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Petroleum Fingerprinting with Organic Markers

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Petroleum Fingerprinting with Organic Markers

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Frances D. Hostettler , Thomas D. Lorenson & Barbara A. Bekins
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US Geological Survey , Menlo Park , CA , USA
Published online: 20 Nov 2013.

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 Environmental Forensics, 14:262–277, 2013
ISSN: 1527-5922 print / 1527-5930 online
DOI: 10.1080/15275922.2013.843611

Invited Articles

Petroleum Fingerprinting with Organic Markers

Frances D. Hostettler, Thomas D. Lorenson, and Barbara A. Bekins

US Geological Survey, Menlo Park, CA, USA

Petroleum fingerprinting is an invaluable tool in forensic geochemistry. This article summarizes applications of fingerprinting in several
oil spills and natural oil seepages that we have studied during the last 25 years. It shows how each unique chemical fingerprint can be
used to correlate or differentiate oils. Fingerprints can provide information about processes in the environment that impact oils such
as weathering and microbial degradation. They can be used to evaluate organic matter that contributed to oils, and classify oils with
Downloaded by [Barbara Bekins] at 09:32 21 November 2013

regard to the geological framework of their source, such as evaluating geological facies, age, lithology, and depositional environment.

Keywords: petroleum fingerprinting, tarballs, depositional environment, biomarkers, diesel, biodegradation

Introduction Throughout 25 years our laboratory has utilized many differ-

Crude oil (petroleum), refined petroleum products, natural oil
seeps, and petrogenic sediments all contain thousands of di-
verse organic compounds. Although there are similarities in
the chemicals and chemical families contained in various pet-
rogenic species, there are also individual differences in con-
centrations and relative amounts of the oil constituents. These
differences can be measured, allowing a unique chemical fin-
gerprint to be determined for each petroleum entity. Diagnostic
ratios of constituent oil components are most commonly used
in an oil fingerprint. The numerical values of ratios allow math-
ematical and statistical operations to be applied to compare ele-
ments within a data set. In some cases, specific oil components,
such as individual markers or a profile of a homologous series
of related compounds, not incorporated in a ratio, are used in
characterizing the oil. Carbon isotope values of whole oils or
compound-specific values (δ 13C) are also useful as part of the oil
fingerprint. In general, multiple criteria are needed for a chem-
ical fingerprint, and selecting and applying appropriate param-
eters allows fine-tuning of each fingerprint. The fingerprints,
then, provide a powerful forensic tool that can be used to differ-
entiate oils, to correlate oils from the same or similar sources, to
follow degradation pathways after exposure of the oil to weath-
ering in the environment, to investigate geological conditions
under which the oil was formed, and to characterize different
refinery products. They are also useful in distinguishing petro-
genic hydrocarbons from biogenic and pyrogenic (combustion)
hydrocarbons.
This article not subject to US copyright law.
Address correspondence to Frances D. Hostettler, US Geological
Survey, 345 Middlefield Road, Menlo Park, CA 94025, USA. E-mail:
fdhostet@usgs.gov
262
ent chemical parameters in forensic fingerprints to investigate
and characterize several petroleum systems, such as oil spills,
natural petroleum seeps, and production oils. In the sections be-
low we will discuss the wide range of compounds and compound
classes that we have used in various petroleum fingerprints or
used to track changes like biodegradation within an oil system.
We will list the various molecular ratios or markers that have
been included in data sets of multiple petroleum entities and the
statistical methods used to correlate, differentiate, or otherwise
evaluate them. Finally, we will describe several studies where
we have applied these techniques and the kinds of questions that
forensic fingerprinting has helped to answer.
Characteristic Compounds and Derived Parameters
in an Oil Fingerprint
These are the categories of oil compounds that we have found
useful with respect to chemical fingerprints. Aliphatic and aro-
matic hydrocarbon classes of compounds are included; inor-
ganic parameters were not utilized. Structures of compounds
discussed below are given in Appendix 1.
From these various oil components, diagnostic fingerprint
parameters were determined, such as component ratios, specific
markers, and homolog profiles. Carbon isotope values, both
of whole oils and compound-specific were utilized in some of
the studies. The parameters used in our studies are defined in
Appendix 2.
Aliphatic Hydrocarbons
n-Alkanes
This is the simplest hydrocarbon family, containing just car-
bon and hydrogen in a straight carbon chain configuration. The
 Petroleum Fingerprinting 263

family begins with methane (C1 ) and contains homologs up to

C40 or C50 or higher. n-Alkanes are usually the most prominent
components of an oil or oil product accumulation that has not
been exposed to any environmental degradation. The n-alkane
distribution can easily be traced by GC/MS by monitoring m/z
57 on an extracted ion chromatogram (EIC). In crude oils, espe-
cially thermally mature oils, the n-alkane distribution can cover
a wide range, frequently has a roughly bell-shaped distribution,
with a mid-range homolog maximum (Cmax), and in most cases
no odd or even carbon number preference throughout the distri-
bution (Peters and Moldowan, 1993). This lack of an odd-even
predominance is different from many biogenic (plant) n-alkane
distributions, which frequently have a distinct odd carbon num-
ber predominance. In addition, plant n-alkane distributions seem
to have a natural protection from losses to biodegradation and
thus maintain their distributions in the environment longer than
petrogenic n-alkanes.
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In petrogenic accumulations exposed to weathering, n-

alkanes are subject to rapid degradation; indeed, they are the
first group of compounds to be lost to degradation (Kaplan
et al., 1997). A typical loss with time is shown for the oil spill
at Bemidji, MN in Figure 1 (adapted from Bekins et al., 2005).
Therefore, petrogenic n-alkanes are useful for correlative finger-
printing only if they have not been exposed to aerobic or anaero-
bic biodegradation or other kinds of weathering. However, they
are quite useful in assigning or tracking early stages of biodegra-
dation. Knowledge of the biodegradation state of a spilled oil
is essential in order to evaluate which fingerprint parameters
remain constant and thus are still reliable for forensic compar-
isons. Under aerobic oxidation conditions n-alkanes are well
known to show progressive losses from the low end of the distri-
bution (Kaplan et al., 1997, Peters and Moldowan, 1993). This
appears to also be true under anaerobic conditions up through
sulfate oxidation (Davidova et al., 2005). However, under anaer-
obic methanogenic conditions, commonly found in the environs Figure 1. Constituent extracted ion chromatograms (m/z 57) of oil samples
of long-term confined sub-surface oil spills depleted in oxygen collected in 1983 and 1999 from the same location within the oil column
like that in Bemidji, as well in a fuel oil spill in Mandan, ND, in the Bemidji oil spill. The 1983 sample was only slightly biodegraded
with n-alkane (C10 -C32 ) levels greater than isoprenoids (pristane, Pr and
some studies have shown that losses progress from the high end phytane, Ph), whereas in the 1999 sample n-alkanes have all been lost to
of the distribution (Hostettler and Kvenvolden, 2002; Siddique biodegradation. Figure adapted from Hostettler et al., 2008.
et al., 2006), and may even result in enhancement of low-end
homologs (Hostettler et al., 2007; Stout and Lundegard, 1998).
This enhancement is very important to recognize in assigning Cyclic alkanes
contaminant refinery products contributing to a long-term fuel This diverse family includes single-ring compounds, such as
oil spill. cyclopentanes or cyclohexanes, and fused ring compounds with
up to five or six rings. The following are particularly prominent
in oils and have been useful in our studies.

Branched chain alkanes n-Alkylcyclohexanes. This subgroup occurs in crude oils as a

These compounds are hydrocarbons consisting of a central
carbon chain with branch attachments of methyl, ethyl, and/or
other small hydrocarbon groups. The most prominent family
of branched chain hydrocarbons found in oils is the isoprenoid
family, usually dominated by the C19 and C20 members, pristane
and phytane. They are ubiquitous in oils and are somewhat more
refractory than n-alkanes (Kaplan et al., 1997).
homologous series like the n-alkanes, although at lower con-
centrations. Its members have a cyclohexane ring with a ho-
mologous n-alkyl side chain having lengths from C1 to C24 or
higher. Their distribution can be profiled by GC/MS by mon-
itoring m/z 83 on an EIC. As with n-alkanes these homologs
frequently have a quasi bell-shaped distribution with an ap-
proximately mid-range Cmax. Since they are somewhat more
 264 F. D. Hostettler et al.
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Figure 2. Chromatograms of typical tarball samples from offshore southern California. Total ion chromatogram of aliphatic (A) and aromatic (B)
fractions, selected ion monitoring (SIM) chromatograms of m/z 191 (C), and m/z 217 (D,E,F). Compounds identified in Appendix 1 and 2. Figure adapted
from Hostettler et al., 2004.
resistant to weathering than n-alkanes, their distributions can be
used to follow the progress of oil biodegradation beyond loss
of n-alkanes. They are currently being effectively used to evalu-
ate the progression of methanogenic biodegradation in concert
with other physical measurements at the Bemidji oil spill site
(Bekins et al., 2012). As with n-alkanes in a methanogenic en-
vironment, the distribution experiences progressive preferential
losses from its high end (Hostettler and Kvenvolden, 2002) and
enhanced levels at the low end (Hostettler et al., 2007; 2008).
Again, knowledge of this progression is important in assigning
co-contaminant input in petroleum product spills, since the in-
creases at the low end of the distribution can mimic input from
lower temperature refinery products.
Cyclohexanes, Other Alkyl-Substituted. Another family of sub-
stituted cyclohexanes were frequently present in many of the
southern California shoreline tarballs and seep oils, namely the
1,1,3-trimethyl-2-alkyl (isoprenoidal, C4 -C11 side chain) cyclo-
hexanes (Hostettler et al., 2004). These compounds served as
markers for some of the Monterey Miocene oil and tarball fam-
ilies (see the distribution in Figure 2A), but they are subject
to weathering loss after n-alkanes and isoprenoids and are not
useful for diagnostic ratios in the fingerprint, since many tar-
ball samples are weathered beyond the stability of this family
group.
Bicyclic Alkanes. There are a wide variety of bicyclic alkanes
found in petroleum and petroleum products, including sesquiter-
penes. Many of these are biomarkers, marking specific oil fami-
lies, depositional environments, maturity, diagenesis or other oil
characteristics. They are common in mid-range refinery prod-
ucts like diesel oil. One family of markers found in diesel are the
drimanes, monitored at m/z 123 (Figure 3). These compounds
can be used in the fingerprint to correlate diesel oil samples in
a spill (Wang et al., 2005, Hostettler et al., 2007).

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Figure 3. A typical extracted ion chromatogram at m/z 123 of the drimane
sesquiterpane series, with a cross-plot of suggested ratios to compare the
Mandan, ND, samples with unrelated diesel standards. Figure adapted from
Hostettler et al., 2007.
Tri-, Tetra-, and Pentacyclic Biomarkers. Biomarkers, or
molecular fossils, are organic compounds in petroleum and
sediments that are of biogenic origin. The precursor biogenic
molecules lose their functional groups and are reduced to sat-
urated hydrocarbons during diagenesis and catagenesis as the
organic matter matures and forms oil during burial. They retain
their hydrocarbon skeletons, but their stereochemistry changes
from a biological configuration to geological epimers. A very
thorough compilation of biomarkers and their GC/MS spec-
tra and likely sources is given in Philp (1985), including some
biomarkers mentioned above (e.g., isoprenoids, drimanes). The
biomarkers most widely used in petroleum fingerprinting are the
ubiquitous families of terpanes (including hopanes) and ster-
anes. Their usefulness comes from their universal presence in
oils and their highly refractory nature; they have relatively high
molecular weights and are among the last groups of petrogenic
compounds to be lost to weathering or biodegradation (Kaplan
et al., 1997).
Hopanes. These are tri-, tetra-, and pentacyclic fused ring
compounds, derived from the biogenic bacteriohopanetetrol
found in the lipid membranes of prokaryotic organisms (Pe-
ters and Hostettler, 2005). Several of their structures are shown
in Appendix 1; stereochemistry is not shown, but it is included in
the geochemical parameter list, Appendix 2. A typical GC/MS
profile, m/z 191, is shown in Figure 2C. Diagnostic ratios of
hopanes that we have commonly used in fingerprinting are given
in Appendix 2.
Steranes. These fused ring compounds are derived from bio-
genic sterols common to eukaryotes, higher organisms such as
algae, plants and animals. In oils the most commonly found ster-
Petroleum Fingerprinting 265
anes are epimers of C27 , C28 , and C29 cholestane, although other
smaller and larger molecular weight steranes are known. Typical
GC/MS profiles, m/z 217, are given in Figure 2D and 2F, and a
severely biodegraded profile in Figure 2E. The diagnostic ratios
we have used in petroleum fingerprinting appear in Appendix 2.
Aromatic Hydrocarbons
Single-ring aromatics
This group is composed of benzene and alkylated benzene
derivatives. Of use in petroleum fingerprinting studies are the
following:
BTEX Compounds. This group includes benzene, toluene,
ethylbenzene and the three xylene isomers. They are gener-
ally too volatile, water-soluble or biodegradable to be useful in
an oil fingerprint, but their evolving concentrations in ground-
water plumes are widely used to trace or evaluate contaminant
migration and degradation processes after oil spills (e.g., Essaid
et al., 2011, and references therein).
n-Alkyl Benzenes. Oils frequently contain a sequence of homol-
ogous n-alkylated benzenes similar to the n-alkylcyclohexanes
described above. These compounds are also subject to progres-
sive biodegradation losses like the n-alkylcyclohexanes, and
can be used to follow the degradation process (Hostettler et al.,
2007).
Isoprenoidal Benzenes. A series of 2-isoprenoidal-1,3,4-
trimethyl benzenes were found to be useful as markers for De-
vonian oils in some Kentucky oils and source rocks (Taylor and
Hostettler, 2002).
Multi-ring aromatics
Polycyclic Aromatic Hydrocarbons (PAHs). Naphthalene (N),
phenanthrene (P), dibenzothiophene (D) and chrysene (C)
and their alkylated derivatives (C0 (parent), C1 (monomethyl),
C2 , and C3 ) are the most prominent groups of aromatics in
petroleums. Bar graphs showing the concentrations of each of
these suites of compounds, and specific compound ratios have
both been found useful in oil fingerprints (Hostettler et al.,
2001). The PAHs in oils are impacted by degradation in the
order of increasing molecular weights, i.e., N>P∼ = D>C and
C0 >C1 >C2 >C3 . Another PAH, perylene, is also occasionally
useful in fingerprints. This PAH, however, is generally not in-
trinsic to an oil, but derives from biogenic input to near-surface
sediments. Shallow seep oils can pick it up from sediments as
the oil migrates (Venkatessan, 1988), and so it can be used as an
indicator of a shallow-sourced oil rather than a deep horizon oil.
Aromatic Steranes. Monaromatic steroids (MAS) and triaro-
matic steroids (TAS) are derived from the progressive aromati-
zation of steranes during diagenesis and catagenesis (Peters and
Hostettler, 2005). They are among the most recalcitrant com-
pounds in the oil matrix. MAS are found in both the aliphatic
 266 F. D. Hostettler et al.
and aromatic fractions of oils (Figures 2A and 2B) because they
have both aliphatic and aromatic characteristics in their struc-
tures; they are specifically monitored at m/z 253. TAS are found
in the aromatic fraction of oils (Figure 2B) and are monitored at
m/z 231. MAS and TAS are most commonly used as maturity
indicators in oils because MAS diminish and TAS increase with
thermal maturity (Peters and Moldowan, 1993).
Polar organics
These compounds, aromatic molecules that contain oxygen,
nitrogen or sulfur atoms, are very minor constituents of oils
and refined oil products, and so are almost never used for oil
fingerprinting. However, a novel method of utilizing polar com-
ponents, which are different in various refinery products due to
the different ranges of distillation temperatures used in each re-
finery cut (e.g., Figure 4), uses negative electrospray ionization
mass spectrometry. Most oil hydrocarbons are invisible to this
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technique, allowing the method to search out the very minor
polar constituents, giving simple spectra of the dominant polar
organics in each refinery fuel. For example, it was found that
gasoline was dominated by C1 , C2 and C3 alkylated phenols, jet
fuel by higher molecular weight alkylated phenols, kerosene by
an unknown compound, and diesel by alkylated carbazoles. This
method provides a very simple and fast way of distinguishing
between different refinery products (Rostad, 2006).
Methods for Statistically Sorting Large Data Sets
In several of our studies, especially when the data set was rela-
tively small, the samples were sorted by inspection of applicable
parameter ratios, looking for values that agreed within a narrow
range, e.g., approximately +/-10%. Sample groupings were es-
tablished by a similarity of multiple parameter ratios.
Later studies used multivariate and factor analysis (software
JMP Statistical Discovery using hierarchal cluster analysis and
principal component analysis) on a table of data calculated from
applicable parameters to sort the samples into groups, again by
Figure 4. Refinery distillation progression for fuel oil products, from
Volatile to Refractory. Diesel fuel and kerosene are mid-range distillates
(data from Kaplan et al., 1997).
a similarity of many parameter ratio values. The narrow ratio
ranges were determined by the statistical protocols of the soft-
ware used. When the groupings were established, the ranges
were again seen to be +/-10% or less (e.g., Hostettler et al.,
2004). These techniques can also group the parameters accord-
ing to each parameter’s contribution to the variance, and thus
allow interpretation about the geochemical process that the pa-
rameter might reflect, both with respect to the specific com-
pounds and to the oil itself.
For the largest data sets a more extensive chemometric
method was used (Peters et al., 2008; Lorenson et al, 2011).
This method incorporated hierarchical cluster analysis (HCA)
and principal component analysis (PCA), along with K-nearest
neighbor (KNN) and soft independent modeling of class analogy
(SIMCA), in a commercial software package from Infometrix,
Inc. Starting with a data base of nearly 700 oil and tarball
samples from the borderlands of southern California, a smaller
subset of samples (388) was chosen as a “training set”. These
samples were culled from the larger group on the basis that
biodegradation of their suite of sterane components had not yet
occurred (i.e., lower than rank 6 on the 1-10 biodegradation
scale of Peters and Moldowan, 1993). Nineteen parameter ra-
tios from this fingerprint data compilation were then compared
using a chemometric decision tree and the results used to estab-
lish genetic oil families (Table 1). The repeatability and standard
deviation of each parameter are included in Peters et al., 2008.
Three major groups (“tribes”) were observed with several in-
ternal groups (“families”) in each. After the training set was
established, the remaining samples were evaluated using the
chemometric decision tree, and most could be classified within,
or closely related to, one of the three tribes and their subsets of
families.
Results: Examples of Specific Studies Using Chemical
Fingerprints
Exxon Valdez Oil Spill (EVOS), 1989
Within a few months after the EVOS US Geological Survey
(USGS) scientists began collecting samples of beached tars and
oil residues along the coastline of Prince William Sound (PWS).
The aim was to characterize oil in the geological record of the
shore to see if it was spill-related. Preliminary screening of
the oils by measuring the bulk carbon isotope (δ 13C) parameter
values showed two distinct oils were present, one the spilled
EVO with values centering on –29.2% and the other a heavier
oil with values averaging -23.8%. Other fingerprint parameters
used to correlate the oils are given in Table 1; δ 13C and the
m/z 191 “Triplet” (example of the Triplet can be seen in Fig-
ure 2C) were particularly diagnostic. Further investigation on
samples collected from 1989 to 1997, led to the conclusion that
the heavier oil/tar was Monterey Formation oil from California
(Kvenvolden et al., 1993). This crude oil was used in Alaska
before North Slope Crude was discovered in 1968 and subse-
quently developed in 1974. Oil from California was shipped
 Petroleum Fingerprinting 267

Table 1. Fingerprinting parameters used in different studies (see Appendix 1 and 2 for chemical structures and parameter definitions)

Exxon Valdez Oil Spill studies

a. Initial screening: δ 13C, m/z 191 Triplet
b. USGS samples from 1989-1997: δ 13C; m/z 191: Tm/Ts, Triplet, C30 /C29 , C31 S/(S+R), BTO; m/z 217: C29 S/(S+R), C28 /C29
c. Petrogenic hydrocarbons in northern GOA continental shelf sediments: [PAH], [TPAH], MSE, DPI ( = C2D/C2P), OI, PAH-RI
Coastal California studies
a. Coastal tar residues and sediments in the Monterey Bay National Marine Sanctuary:
δ 13C; Pr/Ph; m/z 191: Tm/Ts, Triplet, 23T/C30 , C30 /C29 , C31 S/(S+R), BI, OI, GI; m/z 217: C29 S/(S+R), C28 /C29 ; PAH-RI
b. Refinery oil spill in San Francisco Bay:
m/z 191: Tm/Ts, 23T/C30 , C29 /C30 , C31 S/(S+R); m/z 217: βαDC27 /αααC29 , C29 S/(S+R); aromatic: MP/P, DMP/P, T/DMP
c. Santa Barbara Channel Island tarballs (preliminary, informational):
δ 13C, Pr/Ph, Tm/Ts, Triplet, 23Tri/C30 , 23Tri/24Tri, C30 /C29 , C31 S/(S+R), BI, OI, GI, T177 /C30 , C29 S/(S+R), C28 /C29 , Dominant
Sterane(s), α27R/Hop, nor26&27/Hop, α27R/nor27, PAH-RI, T/(T+M), C2D/C2P, C3D/C3P, Pery/Chr
d. Santa Barbara Channel Island tarballs (for HCA: 19 parameters including regular steranes, 15 (bold) excluding regular steranes):
δ 13C; m/z 191: Tm/Ts, Triplet, 23Tri/C30 , 23Tri/24Tri, C30 /C29 , BI, OI, GI, T177 /C30 ; m/z 217: C29 S/(S+R), C28 /C29 ,
α27R/nor27, nor26&27/Hop, α27R/nor27; PAH-RI, T/(T+M), C2D/C2P, C3D/C3P
e. Families of Miocene Monterey crude oil, seep, and tarball samples, coastal California (for chemometric analysis, 19 parameters):
δ 13C; m/z 191: Ts/Tm, C26 /Tet ( = Triplet), C28 /C29 TT, C20 /C23 TT, C22 /C21 TT, C24 /C23 TT, C26 /C25 TT, C31 S/H, C29 H/H,
C35 /C34 S, C29 Ts /C29 H, BNH/H, Ol/H, G/H; m/z 217: C28 /C29 ; aromatic: PAH-RI, C2D/C2P, C3D/C3P
Petroleum hydrocarbons in regional aquifer, Louisville, Kentucky
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Pr/Ph; m/z 191: Tm/Ts, Triplet, C30 /C29 , C31 S/(S+R), GI; m/z 217: C29 S/(S+R), Sterane distribution; PAH-RI
Mandan, ND, diesel fuel investigation
Water Resources Investigations Report: δ 13C, Pr/Ph, n-C17 /Pr, n-Cmax, C1D/C1P, C2D/C2P, C1N/C2N, 1,2,4-TMB/2MN
Forensic Fingerprinting: PAH quantitative profiles, drimane sesquiterpane ratios (Figure 3), C2D/C2P vs. C3D/C3P crossplot;
EIC profiles of n-alkanes (m/z 57), n-alkylcyclohexanes (m/z 83), n-alkylbenzenes (m/z 91), isorenieratane fragments (m/z 133);
Compound-specific carbon isotope (δ 13C) profiles of n-alkanes; mixing ratios of diesel and kerosene: Pr/Ph, C4 Bz/Drimane
2010 Deepwater Horizon oil spill, Gulf of Mexico
Parameters used in chemometric analysis: m/z 191: Ts/Tm, Triplet, 20Tri/23Tri, 22Tri/21Tri, 24Tri/23Tri, 26Tri/25Tri, 28Tri/29Tri,
C30 /C29 , 29D/29H, C31 S/C30 , 35S/34S; m/z 217: C28 /C29 , C27DS/C29S

by barge and stored in huge tanks in places like the port of
Old Valdez on PWS. The tanks were ruptured during the Great
Earthquake (magnitude 9.2) of 1964 and the oil was dispersed
catastrophically into PWS. This spill was never documented,
however, because of the chaos of dealing with the earthquake.
Kvenvolden et al. (1995) was the first paper to document both
oils as primary contributors to the geologic record of PWS.
Other work was done to track the EVO both on shorelines and
in the waters of PWS, both to see where it might have landed
and what chemical changes it might have undergone with time
(Hostettler and Kvenvolden, 1994).
Further work utilizing EVO petrogenic fingerprints followed
when Exxon scientists began publishing studies claiming oil
seeps at Katalla, located just onshore in the Gulf of Alaska
(GOA), were the source of the significant levels of background
hydrocarbons coming from the GOA into deep-water sediments
of PWS (e.g., Page et al., 1995; Douglas et al., 1996; Bence
et al., 1996). This claim was an important environmental issue
because the background hydrocarbons in the sediments include
significant levels of PAHs, some of which are potentially toxic
to benthic biota. From Exxon’s point of view, if there was sub-
stantial petrogenic input already in the sediments, and if that
input was previously bioavailable to benthic organisms, then the
impact of and liability from the EVOS would be diminished. The
claim of Katalla seep oil input was challenged by Short et al.
(1999) using mathematical pattern similarity of PAH concentra-
tions in its fingerprint, and by Hostettler et al. (1999) introduc-
ing the fingerprint parameter PAH-Refractory Index (PAH-RI),
a biomarker parameter defined in Appendix 2. Both of these
studies cast doubt on a Katalla seep oil contribution to GOA
sediments, and both suggested that coal was a more likely con-
tributor, since several parameters matched more closely with
coal. In addition, the benthic background PAHs showed little
sign of weathering, which would not be true of oil contamina-
tion, but would be true of an entity like coal, since PAHs in
coal are tightly bound within the coal matrix and not subject to
weathering. Also, this matrix makes PAHs in species like coal
and shale less bioavailable to benthic biota, whereas PAHs in oil
are more bioavailable and capable of causing adverse effects in
exposed biota.
Coal as the PAH source was challenged (e.g., Bence et al.,
2000), but soon Exxon scientists dropped Katalla seep oil as a
potential PAH source, and suggested onshore seeps at Yakataga.
This was again challenged by Short et al. (2007), both on the
basis of fingerprint elements and that there is insufficient output
of these seep hydrocarbons reaching the GOA to make the seeps
an important contributor to the benthic background in PWS.
Ultimately, Short et al. (2007), in agreement with a prior sug-
gestion of its potential contribution by Boehm et al. (2001), pro-
posed that glacial flour, derived from the erosion of formations
like the organic-rich shale of the Kultieth Formation overrid-
den by the Malaspina Glacier, is the dominant source of the
benthic hydrocarbons in PWS. The geochemical fingerprints
of the glacial flour closely matches that of the benthic sedi-
ments (Boehm et al., 2001), its shale matrix, like that of coal,
would protect against weathering, and its input would constitute
 268 F. D. Hostettler et al.
a massive hydrocarbon influx to the northern GOA sediments.
A longer summary of this evolved research study is given in
Peters et al. (2005).
The body of work involving PAHs also illustrates, in agree-
ment with comments from one of the reviewers of this paper, that
PAH profiles alone, especially in an extremely complex matrix
like benthic sediments, do not serve well in forensic research.
PAHs are ubiquitous in the environment with very diverse pet-
rogenic, pyrogenic (combustion) and biogenic sources, and have
highly variable susceptibility to natural weathering.
Tarballs, Natural Oil Seeps and Production Oils From
California
Extending the work on California Monterey Formation oil in
Alaska, USGS undertook several studies of tarballs, oils and
natural oil seeps along the California coast. One goal was to try
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to differentiate between products of natural seeps and anthro-
pogenic contamination. The studies included:
Coastal tar residues from central California
Kvenvolden et al. (2000) looked at tar residues along the
coastline of the Monterey Bay National Marine Sanctuary (MB-
NMS). This is an area where production and distribution of
petroleum is prohibited, and no significant offshore oil seeps
were known at the time (Lorenson et al., 2002), so it might
be expected to be relatively free of petrogenic contamination.
However, tar residues were found at high-tide lines at many
locations along the coast. Chemical fingerprints of each sam-
ple were used to correlate the samples, and then compare
them to the fingerprints of oils and tars from possible local
near-shore sources. Although all the tars, oils, and potential
source tars were clearly shown to be derived from the Mon-
terey Formation, no specific source could be attributed to the
beached tarballs. However, the suggestion of long distance ocean
transport from offshore natural seeps was raised for further
consideration.
In addition, a study of chemical fingerprints of organic
matter in recent sediments in MBNMS was performed for
baseline information (Kvenvolden et al., 2002). Here it was
found that the near-surface sediment had low levels of or-
ganic compounds dominated by biogenic hydrocarbons from
marine and terrigenous sources. A few samples near the mouth
of San Francisco Bay included an anthropogenic combustion
signature, that is, prominent non-alkylated PAHs fluoranthene
and pyrene. All the samples contained low background lev-
els of petroleum-related biomarkers, which included oil-mature
hopanes with Monterey Formation markers 28,30-bisnorhopane
and oleanane, and Triplet parameter values consistent with
Monterey-sourced crude oil, in addition to immature steranes,
as well as triaromatic steroids. Kvenvolden et al. (2002) sug-
gested that these petroleum-related compounds came from
eroded Monterey Formation rocks or traces of natural petroleum
seepage.
Refinery oil spill into San Francisco Bay, California
In April, 1988, approximately 1500 m3 of a San Joaquin
Valley crude oil were accidentally released from a refinery near
Martinez, CA. The oil flowed into Carquinez Strait and Suisun
Bay in northern San Francisco Bay. Sediment and oil samples
were collected and analyzed for petroleum marker compounds
in order to track the chemical fingerprint of the oil in the bay
sediment. The results showed that the oil impact to bay sediments
was extremely patchy, even within an area of heavy oil exposure
(Hostettler et al., 1992).
Tarballs and seep oils in the Santa Barbara Channel
The southern California coastal area near Santa Barbara and
the Channel Islands is known to be an extremely productive
oil-generating area, particularly from the carbon-rich Miocene
Monterey Formation. Natural offshore oil seeps leak oils that
are continually weathered and washed up on local beaches as
tarballs. Offshore oil platforms produce oil along the shoreline
from offshore Huntington Beach to Point Arguello. The question
of sources of beached tarballs is ongoing, with the possibility of
contamination from natural seeps or accidental anthropogenic
spillage from oil platforms or oil transportation. USGS began a
cooperative study with the US Minerals Management Service,
now the Bureau of Ocean Management (BOEM) and the Uni-
versity of California, Santa Barbara, to investigate these tarballs,
along with seep oils and platform oils, to see if specific source
groups could be determined. Hostettler et al. (2004) describes
early results from this study.
Chemical fingerprints of 128 samples of seep oils and tar-
balls were analyzed by HCA using 19 fingerprint parameters
(Table 1). In the process, it was observed from fingerprint pa-
rameters and GC/MS chromatograms that many samples were
quite similar except for differing m/z 217 (sterane) profiles,
indicating that biodegradation of sterane components was an
important factor impacting some but not all of the tarballs (ster-
ane chromatograms of three different tarball samples are given
in Figure 2D, 2E, and 2F). This meant that sterane parameters
were undependable as correlation factors. Therefore the four
regular sterane parameters were removed from the fingerprints
and a new statistical analysis done with the 15 remaining param-
eters. Then the samples separated into seven different groups.
Four of the groups were very small. Mapping the locations of
the samples within each group gave considerable information
about possible source locations of seepage, chemical character
of the groups, degradation processes impacting tars, and prob-
able long-distance dispersal of some of the tarballs by ocean
currents. The chemical fingerprints of samples in this study
began a library of oil fingerprints for future work on natural and
anthropogenic oils along the southern California coastline.
Age, lithology, organic matter input and depositional
environment of coastal California oils
The data set from the tarball study was expanded to include
additional tarballs, production oils, potential source rocks and
more natural seeps (Peters et al., 2008). In total 676 samples were

included in this aspect of the study. The large sample set was
treated statistically as described above. This analysis resulted
in separation of the oil samples into three major divisions, or
“tribes”, with subsets of “families” in each tribe. These, in turn,
could be further classified through each group’s fingerprint pa-
rameters and mapping of the samples to give information about
the age, depositional environment and source rock lithologies
under which the oils were formed. Tribes 1, 2, and 3 were postu-
lated to originate from suboxic marine shale, suboxic to anoxic
marl, and anoxic carbonate source rock lithologies, respectively.
Fingerprint parameters that were particularly helpful in delineat-
ing these characteristics were: C22 /C21 TT, C24 /C23 TT, C29 H/H,
and C35 /C34 S; C26 /Tet ( = Triplet), and PAH-RI also show dif-
ferences in anoxic origins, with Triplet values diminishing with
increasingly anoxic lithologies and PAH-RI increasing. Geo-
graphically, samples from Tribes 1 and 2 occur mainly south
and Tribe 3 north of Pt. Conception. It is mostly Tribe 3 tarballs
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that are found in MBNMS and north up to Point Reyes, per-
haps transported long distances by ocean currents. Information
on the age, lithology and depositional environment interpreted
from the parameters and geographic locations of the oils and
tars contributed substantially to interpretations about the geo-
logic setting of the Monterey Formation in offshore California.
Distinguishing naturally occurring seep oils from
anthropogenically derived platform oils
Lorenson et al. (2009, 2011) have added direct submarine
seep samples, production oils, and random tarballs from a storm
event to the coastal California data set, and classified them
within the chemometric decision tree mentioned above. Fig-
ure 5 is a map of all the samples within the data set described
in sections c, d, and e of Table 1, and the Tribes in which
they have been classified. Considering the whole data set, they
found that platform-produced oils fell only within Tribes 1 and
2, that many of the different Tribe’s families could be placed
in distinct geographical locations, and that Tribe 3 is widely
dispersed by ocean currents. Another important conclusion is
that the combination of the chemometric decision tree using the
petroleum fingerprint parameters and the presence or absence of
n-alkanes and isoprenoids are the most useful factors in differ-
entiating anthropogenic production oils from natural seep oils
and tars. Production oils in this sample set all contain n-alkanes
and isoprenoids, whereas the surficially sourced seep oils and
tars have lost theirs to biodegradation. Finally, Lorenson et al.
(2011) concludes that oil seepage from natural offshore seeps
is responsible for the great majority of tarball accumulations on
southern California beaches.
Evaluating Petroleum in the Silurian-Devonian Carbonate
Aquifer, South-Central Louisville, Kentucky
A cooperative study (US Department of Navy and USGS) of
a regional carbonate aquifer near Louisville, Kentucky was un-
dertaken to provide information to environmental regulators and
planners about the ground-water quality and hydrogeology of
Petroleum Fingerprinting 269
the area. Included in this study (Taylor and Hostettler, 2002)
was an investigation into the source of petroleum hydrocarbons
occurring in bedrock strata in the study area. Fingerprinting
analysis of nine shale, limestone, and borehole oil samples indi-
cated that both source rock (shale) and expelled oil (limestone
facies and borehole oils) were present, and that the source rock
samples were significantly less mature than the oil/limestone
samples. However, all the samples are relatable in that they
all share a particular set of markers typical of Devonian oils,
namely a suite of 2-alkyl-1,3,4-trimethyl benzenes (where the
alkyl substituents are homologous isoprenoidal side chains; see
Appendix 1). This correlation indicated that all the petrogenic
samples were of natural and not anthropogenic origin.
Methanogenic Biodegradation Impacting Long-Term Oil
Spills, Mandan, ND, and Bemidji, MN
Chronic spillage (1953–1991) of diesel fuel in and around a
railroad yard and refueling depot in Mandan, ND, resulted in
an estimated accumulation of 1.5-3.0 million gallons of diesel
product constrained within a clay and sand aquifer and float-
ing on the water table about 20 feet below the city’s downtown.
USGS was asked by the ND Dept. of Health to investigate the hy-
drologic setting and characterize the free-phase hydrocarbons,
particularly to determine if the light-nonaqueous-phase-liquid
(LNAPL) was diesel fuel used by the railroad and if there was
any co-contamination of other solvents or petroleum products.
Fingerprint parameters for a diesel fuel (Table 1) are very differ-
ent from those used in all the above studies, which were relevant
to crude oils and production oils. Diesel fuel is a refinery product
(see Figure 4) and its distillation range partitions out any of the
standard sterane and hopane biomarkers used for characterizing
whole oils. In addition, because the Mandan hydrocarbons had
been weathering in the environment for a long time, biodegra-
dation was very likely. Correlative parameters were chosen that
would not have been impacted by biodegradation (Table 1).
Other factors such as loss of n-alkanes or n-alkylcyclohexanes
were used to identify and track the degradation progression.
An extensive evaluation was made. The conclusions reported
to the ND Dept. of Health were: The geochemical analysis of
the LNAPL and correlations with other fuel products and addi-
tives strongly suggest episodic releases of a single, local-source,
diesel fuel into the aquifer over an extended period of time. The
diesel samples had undergone a variable loss of n-alkanes from
biodegradation, but no other co-contaminating fuel entity except
for a small trace of gasoline in one outlying shallow sample was
indicated within the geochemical fingerprints of the samples
(Hostettler et al., 2001).
Further work on the Mandan system tracked the n-alkane
degradation and showed that there was an unusual progression
(Figure 6). Unlike in aerobic systems, the methanogenic condi-
tions of the Mandan spill resulted in n-alkane losses from the
high molecular weight end of the distribution, with enhanced
low-end concentrations until the entire suite is fully degraded.
Also shown in Figure 6, the degradation of the whole oil, as well
 270 F. D. Hostettler et al.
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Figure 5. Map of coastal California showing all of the tarballs, natural seep samples, and production oils in the complete data set and the “tribes” to
which they belong according to statistical analysis. Map adapted from Lorenson et al., 2011.

as of the enhanced low-end n-alkanes (Hostettler et al., 2007)
proceeded with small increases in δ 13C values, a well-known
indicator of biodegradation. The same pattern of biodegradative
loss was also found to occur with the n-alkylcyclohexane suite
of compounds, that is, progressive loss from the high end of the
distribution and enhancement of low-end homologs (Hostettler
et al., 2002, 2007, 2008). In addition, this pattern was found
in the long-term crude oil spill in Bemidji, MN discussed be-
low. The similar losses of n-alkylcyclohexanes at Mandan and
Bemidji are shown in Figure 7.
The enhancement of the low-molecular weight homologs,
if not recognized as a degradative pathway of diesel fuel in a
methanogenic environment, can potentially be misinterpreted in
fuel-oil fingerprinting as deriving from lower distillation-range
fuels or admixture of diesel with other fuels. Indeed, that was the
interpretation of scientists working for the railroad. It was sug-
gested (Stout and Uhler, 2006) that the LNAPL samples from
Mandan away from the railyard contained significant amounts
of the lower temperature distillery product kerosene on the basis
of the increased low end n-alkanes and n-alkylcyclohexanes in
the LNAPL fingerprint. These authors, however, postulated no
potential source of kerosene. They did not recognize the pattern
of n-alkylcyclohexane loss progression in a more degraded sam-
ple from the railyard property where it had been claimed there

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Figure 6. n-Alkane profiles of six representative Mandan, ND, oil sam-
ples. Peaks from GC/MS analysis are normalized to a conserved internal
standard so that all samples are comparable. Samples are placed in order
of progressive overall loss of n-alkanes. The reference standard RR-40 is
non-degraded, and the remaining samples were recovered from sub-surface
wells in spill areas. Bulk δ 13C values are given for each oil. Figure adapted
from Hostettler et al., 2007.
Petroleum Fingerprinting 271
was no kerosene co-contamination. Our application of other
non-degraded biomarker parameters relevant to diesel fuel (e.g.,
drimanes (Figure 3), Wang et al., 2005) along with PAH con-
centration profiles (Hostettler et al., 2008) showed correlation
of all the Mandan LNAPL samples. As for evaluating possi-
ble co-contamination with kerosene, mixture parameters were
evaluated, and even the parameter ratio Pr/Ph helped because
this ratio is impacted (increased) in kerosene due to its refinery
distillation cut-off, and if mixed with diesel would show highly
variable values in the mixtures. All the Mandan LNAPL sam-
ples had consistent Pr/Ph values. Also, no sign of kerosene was
seen in the negative electrospray ionization mass spectrometry
technique mentioned above (Rostad, 2006). All of these many
different aspects of the chemical fingerprint of the petroleum
diesel fuel product contributed significantly to the evaluation of
the oil spill.
Crude Oil Spill Site in Bemidji, MN
In 1979 a crude oil spill from a ruptured pipeline occurred in
Bemidji, MN. The spill site became a USGS study site and has
been intensively monitored over the years, including studying
the chemical fingerprints of the subsurface oil column as it is
changed with biodegradation, the development of the contam-
inant plume in the water table, the microbiology of the sys-
tem, and the environmental impact. Relating to the Mandan
work, the same progression of n-alkane and n-alkylcyclohexane
biodegradation in a methanogenic environment was found to
occur (Bekins et al., 2005; Hostettler et al., 2007). Ongoing
studies at the Bemidji spill site over the years have contributed
greatly to the field of the environmental impact of oil spills, for
example by delineating the impact of microbial processes on
oil spills and contaminant plumes, using changing chemical fin-
gerprints to elucidate degradation processes, evaluating certain
fingerprint parameters (e.g., n-C17 /pristane, which was found
to be unreliable even in a single-incident spill like Bemidji in
determining the age of an oil spill in contrast to Christensen
and Larsen, 1993), evaluating nutrient recharge in driving vari-
ous processes (Bekins et al., 2005), and other discoveries such
as monitoring the scope of hydrocarbon remediation by natural
attenuation (Essaid et al., 2011).
2010 Deepwater Horizon Oil Spill in the Gulf of Mexico
An estimated 4.4 million barrels of crude oil spilled into the
northern Gulf of Mexico from the ruptured British Petroleum
Macondo-1 well beginning April 20. USGS scientists conducted
two studies of oil, tarballs, and sediments in the region, a pre-
impact study for baseline conditions and a reconnaissance post-
impact study after oil had reached some of the shorelines. The
pre-impact samples were collected from 70 sites along the coast-
lines of Texas, Louisiana, Mississippi, Alabama, and Florida that
could potentially be impacted by the spill (Rosenbauer et al.,
2011), and the post-impact sediment samples from a subset
of 48 of the original 70 pre-impact sites (Rosenbauer et al.,
 272 F. D. Hostettler et al.
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Figure 7. Extracted ion chromatograms (m/z 83, n-alkylcyclohexane profiles) of three progressively biodegraded samples from (A) Mandan, ND, and
(B) Bemidji, MN. Figure adapted from Hostettler et al., 2007.
2010). A known sample from the Macondo-1 well was used
as a reference. Petroleum fingerprinting was performed using a
suite of diagnostic petroleum biomarkers (Table 1), and multi-
variate analysis was used to correlate or differentiate the oils.
As with the above-discussed offshore California tars and oil
seeps, this chemical fingerprinting process allowed differentiat-
ing local oils in the Gulf. However, this study was not nearly as
comprehensive as the California tarball work, so oils potentially
derived from small seeps near the M-1 well were not addressed.
In the pre-impact study trace levels of three different oils, none
of which correlated with Macondo-1 well oil, were found in the
sediment record. In the post-impact study 11 of 49 sediment
samples and 17 of 20 tarballs from along the coasts of Alabama,
Mississippi, Louisiana and Florida were shown to be genetically
linked to the M-1 well oil, and six other samples were perhaps
a mixture of the M-1 oil with another oil. None of the sediment
hydrocarbon extracts from Texas correlated with the M-1 oil. All
this work helped delineate the areal extent of this enormous oil
spill and helped define the hydrocarbon background throughout
the impacted area.
Conclusions
Chemical fingerprints of petroleum and petroleum products are
shown to be a very valuable forensic tool with a wide variety of
applications. Fingerprinting was applied to several oil spills or
oil occurrences, including: Prince William Sound and the Gulf
of Alaska in the aftermath of the Exxon Valdez oil spill and the
Deepwater Horizon oil spill in the Gulf of Mexico in 2010; tar-
balls and oils along coastal California in a very large data set that
gave information about sources of oil contamination and ocean
current oil dispersal, as well as inferences drawn from the fin-
gerprint parameters and locations of the beached tarballs about
the geologic setting of the Monterey Formation offshore south-
ern California; petroleum in the Silurian-Devonian Carbonate
aquifer, South-Central Louisville, Kentucky; a large diesel fuel
spill in Mandan, ND; and, a crude oil spill from a ruptured
pipeline in Bemidji, MN. The Mandan and Bemidji spills pro-
vided new information about methanogenic biodegradation of
oil and oil products, along with other new discoveries about the
fate of oil as it ages in the environment.
Acknowledgment
The authors thank Keith Kvenvolden who began and
led much of the oil fingerprinting research, Robert
Rosenbauer and Kenneth Peters who made invaluable contri-
butions to the southern California tarball study, Colleen Rostad
for her contributions to the Mandan study, and Jeanne Dileo and
Florence Wong for their help with the graphics.

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Appendix 1
Constituents of petroleum useful in fingerprinting
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 276 F. D. Hostettler et al.

Appendix 2
Geochemical Parameters from Isotope and GC/MS Data

Whole oil:
δ 13C: carbon isotopic composition of whole-oil/tar residues—useful for oil-oil and oil-source correlations and as an indication of systemic
biodegradation (Peters and Moldowan, 1993; Stout and Lundegard, 1998; Hostettler et al., 2007).
Saturate fraction:
Pr/Ph: pristane/phytane: This is a widely used source parameter (Peters and Moldowan, 1993) based on the two most common isoprenoids in
unweathered crude oils. It can be used to infer oxicity of the depositional environment. These compounds are relatively quickly lost to degradation,
so are limited in their use for fingerprints. Due to their respective volatilities they are partitioned during refinery distillation at the high temperature
end of the kerosene cut-off, diminishing the phytane content and resulting in significantly higher values of the parameter in kerosene relative to
diesel fuel (Hostettler et al., 2008).
n-C17 /Pr: n-C17 /pristane: Commonly used parameter to evaluate approximate progress of biodegradation in spilled oils (Kaplan et al., 1997). It has
been used to estimate how long a spill might have been in the environment (Christensen and Larsen, 1993), but needs to be used cautiously (Bekins
et al., 2005).
n-Cmax: A descriptive parameter indicating the highest peak in an n-alkane or an n-alkylcyclohexane distribution.
n-alkane profile: m/z 57 extracted ion chromatogram used to follow degradation progression.
n-alkylcyclohexane profile: m/z 83 extracted ion chromatogram used to follow degradation progression.
Compound specific carbon isotope ratios: Calculated for individual n-alkanes to follow the degradation pathway.
Triterpanes (hopanes), m/z 191 SIM chromatograms:
Tm/Ts: 18α-22,29,30-trisnorneohopane/17α-22,29,30-trisnorhopane (sometimes calculated as Ts/Tm or Ts/(Ts+Tm). This ratio is used as both a
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source and maturity parameter (Seifert and Moldowan, 1978).

Triplet: (also called C26 /Tet) [C26 -tricyclic terpanes (22S+22R)/C24 -tetracyclic terpane]. This source parameter was first noted in Kvenvolden et al.,
(1985) and then was used to distinguish coastal tar residues in Prince William Sound (Kvenvolden et al., 1995). Abundant C24 tetracyclic is cited
(Peters et al., 2005) as indicating carbonate and evaporite source facies; therefore, lower values of this ratio indicate this characteristic.
23Tri/C30 : C23 tricyclic terpane/17α,21β(H)-hopane. This ratio is a source parameter adapted from Peters and Moldowan (1993).
23Tri/C29 : C23 tricyclic terpane/17α,21β(H)-30-norhopane. This ratio is a source parameter adapted from Peters and Moldowan (1993).
20Tri/23Tri: (also called C20 /C23 TT) tricyclic terpane/C23 tricyclic terpane. Source parameter.
22Tri/21Tri: (also called C22 /C21 TT) C22 tricyclic terpane/C21 tricyclic terpane. Source parameter, used by Peters et al., 2008, to help distinguish
lithofacies.
24Tri/23Tri: (also called C24 /C23 TT) C24 tricyclic terpane/C23 tricyclic terpane. Source parameter, used by Peters et al., 2008, to help distinguish
lithofacies.
26Tri/25Tri: (also called C26 /C25 TT) C26 tricyclic terpane pair/C25 tricyclic terpane pair, peak areas. Source parameter; high values (>1) indicate a
lacustrine depositional environment, whereas lower values indicate a marine source.
28Tri/29Tri: (also called C28 /C29 TT) C28 tricyclic terpane pair/C29 tricyclic terpane pair, peak areas. Source parameter.
C30 /C29 : 17α,21β(H)-30-norhopane/17α,21β(H)-hopane. Sometimes calculated as C29 /C30 , and called C29 H/H). This ratio is a source parameter
adapted from Palacas et al. (1984).
29D/29H: (also called C29 Ts /C29 H) 18α(H)-30-norneohopane/17α,21β(H)-30-norhopane. Source parameter.
C31 S/(S+R): 17α,21β(H)-homohopane(22S)/17α,21β(H)-homohopane (22S+22R). This epimer ratio is a hopane maturity parameter used
extensively in petroleum geochemistry; the equilibrium ratio at full maturity is ∼0.6 (Ensminger et al., 1974; Mackenzie, 1984).
C31 S/C30 : (also called C31 S/H) 17α,21β(H)-homohopane(22S)/17α,21β(H)-hopane. Source parameter.
35S/34S: (also called C35 /C34 S) 17α,21β(H)-29-pentakishomohopane (22S)/17α,21β(H)-29-tetrakishomohopane(22S). Higher C35 than C34 22S
homohopanes is an indication of carbonate/evaporite facies or anoxic depositional environment.
BI: Bisnorhopane Index (also called BNH/H) 28,30-bisnorhopane/17a,21b(H)-hopane. This source ratio has been used to characterize oils from the
Monterey Formation. The presence of 28,30-bisnorhopane, in addition to indicating a marine, highly reducing depositional environment (Curiale,
Cameron, and Davis 1985), is reported to be passed on from bitumen rather than generated from kerogen and, therefore, decreases with thermal
maturity (Peters and Moldowan, 1993). Therefore, this ratio would be higher in oils sourced from near-surface facies.
OI: Oleanane Index, 18α+β(H)-oleanane/17α,21β(H)-hopane. This commonly used source parameter indicates a contribution from Cretaceous and
younger plant material (Peters and Moldowan, 1993). In the California coastal tars, oleanane is generally present, but in low amounts.
BTO: A marker parameter to indicate the presence or absence of three markers for Monterey Miocene oils: B = 17α,18α,21β(H)-28,30-bisnorho-
pane; T = 17α,18α,21β(H)-25,28,30-trisnorhopane; O = oleanane.
GI: (also called G/H) Gammacerane Index, gammacerane/17a,21b(H)-hopane. This ratio is used as a source parameter; abundant gammacerane is a
carbonate/evaporite facies indicator and a marker for highly reducing, hypersaline depositional environments (Peters and Moldowan, 1993).
Steranes, m/z 217 SIM chromatograms:
C29 S/(S+R): 24-ethyl-5α,14α,17α(H)-cholestane (20S)/ 24-ethyl-5α,14α,17α(H)-cholestane (20S+20R). This sterane epimer ratio is commonly
used as a maturity parameter; the equilibrium value at full maturity is ∼0.5 (Mackenzie et al., 1980).
C28 /C29 : 24-methyl-5α,14α,17α(H)-cholestane (20R)/ 24-ethyl-5α,14α,17α(H)-cholestane (20R). This source parameter has been modified from
discussions in Grantham and Wakefield (1988) and Waples and Machihara (1991).
α27R/Hop: a Sterane Index, 5α,14α,17α(H)-cholestane/17α,21β(H)-hopane. This parameter gives an indication of relative proportions of a common
regular sterane to hopane. It can help track sterane biodegradation relative to hopane.
nor26&27/Hop: another Sterane Index, two tentatively identified steranes more refractory than regular steranes, C26 24-nor-5α-cholestane (Moldowan
et al., 1991) and C27 27-nor-24-methyl-5α-cholestane (Schouten et al., 1994), indexed to hopane. This is a source parameter and may serve as a
maturity parameter.
α27R/nor27: 5α,14α,17α(H)-cholestane/C27 27-nor-24-methyl-5α-cholestane. A sterane parameter that also tracks sterane biodegradation.
%27,%28,%29: Percentage of C27 , C28 , and C29 steranes, from the m/z 218 extracted ion profile.
Sterane distribution or Dominant Sterane(s): Descriptor indicating which steranes are the most prominent.
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 Petroleum Fingerprinting 277

(Continued)

Aromatic fraction
PAH-RI: Polycyclic Aromatic Hydrocarbon-Refractory Index, the ratio of the second, usually major, peak containing the C26 R and C27 S members in
the C26 to C28 triaromatic sterane suite (TAS, m/z 231) to that of the first, usually dominant, peak in the monomethyl chrysenes (m/z 242)
(Hostettler et al., 1999). These two suites of oil constituents are among the most refractory constituents in oils. This index is a source parameter, but
it also reflects a specific facies characteristic. PAH-RI goes from low values in shale, mid values in marl, and high values in carbonate (increasingly
anoxic facies) environments (Peters et al., 2008). Since PAH-RI compares TAS to a typical petrogenic C1 PAH, high values indicate higher levels of
TAS. TAS are known to be a stable product of diagenesis of steranes in a reducing or anoxic environment. Therefore, PAH-RI is another indicator of
the anoxic nature of the source environment.
T/(T+M): T = triaromatic steranes (peak areas), C26 to C28 , m/z 231; M = monoaromatic steranes (areas), C26 to C28 , m/z 253. Aromatic steroid
parameter. This is a thermal maturity and source parameter, widely used, modified from that described in Peters and Moldowan (1993). Low values,
reflecting relatively higher levels of the monoaromatic steroids, indicate low thermal maturity.
C1N/C2N: methyl naphthalenes (m/z 142)/dimethyl naphthalenes (m/z 156). Parameter to show if early weathering is occurring, since the C1
napthalenes will diminish before the C2 naphthalenes.
C1D/C1P: methyl dibenzothiophenes (m/z 198)/methyl phenanthrenes (m/z 192). Source parameter, as the two following parameters (Kaplan
et al., 1997).
C2D/C2P: dimethyl dibenzothiophenes (m/z 212)/dimethyl phenanthrenes (m/z 206). Source parameter indicating relative levels of a
sulfur-containing PAH to a regular PAH (Kaplan et al., 1997; Bence et al., 1996).
C3D/C3P: trimethyl dibenzothiophenes (m/z 226)/trimethyl phenanthrenes (m/z 220). Source parameter like C2D/C2P.
1,2,4-TMB/2MN: 1,2,4-trimethylbenzene/2-methylnaphthalene. A source parameter in diesel fuel, using two fairly refractory aromatic compounds.
Pery/Chr: a PAH parameter, perylene normalized to chrysene, a common oil PAH. Perylene helps distinguish shallow-seeping oils from deeper oils.
Perylene has a biogenic origin and is associated with near-surface bitumens (Ventakesan, 1988). It is known to be present in variable amounts in
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shallow Monterey sediments (Kvenvolden et al., 2002).

[PAH]: Absolute concentrations of 2-5 ring PAH and their alkylated derivatives in sediments and petroleum of PWS and GOA. 37 PAH were
quantitated and 14 were chosen for similarity indices (Short et al., 1999).
[TPAH]: Total PAH concentrations used by Short et al. (1999).
MSE: Pattern similarity index of 14 selected PAH, applied to Katalla oil (Kat) and Constantine Harbor (CH), used by Short et al. (1999).
MP/P: methyl phenanthrene/phenanthrene. Evaluating petrogenic vs. combustion PAH (Prahl and Carpenter, 1983).
DMP/P: dimethyl phenanthrene/phenanthrene. Evaluating petrogenic vs. combustion PAH (Killops and Howell, 1988)
T/DMP: triaromatic sterane/dimethyl phenanthrene. Comparing triaromatic steranes (high levels in oil vs. low levels in sediments) to
C2-phenanthrene as source parameter.

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