B
Biomarkers: Assessment of Petroleum Source- systems (e.g., Magoon and Dow 1994), thus reducing petro-
Rock Age and Depositional Environment leum exploration risk. Correlations involving large collec-
K.E. Peters1,2, C.C. Walters3 and J.M. Moldowan4
1
Schlumberger, Mill Valley, CA, USA
2
Department of Geological Sciences, Stanford University,
Stanford, CA, USA
3
ExxonMobil Corporate Strategic Research, Annandale, NJ,
USA
4
Biomarker Technologies, Inc., Rohnert Park, CA, USA
Definition
Biological markers (biomarkers) are molecular fossils from
once-living organisms found in crude oils and solvent extracts
of petroleum source rocks. Source-related biomarkers are
hydrocarbons that are diagnostic for specific taxa of organ-
isms and/or specific depositional settings. Taxon specificity
may be as narrow as individual species or as broad as a
kingdom. Depositional conditions can be inferred from the
type of biotic input or environmental conditions that influence
the preservation and/or diagenetic alteration of specific bio-
markers. Age-specific biomarkers are taxon-specific and
indicative of the age of evolutionary emergence of that
taxon based on the geologic fossil record.
Source- and age-related biomarkers can be used for direct
correlation of crude oil samples to other oils or to solvent
extracts from thermally mature source rock. When samples of
prospective source rock are unavailable, source- and age-
related biomarkers in oil can be used for indirect correlation
to the source rock because they provide useful genetic infor-
mation, including the type of organic matter input, redox
conditions in the depositional environment, and constraints
on geologic age. Geochemical correlations of oils and source
rocks (oil-oil and oil-source rock correlation) are based
mainly on biomarker and isotopic measurements, which
yield valuable insight that can be used to establish petroleum
# Springer International Publishing AG 2017
R. Sorkhabi (ed.), Encyclopedia of Petroleum Geoscience,
DOI 10.1007/978-3-319-02330-4_9-1
tions of source- and age-related geochemical data for many
samples can be facilitated using chemometrics (multivariate
statistics).
Introduction
Under certain depositional conditions (e.g., Demaison and
Moore 1980), significant amounts of organic matter from
one or a few species of organisms may be deposited and
preserved in marine or lacustrine sediment. If the organic-
rich sediment undergoes burial diagenesis and catagenesis, it
may become a petroleum source rock that expels oil rich in
biomarkers inherited from biochemical precursors in the con-
tributing organisms. Diagenesis consists of chemical, physi-
cal, and biological changes during sedimentation and
lithification, but prior to significant alteration of organic mat-
ter by burial heating. Catagenesis consists of thermal alter-
ation of organic matter in the range of ~50–150  C.
Table 1 shows selected, commonly used source- and age-
related biomarker ratios that can be measured in crude oil to
describe the source rock, even when the oil may have
migrated to a reservoir far from the source rock. Interpreta-
tions for all of the parameters in the table are subject to
revision pending further research. In addition to information
on the source rock, some biomarkers also include information
on the geologic age of the organisms that contributed to the
original sediment. These compounds are thus both source-
and age-related biomarkers. Table 2 and Fig. 1 show more
detail for several common age-related biomarkers and their
inferred distributions through geologic time. Peters et al.
(2005) provide an extensive survey of source- and age-related
biomarker parameters.
Chemometrics is a powerful tool for genetic oil-oil and oil-
source rock correlation. In chemometrics, measured proper-
ties (e.g., biomarker and isotope ratios) are mathematically
2 Biomarkers: Assessment of Petroleum Source-Rock Age and Depositional Environment
Biomarkers: Assessment of Petroleum Source-Rock Age and Depositional Environment, Table 1 Selected source-related biomarkers
Source rock
setting Biomarker or biomarker ratio
Marine C42–46 alkyl cylopentanes, odd/even predominance
C30 24-n-propylcholestanes, 24-n-propyldiacholestanes;
chrysophyte algae
Mid-chain monomethylalkanes and dimethylalkanes;
stromatoporids, demosponges, also hot springs
C19–C30 tricyclic terpanes; Tasmanites
Lacustrine Botryococcane, cyclobotryococcanes, polymethylsqualanes;
chlorophyte algae, Botryococcus braunii, brackish/fresh water
C15–C34 macrocyclic alkanes, C17–C26 methylated derivatives;
Botryococcus braunii; brackish/fresh water
Low steranes/hopanes; relative input of eukaryotes
vs. prokaryotes
C26/C25 tricyclic terpanes >1
High tetracyclic polyprenoids; brackish/fresh
Low C3122R homohopane/C30 hopane (C31R/hopane)
C42–46 cyclopentylalkanes, even/odd predominance = saline
lacustrine, even ~ odd = freshwater
Fluvio- Pristane/phytane >3; also coal
deltaic
Algal input Elevated nC15, nC17, nC19 alkanes; lacustrine or marine
High steranes/hopanes; relative input of eukaryotes
vs. prokaryotes
Higher- Elevated nC27, nC29, nC31 alkanes; post-Silurian
plant input Oleananes, lupanes, taraxeranes; angiosperms (flowering plants)
Bicadinanes; angiosperms, Dipterocarpaceae dammar resin
Lupane, norlupanes, bisnorlupanes; angiosperms
Retene, cadalene, tetracyclic diterpanes; gymnosperms
Beyerane, kaurane, phyllocladane, isopimarane (diterpanes);
gymnosperms
C29/(C27–C29) steranes (some exceptions, e.g., Precambrian)
Hypersaline Pristane/phytane <0.5
b-Carotane; carotenoid pigments in halophilic bacteria or algae,
e.g., green alga Dunaliella salina in sea salt fields or evaporative
lakes
High gammacerane; stratified anoxic water, halophilic bacteria,
bacterivorous eukaryotes by gene transfer
2-Methyldocosane; bacteria?
2,6,10,15,19-pentamethyleicosane (PMIa); methanotrophic and
methanogenic Archaea, anoxic, hypersaline (not yet confirmed
in crude oil)
Trimethyl chromans; hypersaline photic zone
References
Carlson et al. (1993), Hsieh and Philp (2001)
Moldowan et al. (1985, 1990), Peters et al. (1986, 1999a)
Shiea et al. (1990), Thiel et al. (1999a)
Aquino Neto et al. (1983), Volkman et al. (1989), De Grande
et al. (1993)
Moldowan and Seifert (1980), Brassell et al. (1985), McKirdy
et al. (1986), Metzger and Largeau (1999), Summons et al.
(2002)
Audino et al. (2002)
Moldowan et al. (1985)
Zumberge et al. (2000), Peters et al. (2005)
Holba et al. (2000, 2003)
Zumberge et al. (2000), Peters et al. (2005)
Carlson et al. (1993), Hsieh and Philp (2001)
Hughes et al. (1995)
Gelpi et al. (1970), Tissot and Welte (1984), Reed et al. (1986)
Moldowan et al. (1985)
Eglinton and Hamilton (1967), Tissot and Welte (1984)
Zumberge (1987), Ekweozor and Udo (1988), Riva et al.
(1988), Moldowan et al. (1994)
Cox et al. (1986), van Aarssen et al. (1990, 1992)
Rullkötter et al. (1982), Curiale (2006)
Noble et al. (1985a)
Noble et al. (1985b), Murray et al. (1998), Zinniker (2005)
Huang and Meinshein (1979), Moldowan et al. (1985),
Czochanska et al. (1988)
ten Haven et al. (1987)
Hall and Douglas (1983), Jiang and Fowler (1986), Koopmans
et al. (1997); Peters et al. (1999a)
Moldowan et al. (1985), Brassell et al. (1988), Sinninghe
Damsté et al. (1995), Grice et al. (1998a), Takishita et al.
(2012)
Connan et al. (1986)
Elvert et al. (1999), Schouten et al. (1997), Thiel et al. (1999b),
Greenwood and Summons (2003), Maslen et al. (2009)
Sinninghe Damsté et al. (1987), Schwark et al. (1998), Grice
et al. (1998a)
(continued)
Biomarkers: Assessment of Petroleum Source-Rock Age and Depositional Environment 3

Biomarkers: Assessment of Petroleum Source-Rock Age and Depositional Environment, Table 1 (continued)
Source rock
setting Biomarker or biomarker ratio References
Anoxic Pristane/phytane <1; phototrophs, commonly hypersaline and ten Haven et al. (1987), Fu Jiamo et al. (1990)
anoxic
C35/C34 homohopanes >1 Peters and Moldowan (1991), Dahl et al. (1994), Sinninghe
Damsté et al. (1995)
Isorenieratane, trimethylaryl isoprenoids, okenane; Summons and Powell (1986,1987), Clark and Philp (1989),
Chlorobiaceae green sulfur bacteria (especially when 13C-rich); Koopmans et al. (1996), Grice et al. (1998b, 2005), Brocks and
photic zone anoxia Schaeffer (2008)
Crocetane, anaerobic methane oxidizing Archaea; photic zone Thiel et al. (1999b, 2001), Greenwood and Summons (2003),
anoxia, gas hydrates, methane-rich mud volcanoes, seeps Maslen et al. (2009)
High V/Ni porphyrins Lewan (1984), Moldowan et al. (1986)
High 25,28,30-trisnorhopane & 28,30-bisnorhopane; Seifert et al. (1978), Katz and Elrod (1983), Moldowan et al.
chemoautotrophic bacteria at oxic-anoxic interface, marine (1984), Curiale et al. (1985), Schoell et al. (1992)
upwelling
C21–C25 regular acyclic isoprenoids; halophilic Archaea, saline Grice et al. (1998a, b)
to hypersaline
C32–C35 hexahydrobenzohopanes, C31–C35 benzohopanes; Connan and Dessort (1987), Schaeffer et al. (1995)
bacteria, anoxic carbonate-anhydrite
Methyl n-pristanyl and methy i-butyl maleimides; Grice et al. (1996, 1997), Pancost et al. (2002)
Chlorobiaceae anaerobic green sulfur bacteria, photic zone
anoxia
Carbonate C29/C30 hopanes >1 Fan Pu et al. (1987), Clark and Philp (1989), Subroto et al.
vs. Shale (1991)
Low diasteranes/steranes Rubinstein et al. (1975), Hughes (1984), van Kaam-Peters et al.
(1998), Wang et al. (2015)
Dibenzothiophene/phenanthrene >1 typical of carbonate (and Hughes et al. (1995)
Pr/Ph < 1), values <1 typical of shale
High 2a-methylhopanes; cyanobacterial oxygenic Summons et al. (1999)
photosynthesis
Benzothiophenes, alkyldibenzothiophenes; carbonate-evaporite Hughes (1984)
High C22/C21 and low C24/C23 tricyclic terpanes Peters et al. (2005)
(Pregnane + homopregrane)/steranes; sulfur-rich anoxic Wang et al. (2015)
carbonate
Other High nC13–nC19 alkanes, C15–C23 cyclohexylalkanes, little or Reed et al. (1986), Hoffmann et al. (1987), Fowler (1992)
no pristane, phytane; Gloeocapsomorpha prisca marine
phytoplankton, Cambrian-Devonian but mainly Ordovician
2,6,15,19-tetramethylicosane (TMI), similar to PMI; Archaea Kuypers et al. (2001), Vink et al. (1998)
(not yet confirmed in crude oil)
24-isopropylcholestane; stromatoporids (related to modern McCaffrey et al. (1994), Peters et al. (1995)
Porifera), high 24-isopropyl/n-propylcholestane ratios are
typical of Infracambrian
Cryostane (26-methylcholestane); demosponges (not yet Brocks et al. (2016)
confirmed in crude oil)
5,5-diethylalkanes with odd:even predominance (formerly Brocks and Summons (2003), Greenwood et al. (2004)
incorrectly reported as 3,7- or 3,w7-dimethylalkanes); benthic
microbial mats
C30 dinosteranes (4a,23,24-trimethylcholestanes); marine or Summons et al. (1987, 1992), Goodwin et al. (1988)
lacustrine dinoflagellates, common in Mesozoic but rare in
Paleozoic rocks and oils
C30 4a-methyl-24-ethylcholestane; marine or lacustrine Goodwin et al. (1988), Brassell et al. (1988)
dinoflagellates or prymnesiophyte algae
C20, C25, C30, C35 highly-branched isoprenoid alkanes, HBIb Nichols et al. (1988), Rowland and Robson (1990), Volkman
(and thiophenes, anoxia); Rhizosolenid diatoms, post- et al. (1994), Belt et al. (2000), Sinninghe Damsté et al. (1989,
Cenomanian 2004)
24-Norcholestanes, 24-nordiacholestanes; diatoms, 24/(24 + 27) Holba et al. (1998)
nordiacholestane ratios >0.25 and >0.55 typify oils from
Cretaceous or younger and Oligocene or younger source rocks,
respectively
a
PMI = 2,6,20,15,19-pentamethylicosane (IUPAC nomenclature), previously spelled pentamethyleicosane (PME)
b
C20 HBI = 2,6,20-trimethyl-7-(3-methylbutyl)-dodecane, C25 HBI = 2,6,10,14-tetramethyl-7-(3-methyl)-pentadecane
4 Biomarkers: Assessment of Petroleum Source-Rock Age and Depositional Environment

Biomarkers: Assessment of Petroleum Source-Rock Age and Depositional Environment, Table 2 Details for selected age-related
biomarkers
Biomarker or biomarker ratio Biotic origin Diagnostic age References
Botryococcane and a monoaromatic hydrocarbon Botryococcus Presence: Eocene+ Volkman (2014)
produced from lycopadiene-related lipids
C25 highly-branched isoprenoid (HBI) Rhizosolenid diatoms Presence: Upper Turonian+ Sinninghe Damsté et al.
(2004)
Oleanane Index Angiosperms >10%: Mid-Cretaceous+ Moldowan et al. (1994)
>20%: Tertiary
Bicadinanes Dipterocarpaceae, Abundant: Oligocene+ van Aarssen et al. (1990),
extinct angiosperms Presence: Mesozoic+ Armanios et al. (1995)
Triaromatic 23,24-dimethylcholesteroids and Dinoflagellates, TA-DMC >0 Mesozoic+ Barbanti et al. (2011)
triaromatic dinosteroids haptophytes, diatoms TA-dinosteroid ratio > 0.3
Mesozoic+
C26 24-norcholestanes and C26 24-nordiacholestanes Dinoflagellates, NDR > 0.25, NCR > 0.35: Holba et al. (1998), Rampen
diatoms Mid-Jurassic+ et al. (2007)
NDR > 0.52, NCR > 0.60:
Tertiary+
Phyllocladane and related diterpanes Gynmosperms Presence: Devonian+ Noble et al. (1985a),
Zinniker (2005), Auras et al.
(2006)
Retene, tetrahydroretene, cadalene, simonellite, Land plants Presence: Silurian+ Romero-Sarmiento et al.
isohexylalkylnaphthalene (2011)
C11–C19 odd n-alkane enrichment Gloeocapsomorpha Ordovician predominance Fowler et al. (2004)
prisca but also in Silurian-
Devonian
“+” includes younger ages
TA-DMC = Triaromatic-23,24-dimethylcholesteroids/(Triaromatic-23,24-dimethylcholesteroids + C28 Triaromatic-steroid 20S)
TA-dinosteroid ratio = Triaromatic-dinosteroids /(Triaromatic-dinosteroids + C28 Triaromatic-steroid 20S)
NDR = ba-24-nordiacholestanes (20S + 20R)/[ba-24-nordiacholestanes (20S + 20R) + ba-27-nordiacholestanes (20S + 20R)]
NCR = (aaa + abb) 24-norcholestanes (20S + 2R)/ [(aaa + abb) 24-norcholestanes (20S + 2R) + (aaa + abb) 27-norcholestanes (20S + 2R)]
Oleanane Index = %(a + b)-oleanane/[(a + b)-oleanane + ab-hopane]

modeled to reveal underlying relationships and association in
complex data sets. Various techniques are available, but the
most common are hierarchical cluster analysis and principal
component analysis. For example, Peters et al. (2007) ana-
lyzed source- and age-related biomarker and isotopic data for
more than 1000 oil samples collected from the circum-Arctic
(>55oN). A multitiered chemometric decision tree allowed
automated classification of 31 genetically distinct oil families
based on a 622-sample training set. Decision-tree
chemometrics uses principal component analysis and tiers of
K-nearest neighbor and SIMCA (soft independent modeling
of class analogy) models to classify and assign confidence
limits for newly acquired samples of oil or source-rock
extracts.
Taxon-Specific Biomarkers
Taxon-specific biomarkers are a class of source-related bio-
markers that can be directly related to precursor organisms.
Taxon-specific biomarkers commonly occur in rocks depos-
ited during or after the biotic radiation of the precursor organ-
isms, but they may also occur in low concentrations in older
rocks (Moldowan 2000). For example, dinosteroids occur in
pre-Triassic rocks, although they are presumed to originate
from dinoflagellates whose cysts are found only in Triassic or
younger rocks (Moldowan et al. 1996; Barbanti et al. 2011).
24-Norcholestanes occur in some lower Phanerozoic rocks,
whereas fossil evidence for their presumed precursor organ-
isms (diatoms) first appears in Jurassic rocks (Holba et al.
1998). Small amounts of oleanane can be found in some
Paleozoic rocks (Taylor et al. 2006), although the precursor
compounds occur only in angiosperms and first appear in
small amounts in Lower Cretaceous rocks. Biomarkers in
rocks that predate the first macrofossil evidence for their
precursor organisms might be explained as (1) contamination
by younger, migrated oil, (2) older fossils of the presumed
precursor organism that have not yet been found, or (3) bio-
synthetic pathways for the precursor of the biomarker existed
in other organisms prior to evolution of the recognized fossil
morphology of the precursor organism.
The evolution of life is characterized by new biochemical
synthetic pathways and many compounds that might become
age-diagnostic biomarkers. However, only a few biomarkers
are known to be reliable age indicators (Table 2) because they
must (1) originate from a biochemical uniquely synthesized
Biomarkers: Assessment of Petroleum Source-Rock Age and Depositional Environment
Biomarkers: Assessment of Petroleum Source-Rock Age and
Depositional Environment, Fig. 1 Several common age-related bio-
markers and their approximate temporal range in millions of years before
present (Ma). When present in samples, age-related biomarkers can be
used to infer the age and identify of the source rocks for crude oils.
by organisms having a known geologic age range, (2) be
preserved over geologic time, and (3) contribute sufficient
biomass to the source rock to be detectable in related crude
oil. Most common biomarkers originated from membrane
lipids produced by biosynthetic pathways that evolved in
the Proterozoic. Their occurrence in Precambrian strata may
help resolve when certain organisms first evolved, such as
Eukarya or cyanobacteria, but these compounds are ubiqui-
tous in younger rocks and crude oils. Grantham and Wake-
field (1988) observed that the C28/C29 sterane ratio in crude
oils generally increases through Phanerozoic time, which they
ascribed to increasing biodiversity of phytoplankton. Some
biomarkers have complex temporal relationships.
Dinosteranes and triaromatic dinosteroids are derived from
dinosterols that today are nearly exclusively produced by
dinoflagellates. Many dinoflagellates produce a resting stage
or cyst that can be fossilized. These organisms became impor-
tant contributors to the Mesozoic fossil record based on the
abundance of dinosterol-derived biomarkers (Moldowan
et al. 1996, 2001). For example, the dinosterane/[dinosterane
+ (20R)-3b-methylstigmastane] ratio in extracts of source
rocks is less than 0.35 from the Silurian through the Permian
5
Absence of such compounds cannot strictly be used to interpret age, but
may still be useful to support an age assessment when combined with
other data. See Peters et al. (2005) for further details on each parame-
ter.? = uncertain occurrence (Figure modified from Walters et al. (2017))
and tends to exceed this value thereafter. However, similar
high values characterize older strata in the Neoproterozoic,
suggesting that either non-cyst-forming dinoflagellates
evolved much earlier than their cyst-forming counterparts or
that these compounds were produced by extinct acritarchs,
organic-walled microfossils of unknown affinity. It is unclear
whether the acritarchs represent an early form of dinoflagel-
lates or whether the biosynthetic pathways for dinosterols
evolved independently in these two lineages.
Source rocks and related crude oils dominated by input
from Gloeocapsomorpha prisca are characterized by a strong
odd carbon-number preference of n-alkanes from C11 to C19
and unusually low amounts of higher hydrocarbons. This
organism probably evolved in the Late Cambrian and
flourished in the Ordovician where it contributed nearly all
of the organic matter in some organic-rich shales (Fowler
1992). Although G. prisca dominance is mostly restricted to
the Ordovician, it is rarely reported in the Silurian, and the
organism became extinct in the Late Devonian (Fowler
et al. 2004).
Several age-related biomarkers signal the evolution of land
plants. Some biomarkers indicate the earliest emergence of
6 Biomarkers: Assessment of Petroleum Source-Rock Age and Depositional Environment
land plants (Romero-Sarmiento et al. 2011), while others
trace the emergence of gymnosperms (e.g., conifers), charac-
terized by certain tricyclic diterpanes (Zinniker 2005; Auras
et al. 2006), or angiosperms (flowering plants), characterized
by certain pentacyclic triterpenoids. For example, abundant
oleanane marks the radiation of angiosperms in the Late
Cretaceous and Early Tertiary, and the oleanane index is one
of the most widely used age-related parameters (Moldowan
et al. 1994). However, small amounts of oleanane occur in
older rocks. The angiosperm fossil record extends into the
Early Mesozoic, and limited oleanane in Paleozoic strata
supports an even earlier evolution as indicated by DNA
phylogenetic analyses of living plants (Peterson et al. 2007).
Similarly, bicadinanes occur throughout Mesozoic strata and
also indicate angiosperms, but Dipterocarpaceae synthesize
resins that yield bicadinanes and their abundance in oil or
source-rock extracts suggest Oligocene or younger age.
The record for C26 24-norcholestanes and
24-nordiacholestanes extends to the Neoproterozoic (Zhang
et al. 2002), although concentrations in source rocks remain
low until the Jurassic and can be high in the Tertiary (Holba
et al. 1998). This temporal relationship arises from multiple
taxonomic origins for precursor sterols. Dinoflagellates and
related species contributed these compounds since the Mid-
Precambrian, but the evolution and rise of diatoms in the
Mesozoic provided a second source (Rampen et al. 2007).
Hence, abundance of 24-norcholestanes and
24-nordiacholestanes indicates post-Triassic sediments, par-
ticularly those of Tertiary age deposited at high latitude.
Similarly, C25 highly branched isoprenoids characterize
rhizosolenid diatoms that emerged in the upper Turonian
(Sinninghe Damsté et al. 2004).
The fossil record for Botryococcus extends into the Pre-
cambrian, but biosynthetic pathways for production of
C30–C37 botryococcenes only developed recently by modifi-
cation of the squalene synthase gene. Hence, the presence of
botryococcane and a monoaromatic hydrocarbon produced
from lycopadiene-related lipids are specific for modern races
of Botryococcus braunii and provide the youngest age-related
biomarkers known (Volkman 2014).
Examples of the Application of Source- and Age-
Related Biomarkers
The following discussion gives examples of how diverse
biomarkers in crude oil can be used to describe the source-
rock age and depositional environment.
Marine Versus Lacustrine
An unusual rounded cobble containing brecciated angular
sandstone clasts cemented by heavy oil was collected from a
beach near Brora, Scotland. The cobble originated as fault
gouge from the nearby Helmsdale fault that was eroded and
transported along a stream bed to the beach. Based on bio-
marker source and biodegradation parameters, the oil cement
is a mixture of marine and lacustrine input (Peters et al.
1999a). For example, like oil from the nearby offshore
Beatrice field, the oil cement contains 24-n-propylcholestanes
and ß-carotane, which suggest marine and arid, possibly
lacustrine source rocks, respectively (Table 1). The oil cement
also contains pristane, phytane, residual n-alkanes (mild bio-
degradation), and a complete series of 25-norhopanes (heavy
biodegradation), which also indicate a mixture. The first
charge to the Helmsdale fault consisted of oil from a nearby
Devonian source rock that was heavily biodegraded after it
migrated to shallow depth. The origin of the second charge is
unclear. Unlike Beatrice oil, the oil cement contains oleanane
and shows a higher 24-nordiacholestane ratio, suggesting
input from a Cretaceous or younger, paralic marine shale
source rock (Table 2, Fig. 1). Although Cretaceous and Paleo-
cene source rocks are inferred to exist in various depocenters
in the northeast Atlantic margin, subcrops of these rocks
offshore Brora are thermally immature. Alternatively, the
second charge could have originated from an effective Middle
Jurassic source rock that contained oleanane. Mass spectrom-
etry of extract from the nearby Middle Jurassic Brora coal
confirms small amounts of oleanane. This is one of only a few
pre-Cretaceous source-rock extracts that contain low levels of
oleanane.
Carbonate Versus Shale
Peters et al. (2008) used biomarker and stable carbon isotope
ratios to determine the age, organic matter input, lithology,
and depositional environment of source rocks for 388 samples
of crude oil, seep oil, and stranded tarballs in coastal Califor-
nia. Chemometric analysis of the data identified three families
of 13C-rich oil that originated from thermally mature equiva-
lents of three members of the Miocene Monterey Formation
like that exposed at Naples Beach near Santa Barbara. Oil
families 1, 2, and 3 correspond to the clayey-siliceous, carbo-
naceous marl, and lower calcareous-siliceous members that
represent shale, marl, and carbonate source rocks, respec-
tively, based on C22/C21 and C24/C23 tricyclic terpane ratios
(Table 1). Other biomarker ratios support these interpreta-
tions. For example, Ts/Tm and Ol/H, which are sensitive to
clay content and angiosperm (flowering plant) input respec-
tively, show high, intermediate, and low values for families 1,
2, and 3, respectively, consistent with the progression from
nearshore to deep water organofacies of the same source rock.
Stable carbon isotope ratios for saturate and aromatic hydro-
carbons from the oil samples and the calculated canonical
variable (Sofer 1984) are consistent with 13C-rich Monterey
Formation source rock dominated by marine organic matter.
Biomarkers: Assessment of Petroleum Source-Rock Age and Depositional Environment
Photic Zone Anoxia
Enhanced bioproductivity and restricted water circulation in
marine or lacustrine settings commonly result in anoxia
(<0.5 ml oxygen/L water) or euxinia (anoxic with abundant
hydrogen sulfide from microbial sulfate reduction), which
contributes to preservation of organic matter due to elimina-
tion of benthic metazoan life (Demaison and Moore 1980).
Purple and green sulfur bacteria (Chromatiaceae and
Chlorobiaceae, respectively) may thrive when water column
euxinia occurs within the photic zone. Photosynthetic pig-
ments in these organisms include aromatic carotenoids, such
as isorenieratene, renieratene, renierapurpurine, okenone, and
chlorobactene (Schaeffer et al. 1997; Sinninghe Damsté et al.
2001; Brocks and Schaeffer 2008). Diagenesis of these pre-
cursors in hydrogen sulfide-rich sediments facilitates their
incorporation into the kerogen via sulfur-carbon bonds.
These bonds are readily broken during catagenesis of the
source rock, yielding various products, including saturated
biomarkers that can be used to interpret marine photic zone
anoxia (Table 1). For example, crude oil generated from
Aptian source rocks in the Sergipe-Alagoas Basin, Brazil
(Sousa Júnior et al. 2013), shows low pristane/phytane
(reducing), abundant gammacerane, and ß-carotane (saline
to hypersaline), as well as various carotenoid derivatives,
including isorenieratane and aryl and diaryl isoprenoids
(photic zone anoxia).
Tertiary Versus Mesozoic
Source-related biomarkers, such as distributions of C27–C29
steranes and diasteranes, C31–C35 homohopanes, and the
occurrence of C30 n-propylcholestanes, identify two marine
petroleum systems in the Czech Republic, one from Jurassic
and the other from Paleogene source rocks (Picha and Peters
1998). Two oils from the sub-Carpathian foreland plate
(Lubna-18 and Dolni Lomna-1) have similar geochemical
compositions, including elevated oleanane and
24-nordiacholestane age-related biomarker ratios (Table 2,
Fig. 1), consistent with an origin from Paleogene source
rock. These rocks were inferred to be either the Menilitic
shales of the Carpathian thrust belt or autochthonous Paleo-
gene deposits buried below the thrust belt. Two other oils
from the sub-thrust plate (Zdanice-7 and Damborice-16) cor-
relate geochemically with extracts of thermally mature Juras-
sic source rocks in the study area. Like the rock extracts, these
two oils lack oleanane and show low 24-nordiacholestane
ratios, supporting an origin from Jurassic marl source rock.
One oil sample from the Vienna Basin (Tynec-34) appears to
be a mixture with contributions from both source rocks.
Biomarker geochemistry reveals genetic relationships
among crude oil samples from eastern Indonesia and their
source-rock ages and depositional environments (Peters et al.
1999b). Chemometric analysis was based on 13 source-
related geochemical parameters, including stable carbon
7
isotope ratios of saturate and aromatic hydrocarbons
(d13Csaturates, d13Caromatics), distributions of C27–C29 steranes
and diasteranes, oleanane/(oleanane + hopane), and several
tricyclic and tetracyclic terpane ratios, which effectively dif-
ferentiate the two principal oil groups. Oils inferred to origi-
nate from Tertiary and Triassic–Jurassic source rocks in the
study area occur north and south of 2 S latitude, respectively.
This approximately corresponds with the famous Wallace
Line, which separates Oriental and Australian faunal regions.
The data indicate that 20 low-sulfur oils mainly from Sula-
wesi and Irian Jaya originated from Tertiary marine marlstone
source rock deposited under suboxic conditions, probably the
upper Miocene Klasafet Formation. These oils show 13C-rich
carbon isotope ratios and high oleanane, 24-nordiacholestane,
and pristane/phytane ratios (Tables 1 and 2), which together
are diagnostic of Tertiary oils and source rocks. Five high-
sulfur oils from Seram were interpreted to originate from
Triassic–Jurassic marine carbonate source rock deposited
under anoxic conditions. These oils lack oleanane and show
low 24-nordiacholestane and pristane/phytane ratios. Low-
sulfur Aliambata seep oil from Timor originated from a
more oxic, terrigenous-influenced marine clastic equivalent
of this carbonate source rock.
Infracambrian Versus Phanerozoic
Based on biomarker and isotope data, nonbiodegraded, heavy
oil from the Baghewala-1 well in northwestern India origi-
nated from anoxic marine carbonate-rich source rock that
contained algal and bacterial organic matter with no higher-
plant input (Peters et al. 1995). Age-related biomarkers in the
oil indicate that the source rock was Infracambrian in age.
Geochemical characteristics of the Baghewala-1 oil are sim-
ilar to those of Huqf-sourced oils from southern Oman,
including strong predominance of C29 steranes, pristane/phy-
tane ratios generally <1.0, low diasteranes, and very negative
stable carbon isotope ratios in the range 32 to 36‰. The
oil lacks oleanane, dinosteranes, and aromatic dinosteroids,
indicating Triassic or older source rock (Table 1, Fig. 1). It
shows high C29/(C27–C28) regular sterane and monoaromatic
steroid ratios, typical of many Devonian or older oils and
source rocks (Moldowan et al. 1985). High C29 steranes in
Tertiary crude oils commonly indicate a land-plant source
(e.g., Huang and Meinschein 1979; Czochanska et al. 1988),
but the Baghewala-1 oil shows no evidence of land-plant
input. The oil originated from Infracambrian source rock
because it contains abundant 24-isopropylcholestanes and
shows an elevated 24-isopropyl/n-propylcholestane ratio
(Table 1), typical of oils from Vendian (upper Precambrian)
to lower Cambrian carbonate source rock (e.g., McCaffrey
et al. 1994). Many oils and rock extracts of Vendian to Early
Cambrian age from Siberia, the Urals, Oman, Australia, and
the Baghewala-1 oil have high 24-isopropyl/
n-propylcholestane ratios (1), whereas younger and older
8 Biomarkers: Assessment of Petroleum Source-Rock Age and Depositional Environment
samples have lower ratios (0.4). McCaffrey et al. (1994)
suggest that abundant 24-isopropylcholestanes in these sam-
ples originate from archaeocyathids (i.e., Porifera or
sponges), which were important shallow marine reef-building
organisms during the Late Precambrian and Early Cambrian.
Conclusions
A common occurrence during petroleum exploration is the
discovery of crude oil that may have migrated to the surface as
a seep or to a porous and permeable reservoir rock far from its
origin in an organic-rich, thermally mature petroleum source
rock. Exploration risk for additional resources can be reduced,
provided that one can link the oil sample to a source rock in
the basin, thus establishing a petroleum system and effective
migration pathways that may include additional traps and
reservoirs. Despite complexity introduced by migration, a
petroleum system can be established by direct oil-source
rock correlation, provided that the oil and an extract of the
mature source rock are available for biomarker analysis. Even
when samples of the source rock are unavailable, biomarkers
in oil that were inherited from the source rock can be used for
indirect correlation because they provide information on its
character, including the type of organic matter, lithology,
redox conditions during deposition, and age.
Cross-References
▶ Biomarkers in Sediments and Petroleum
▶ Biomarkers: Assessment of Thermal Maturity
▶ Depositional Environments
▶ Geologic Timescale
▶ Petroleum Source Rocks
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