Hansen, A.B., Stout. S.A., 2002.
Improved and standardized methodology for oil spill fingerprint-
ing. In: Proceedings of the 25th Arctic and Marine Oil Spill
Program (AMOP) Technical Seminar, Environment Canada,
Ottawa, pp. 429–454.
Douglas, G.S., Bence, A.E., Prince, R.C., McMillen, S.J., Butler, E.L.,
1996. Environmental stability of selected petroleum hydrocarbon
source and weathering ratios. Environ. Sci. Technol. 30, 2332–
2339.
Dowling, L.M., Boreham, C.J., Hope, J.M., Marry, A.P., Summons,
R.E., 1995. Carbon isotope composition of hydrocarbons in ocean
transported bitumen from the coastline of Australia. Org. Geo-
chem. 23, 729–737.
EPA Methods for chemical analysis of water and wastes, EPA-600-4-
79-020, Environmental Monitoring and Support Laboratory.
Cincinnati, OH, 1983.
EPA Methods for Chemical Analysis of Water and Wastes 1986. US
EPA, Washington, DC, 1986.
EPA test methods for evaluating solid waste (SW-846). Update III, US
EPA, Office of Solid Waste and Emergency Response, Washington,
DC, 1997.
EPA Method, 1664, Revision A: n-Hexane extractable material and
silica gel treated n-hexane extractable material by extraction and
gravimetry. EPA-821-R-98-002, US EPA, Office of Water, Wash-
ington, DC, 1999.
Etkin, D.S. (Ed.), 1998. Nearly 300 million gallons of oil spilled into
US marine waters since 1960s. Oil Spill Intelligence ReportÕs White
Paper Series, vol. 2(2), Cutter Information Corp.
Fayad, N.M., Overton, E., 1995. A unique biodegradation pattern
of the oil spilled during the 1991 Gulf war. Mar. Pollut. Bull. 30,
239–246.
Fingas, M., 1995. A literature review of the physics and predictive
modelling of oil spill evaporation. J. Hazard. Mater. 42, 157–175.
Gains, R.B., Frysinger, G.S., Hendrick-Smith, M.S., Stuart, J.D.,
1999. Oil spill source identification by comprehensive two-dimen-
sional gas chromatography. Environ. Sci. Technol. 33, 2106–
2112.
Garrett, P.M., Pickerring, I.J., Haith, C.E., Prince, R.C., 1998.
Photooxidation of crude oils. Environ. Sci. Technol. 32, 3719–
3723.
Gonzalez-Vila, F.J., Lopez, J.L., Martin, F., del Rio, J.C., 1991.
Determination in soils of PAH produced by combustion of
biomass under different conditions. Frenes. J. Anal. Chem. 339,
750–753.
Gough, M.A., Rowland, S.J., 1990. Characterization of unresolved
complex mixture of hydrocarbons in petroleum. Nature 344, 648–
650.
Gough, M.A., Rowland, S.J., 1991. Characterization of unresolved
complex mixtures of hydrocarbons from lubricating oil feedstocks.
Energy Fuels 5, 869–874.
Hayes, J.M., Freeman, K.H., Popp, B.N., Hohan, C.H., 1990.
Compoundspecific isotope analysis: a novel tool fpr reconstruction
of ancient biogeochemical process. Org. Geochem. 16, 1115–1128.
Hostettler, F.D., Rosenbauer, R.J., Kvenvolden, K.A., 1999. PAH
refractory index as a source discriminant of hydrocarbon input
from crude oil and coal in Prince William Sound, Alaska. Org.
Geochem. 30, 873–879.
Howells, S., Patey, J., Turner, C., Dodd, N.M., 1986. Oil Pollution
Research Unit Report 27. Field Studies Council, Angle, Dyfed,
Wales.
Jordan, R.E., Payne, J.R., 1980. Fate and Weathering of Petroleum
Spills in the Marine Environment: A Literature Review and
Synopsis. Ann Arbor Science Publishers, Ann Arbor, Michigan.
Jokuty, P., Whiticar, S., Wang, Z.D., Fingas, M., Fieldhouse, B.,
Lambert, P., Mullin, J., 1999. Properties of Crude Oils and Oil
Products (Report Series No. EE-165). Environment Canada,
Ottawa, ON.
Kaplan, I.R., Alimi, M., Galperin, Y., Lee, R.P., Lu, S., 1995. Pattern
of chemical changes in fugitive hydrocarbon fuels in the environ-
ment. In: Presented at the 1995 SPE/EPA Exploration and
Production Environmental Conference, Houston, TX, March 27–
29, 1995, SPE Paper No. 29754.
Kaplan, I.R., Galperin, Y., Alimi, H., Lee, R.P., Lu, S., 1996. Pattern
of chemical changes during environmental alteration of hydrocar-
bon fuels. Ground Water Monitor. Remediat. Fall, 113–124.
Kaplan, I.R., Galperin, Y., Lu, S., Lee, R.P., 1997. Forensic
environmental geochemistry differentiation of fuel-types, their
sources, and release time. Org. Geochem. 27, 289–317.
 Z. Wang, M.F. Fingas / Marine Pollution Bulletin 47 (2003) 423–452
Kennicutt II, M.C., 1998. The effect of biodegradation on crude oil
bulk and molecular composition. Oil Chem. Pollut. 4, 89–112.
Kolattukudy, P.E., 1976. Chemistry and Biochemistry of Natural
Waxes. Elsevier, New York.
Krahn, M.M., Ylitalo, G.M., Buzitis, J., Chan, S., Varanasi, U., 1993.
Rapid HPLC methods that screen for aromatic compounds in
environmental samples. J. Chromatogr. 642, 15–32.
Kvenvolden, K.A., Rapp, J.B., Bourell, J.H., 1985. In: Magoon, L.B.,
Claypool G.E. (Eds.), Alaska North Slope Oil/Rock Correlation
Study, American Association of Petroleum Geologists Studies in
Geology, No. 20, pp. 593–617.
Kvenvolden, K.A., Hostettler, F.D., Rapp, J.B., Carlson, P.R., 1993.
Hydrocarbon in oil residues on beaches of islands of Prince
William Sound. Alaska Mar. Pollut. Bull. 26, 24–29.
Kvenvolden, K.A., Hostettler, F.D., Carlson, P.R., Rapp, J.B.,
Threlkeld, C.N., Warden, A., 1995. Ubiquitous tarballs with a
California-source signature on the shorelines of Prince William
Sound. Alaska Environ. Sci. Technol. 29, 2684–2694.
Lake, J.L., Norwood, C., Dimock, C., Bowen, R., 1979. Origins of
PAHs in estuarine sediments. Geochim. Cosmochim. Acta 43,
1847–1854.
Lavine, B.K., Mayfield, H., Kromann, P.R., Faruque, A., 1995.
Source identification of underground fuel spills by pattern recog-
nition analysis of high-speed gas chromatograms. Anal. Chem. 67,
3846–3852.
Leahy, J.G., Colwell, R.R., 1990. Microbial degradation of hydrocar-
bons in the environment. Microbial Rev. 54, 305–315.
Lundanes, E., Greibrokk, T., 1994. Separation of fuels, heavy
fractions, and crude oils into compound classes: a review. J. High
Resolut. Chromatogr. 17, 197–202.
Mansuy, L., Philp, R.P., Allen, J., 1997. Source identification of oil
spills based on the isotopic composition of individual components
in weathered oil samples. Environ. Sci. Technol. 31, 417–3425.
Mazeas, L., Budzinski, H., 2002. Molecular and stable carbon isotope
source identification of oil residues and oiled bird feathers samples
along the Atlantic Coast of France after the Erika oil spill.
Environ. Sci. Technol. 36, 130–137.
McKirdy, D.M., Cox, R.E., Volkman, J.K., Howell, V.J., 1986.
Botryococcane in a new class of Australian non-marine crude oils.
Nature 320, 57–59.
Mudge, S.M., 2002. Reassessment of the hydrocarbons in Prince
William Sound and the Gulf of Alaska: identifying the source using
partial least-squares. Environ. Sci. Technol. 36, 2354–2360.
Munoz, D., Guiliano, M., Doumenq, P., Jacquot, F., Scherrer, P.,
Mille, G., 1997. Long term evolution of petroleum biomarkers in
mangrove soil. Mar. Pollut. Bull. 34, 868–874.
Noble, R.A., Alexander, R., Kagi, R.I., Knox, J., 1986. Identification
of some diterpenoids hydrocarbons in petroleum. Org. Geochem.
10, 825–829.
OÕMalley, V.P., Abrajano, T.A., Hellou, J., 1994. Determination of the
13
C/12 C ratios of individual PAH from environmental samples: can
PAH sources be apportioned? Org. Geochem. 21, 809–822.
OÕMalley, V.P., Abrajano, T.A., Hellou, J., 1996. Stable carbon
isotopic apportionment of individual PAHs in St. JohnÕs harbour,
Newfoundland. Environ. Sci. Technol. 30, 634–639.
Page, D.S., Boehm, P.D., Douglas, G.S., Bence, A.E., 1995. Identi-
fication of Hydrocarbon Sources in the Benthic Sediments of
Prince William Sound and the Gulf of Alaska Following the Exxon
Valdez Spill. In: Wells, P.G., Butler, J.N., Hughes, J.S. (Eds.),
Exxon Valdez Oil Spill: Fate and Effects in Alaska Waters. ASTM,
Philadelphia, PA, pp. 41–83.
Page, D.S., Boehm, P.D., Douglas, G.S., Bence, A.E., Burns, W.A.,
Mankiewicz, P.J., 1996. The natural petroleum hydrocarbon
background in subtidal sediments of Prince William Sound,
Alaska, USA. Environ. Toxicol. Chem. 15 (8), 1266–1281.
Page, D.S., Boehm, P.D., Douglas, G.S., Bence, A.E., Burns, W.A.,
Mankiewicz, P.J., 1999. Pyrogenic PAHs in sediments record past
451
human activity: a case study in Prince William Sound. Alaska Mar.
Pollut. Bull. 38 (4), 247–260.
Page, D.S., Bence, A.E., Burns, W.A., Boehm, P.D., Douglas. G.S.,
2002. A holistic approach to hydrocarbon source allocation in the
subtidal sediments of Prince, William Sound, Alaska, Embay-
ments. In: Proceedings of the 25th Arctic and Marine Oil Spill
Program (AMOP) Technical Seminar, Environment Canada,
Ottawa, pp. 547–563.
Peters, K.E., Moldowan, J.W., 1993. The Biomarker Guide : Inter-
preting Molecular Fossils in Petroleum and Ancient Sediments.
Prentice-Hall, New Jersey.
Philp, R.P., 2002a. Application of stable isotopes and radioisotopes in
environmental forensics. In: Murphy, B.L., Morrison, R.D. (Eds.),
Introduction to Environmental Forensics. Academic Press, Lon-
don, pp. 99–136. Chapter 5.
Philp, R.P., Allen, J., Kuder, T., 2002. The use of isotopic composition
of individual compounds for correcting spilled oils and refined
products in the environment with suspected sources. In: Proceed-
ings of the 25th Arctic and Marine Oil Spill Program (AMOP)
Technical Seminar, Environment Canada, Ottawa, pp. 565–580.
Pond, K.L., Huang, Y., Wang, Y., Kulpa, C.F., 2002. Hydrogen
isotopic composition of individual n-alkanes as an intrinsic tracer
for bioremediation and source identification of petroleum contam-
ination. Environ. Sci. Technol. 36, 724–728.
Prince, R.C., 1993. Petroleum Spill Bioremediation in Marine Envi-
ronment. Crit. Rev. Microbial 19, 217–242.
Prince, R.C., Elmendorf, D.L., Lute, J.R., Hsu, C.S., Haith, C.E.,
Senius, J.D., Dechert, G.J., Douglas, G.S., Butler, E.L., 1994.
17a(H), 21b(H)-hopane as a conserved internal marker for
estimating the biodegradation of crude oil. Environ. Sci. Technol.
28, 142–145.
Sasaki, T., Maki, H., Ishihary, M., Harayama, S., 1998. Vanadium as
an internal marker to evaluate microbial degradation of crude oil.
Environ. Sci. Technol. 32, 3618–3621.
Sauer, T.C., Boehm, P.D., 1991. The use of defensible analytical
chemical measurements for oil spill natural resource damage
assessment. In: Proceedings of the 1991 Oil Spill Conference.
American Petroleum Institute, Washington DC, pp. 363–370.
Sauer, T.C., Brown, J.S., Boehm, P.D., Aurand, D.V., Michel, J.,
Hayes, M.O., 1993. Hydrocarbon source identification and weath-
ering characterization of intertidal and subtidal sediments along
the Saudi Arabian coast after the Gulf war oil spill. Mar. Pollut.
Bull. 27, 117–134.
Sauer, T.C., Boehm, P.D., 1995. Hydrocarbon chemistry analytical
methods for oil spill assessments. Technical Repot 95-032. Marine
Spill Response Corporation, Washington, DC.
Sauer, T.C., Michel, J., Hayes, M.O., Aurand, D.V., 1998. Hydrocar-
bon characterization and weathering of oiled intertidal sediments
along the Saudi Arabian Coast two years after the Gulf war oil
spill. Environ. Int. 24, 43–60.
Seifert, W.K., Moldowan, J.M., Demaison, G.J., 1984. Source
correlation of biodegraded oils. Org. Geochem. 6, 633–643.
Shen, J., 1984. Minimization of interferences from weathering effects
and use of biomarkers in identification of spilled crude oils by
gas chromatography/mass spectrometry. Anal. Chem. 56, 214–
217.
Short, J.W., Jackson, T.J., Larsen, M.L., Wade, T.L., 1996. Analytical
methods used for the analysis of hydrocarbons in crude oil tissues
sediments and seawater collected for the natural resources damage
assessment of the Exxon Valdez oil spill. Am. Fish. Soc. Symp. 18,
140–148.
Short, J.W., Heintz, R.A., 1997. Identification of Exxon Valdez oil in
sediments and tissues from Prince William Sound and the
Northwestern Gulf of Alaska based on a PAH weathering model.
Environ. Sci. Technol. 31, 2375–2384.
Short, J.W., Kvenvolden, K.A., Carlson, P.R., Hostettler, F.D.,
Rosenbauer, R.J., Wright, B.A., 1999. Natural hydrocarbon
452 Z. Wang, M.F. Fingas / Marine Pollution Bulletin 47 (2003) 423–452
background in benthic sediments of Prince William Sound, Alaska:
oil vs. coal. Environ. Sci. Technol. 33, 34–42.
Short, J.W., 2002. Oil identification based on a goodness-of-fit metric
applied to hydrocarbon analysis results. In: Proceedings of the 25th
Arctic and Marine Oil Spill Program (AMOP) Technical Seminar,
Environment Canada, Ottawa, pp. 581–592.
Sicre, M.A., Marty, J.C., Salion, A., Aparicio, X., Grimalt, J.,
Albaiges, J., 1987. Aliphatic and aromatic compounds in aerosols.
Atmos. Environ. 21, 2247–2259.
Stout, S.A., Uhler, A.D., Naymik, T.G., McCarthy, K.J., 1998.
Environmental forensics: unravelling site liability. Environ. Sci.
Technol. 32, 260A–264.
Stout, S.A., Uhler, A.D., McCarthy, K.J., 2001. A strategy and
methodology for defensibly correlating spilled oil to source
candidates. Environ. Forens. 2, 87–98.
Stout, S.A., Uhler, A.D., McCarthy, K.J., Emsbo-Mattingly, S., 2002.
Chemical fingerprinting of hydrocarbons. In: Murphy, B.L.,
Morrison, R.D. (Eds.), Introduction to Environmental Forensics.
Academic Press, London, pp. 137–260. Chapter 6.
Theobald, N., Rave, A., Jerzycki-Brandes, K., 1995. Input of
hydrocarbons into the North Sea by the river Elbe. Fresen. J.
Anal. Chem. 353, 83–87.
Venkatesan, M.I., 1988. Occurrence and possible sources of perylene in
marine sediments––a review. Mar. Chem. 25, 1–27.
Wang, Z.D., Fingas, M., Li, K., 1994a. Fractionation of ASMB oil,
identification and quantitation of aliphatic aromatic and biomar-
ker compounds by GC/FID and GC/MSD. J. Chromatogr. Sci. 32,
361–366 (Part I) and 367–382 (Part II).
Wang, Z.D., Fingas, M., Sergy, G., 1994b. Study of 22-year-old Arrow
oil samples using biomarker compounds by GC/MS. Environ. Sci.
Technol. 28 (9), 1733–1746.
Wang, Z.D., Fingas, M., Sergy, G., 1995a. Chemical characterization
of crude oil residues from an Arctic beach by GC/MS and GC/FID.
Environ. Sci. Technol. 29 (10), 2622–2631.
Wang, Z.D., Fingas, M., 1995b. Use of methyldibenzothiophenes as
markers for differentiation and source identification of crude and
weathered oils. Environ. Sci. Technol. 29 (11), 2841–2849.
Wang, Z.D., Blenkinsopp, S., Fingas, M., Sergy, G., Landriault, M.,
Sigouin, L., Foght, J., Semple, K., Westlake, D.W.S., 1997a.
Chemical composition changes and biodegradation potentials of
nine Alaska oil under freshwater incubation conditions. Symp. Am.
Chem. Soc. 43 (3), 828–835 (preprints).
Wang, Z.D., Fingas, M., Landriault, M., Sigouin, L., Feng, Y.,
Mullin, J., 1997b. Using systematic and comparative analytical
data to identify the source of unknown oil on contaminated birds.
J. Chromatogr. 775, 251–265.
Wang, Z.D., Fingas, M., Blenkinsopp, S., Sergy, G., Landriault, M.,
Sigouin, L., 1998a. Study of the 25-year-old Nipisi oil spill:
persistence of oil residues and comparisons between surface and
subsurface sediments. Environ. Sci. Technol. 32 (15), 2222–2232.
Wang, Z.D., Fingas, M., Landriault, M., Sigouin, L., Castle, B.,
Hostetter, D., Zhang, D., Spencer, B., 1998b. Identification and
linkage of tarballs from the coasts of Vancouver Island and
Northern California using GC/MS and isotopic techniques. J. High
Resolut. Chromatogr. 21, 383–395.
Wang, Z.D., Fingas, M., Blenkinsopp, S., Sergy, G., Landriault, M.,
Sigouin, L., Foght, J., Semple, K., Westlake, D.W.S., 1998c.
Comparison of oil composition changes due to biodegradation and
physical weathering in different oils. J. Chromatogr. A 809, 89–107.
Wang, Z.D., Fingas, M., Page, D., 1999a. Oil Spill Identification.
J. Chromatogr. 843, 369–411.
Wang, Z.D., Fingas, M., Shu, Y.Y., Sigouin, L., Landriault, M.,
Lambert, P., 1999b. Quantitative characterization of PAHs in burn
residue and soot samples and differentiation of pyrogenic PAHs
from petrogenic PAHs––the 1994 Mobile burn study. Environ. Sci.
Technol. 33, 3100–3109.
Wang, Z.D., Fingas, M., Landriault, M., Sigouin, L., Grenon, S., Zhang,
D., 1999c. Source identification of an unknown spilled oil from
Quebec (1998) by unique biomarker and diagnostic ratios of ‘‘source-
specific marker compounds’’. Environ. Technol. 20, 851–862.
Wang, Z.D., Fingas, M., Owens, E.H., Sigouin, L., Brown, C.E., 2001.
Long-term fate and persistence of the spilled Metula oil in a marine
salt marsh environment: degradation of petroleum biomarkers.
J. Chromatogr. 926, 190–275.
Wang, Z.D., Fingas, M., Sigouin. L., 2002. Using multiple criteria for
fingerprinting unknown oil samples having very similar chemical
composition. In: Proceedings of the 25th Arctic and Marine Oil
Spill Program (AMOP) Technical Seminar, Environment Canada,
Ottawa, pp. 639–660.
Whittaker, M., Pollard, S.J.T., Fallick, T.E., 1995. Characterization of
refractory wastes at heavy oil-contaminated sites: a review of
conventional and novel analytical methods. Environ. Technol. 16,
1009–1033.
Whittaker, M., Pollard, S.J.T., Fallick, A.E., Preston, T., 1996.
Characterisation of refractory wastes at hydrocarbon-contami-
nated sites 11: screening of reference oils by stable carbon isotope
fingerprinting. Environ. Pollut. 94, 195–203.
Williams, J.A., Bjorøy, M., Dolcater, D.L., Winters, J.C., 1986.
Biodegradation in South Texas Eocene oils: effects on aromatics
and biomarkers. Org. Geochem. 10, 451–461.
Xu, H., Lesage, S., 1992. Separation of vanadyl and nickel petropor-
phyrins on an aminopropyl column by HPLC. J. Chromatogr. 607,
139–144.
Xu, H., Lesage, S., Brown, S., 1994. Petroporphyrins as chemical
indicators of soil contamination by crude oil. Chemosphere 28,
1599–1609.
Zakaria, M.P., Horinouchi, A., Tsutsumi, S., Takada, H., Tanabe, S.,
Ismail, A., 2000. Oil pollution in the Straits of Malacca, Malaysia:
Application of molecular markers for source identification. Envi-
ron. Sci. Technol. 34, 1189–1196.
Zeng, E.Y., Vista, C.L., 1997. Organic pollutants in the coastal
environment off San Diego, California.1. Source identification and
assessment by compositional indices of polycyclic aromatic hydro-
carbons. Environ. Toxicol. Chem. 16, 179–188.