P

Petroleum: Chemistry and Occurrence components in solution which, in isolation, may occur in a
different phase at STP.
Joseph A. Curiale
Geochemical Advisory Services, Sugar Land, TX, USA (i) Gases – natural gas, including hydrocarbon gases and
higher-mass components dissolved therein, as well as
non-hydrocarbon gases
Definition (ii) Liquids – condensates and conventional crude oils dom-
inated by C6 to C60+ components but also containing
Petroleum is a naturally occurring mixture of hydrocarbon both gases and higher-mass hydrocarbons in solution
and non-hydrocarbon chemical compounds originating in (iii) Solids – solid bitumens generally resulting from early
sedimentary rocks predominantly from the thermal alteration generation/expulsion from rich source rocks or from
of once-living organic matter over time and at elevated pres- degradation of a once-liquid oil
sure. This article concerns the occurrence and composition of
petroleum on and within the earth. Petroleum originates from the action of temperatures in the
range of 50–250  C acting over geologic time periods
(105–109 Ma) on organic matter accumulated in fine-grained
Introduction sedimentary rocks (including coals). This description of ori-
gin excludes the concept of abiotic generation of petroleum,
This definition of petroleum is highly specific; it includes which has been studied by many over the past two centuries.
statements about both composition and origin. Other non- Abiotic petroleum is now considered to be an insignificant
specific terms, often used to indicate petroleum, are not cause of petroleum, is largely of academic interest, and will
appropriate. For example, “hydrocarbon” is a chemical not be discussed in this article.
definition – i.e., a molecule containing only carbon and The progressive thermal destruction of the insoluble
hydrogen – of one type of chemical compound in petroleum, organic matter (kerogen) and high-mass soluble and colloidal
but this term is not synonymous with petroleum (because organic matter (bitumen) in sedimentary rocks commonly
petroleum also contains non-hydrocarbons). Likewise, oil, generates a supercritical fluid which resides in the pore
gas, asphaltenes, aromatics, etc., are phases of petroleum or space of sedimentary rocks in the deep subsurface. This
compound classes within petroleum, but again, these terms supercritical fluid often migrates to lower pressure-
are not synonymous with petroleum. Here we will use “petro- temperature regimes, and along the way it undergoes a
leum” as it is defined above. phase change to gases and/or liquids. The compositional
Petroleum encompasses a compositional continuum characteristics of the resulting mixture depend upon the type
extending from methane and molecular hydrogen at the low of starting organic matter in the source rock and the temper-
molecular mass extreme to very high molecular mass ature and time experienced since its deposition. The infinite
asphaltenes which are present as a colloid in liquid petroleum. varieties of starting organic matter chemistries and time/tem-
Thus, at standard temperature and pressure (STP) petroleum perature combinations lead to an extraordinarily large range
includes three phases as described in Fig. 1 and in more detail of petroleum compositions (Tissot and Welte 1984).
below. In the subsurface each of these phases contains

# Springer International Publishing AG 2017

R. Sorkhabi (ed.), Encyclopedia of Petroleum Geoscience,
DOI 10.1007/978-3-319-02330-4_1-1
2 Petroleum: Chemistry and Occurrence

exceed those recovered from conventional accumulations

(Curiale and Curtis 2016).

Composition: Historical

Early compositional assessments of petroleum originated

from refining efforts and were limited by the analytical capa-
bilities of the mid-twentieth century. Such descriptions often
characterized petroleum by the distribution of its distillation
fractions, yielding cuts described as “gas,” “light distillate,”
and “residual” or “bottoms.” As liquid chromatographic tech-
niques were introduced and expanded in the 1950s and 1960s,
compound classes were defined and named according to the
dominant compound type, and compounds in specific series
were often distinguished by a Greek prefix (Table 1). This led
to compositional descriptions such as “paraffinic,”
“paraffinic-naphthenic,” “aromatic-intermediate,” etc., with
emphasis on the hydrocarbons and non-hydrocarbons sepa-
Petroleum: Chemistry and Occurrence, Fig. 1 Petroleums can be
rated under the prevailing chromatographic conditions
described by composition (to the right) and phase (to the left). Three
fundamental types of chemical analysis are shown here – elemental, (Speers and Whitehead 1969). This compound class termi-
molecular, isotopic – and each analytical type applies to each of the nology has led to several duplicative and overlapping terms;
three petroleum phases at STP this article will emphasize the most commonly used terms.
More refined liquid chromatographic and other separation
Migration of petroleum from its originating source rock, methods have led to the compound class designations in use
along with subsequent changes induced by thermal, micro- today, including aliphatic (saturate) hydrocarbons, aromatic
bial, and evaporative effects, accompanied by variations in hydrocarbons, NSOs (nitrogen-, sulfur-, and oxygen-
pressure and temperature during industrial production of the containing compounds; also called resins), and asphaltenes.
fluid, will further modify its composition. This latter fraction, though accessible via certain chromato-
graphic methods, is generally removed from the petroleum
initially, through excess addition of a low molecular mass
Occurrence solvent (e.g., n-pentane or n-heptane), and is considered to
exist as a colloid in petroleum (Yen 1974). With the progres-
The presence of sedimentary basins on all continents, the sively increasing influence of gas chromatography (GC),
exposure of their fine-grained sediments to elevated temper- mass spectrometry (MS), inductively coupled plasma (ICP)
atures over geologic time, and the occurrence of syn- methods, and various stable isotope measurement techniques
depositional organic matter within these sediments have over the past five decades, these historical depictions of crude
made petroleum a ubiquitous constituent in earth’s crust. oil have given way to descriptions based on elemental com-
Petroleum is present in all phases – supercritical, gas, liquid, position, molecular distribution, and stable isotopic ratios as
and solid – on all continents, both on the surface and in the shown in Fig. 1.
upper 10 km of the crust. Surface and near-surface accumu- Numerous schemes have been proposed for naming the
lations include the vast asphalt and tar sand deposits of west- various compound classes and subclasses of petroleum, and
ern Canada, Madagascar, Venezuela, and elsewhere. Recent these schemes have specific uses in upstream and downstream
economic extraction methods have made many of these segments of the petroleum industry. One example is the
deposits commercially viable. Subsurface petroleums subdivision of hydrocarbons that is abbreviated as PONA
reservoired in carbonates (limestones, dolomites) and and includes paraffins (also called saturate hydrocarbons),
course-grained clastics (sandstones, siltstones) account for olefins (compounds with double bonds between carbon
the majority of commercial accumulations. However, this is atoms), naphthenes, and aromatics (these last two are com-
changing as petroleum is increasingly extracted from fine- pounds with carbon rings in their structures). Most of these
grained source-rock reservoir units. Current estimates in some various schemes have been consolidated in upstream explo-
countries suggest that within the present century the volumes ration efforts in recent decades into that shown in Table 1 and
recovered from these unconventional accumulations will abbreviated as SARA: saturate hydrocarbon, aromatic hydro-
carbons, resins/NSOs, and asphaltenes.
Petroleum: Chemistry and Occurrence 3

Petroleum: Chemistry and Occurrence, Table 1 The compound is, although the saturate fraction, for example, is dominated by hydro-
types in petroleum are often grouped into compound classes. This chart carbons without multiple bonds, some separation procedures yield a
shows the most common terminology for these classes, along with a few saturate fraction that contains some aromatic hydrocarbons. More
alternative names. These class fractions are generally obtained via liquid detailed classification schemes are provided in Tissot and Welte (1984)
chromatographic analysis and often are not selective or exclusive. That and Hunt (1996)
Common class Alternative class
terminology terminology Description Examples
Saturates Aliphatics; Dominantly hydrocarbons, cyclic and acyclic, without multiple n-paraffins; acyclic isoprenoids;
paraffins bonds aliphatic biomarkers
Aromatics Dominantly hydrocarbons with at least one aromatic ring Naphthalenes, phenanthrenes;
aromatic biomarkers
NSOs Resins; polars Dominantly compounds containing heteroatoms, such as Thiophenes; carbazoles; steroidal
nitrogen (N), sulfur (S), or oxygen (O) acids
Asphaltenes Tars Very high molecular weight compounds present in petroleum as
a colloid

Petroleum: Chemistry and Occurrence, Table 2 There are several chain hydrocarbons and their derivative compounds. The italicized “n”
terminological conventions for naming the chemical components of means “normal” and is intended to indicate a straight carbon chain. The
petroleum. This table shows the simplest convention in use, for simple origin of the prefixes for carbon numbers one through four comes from
hydrocarbons with carbon numbers of ten and less. The listing gives the various ancient sources, e.g., “propane” and “butane” are widely thought
number of carbon atoms in the molecule and the names of the ten to derive, respectively, from the Latin word for fat and the Greek word
simplest n-alkanes. All are members of the saturate hydrocarbon com- for butter. Prefixes for carbon numbers of five and greater come from the
pound class. Also shown are the prefixes used to designate these straight Greek language
Prefix Simple n-alkane
1 Meth- methane
2 Eth- ethane
3 Prop- propane
4 But- n-butane
5 Pent- n-pentane
6 Hex- n-hexane
7 Hept- n-heptane
8 Oct- n-octane
9 Non- n-nonane
10 Dec- n-decane

Because of the availability of precise methods of com-

pound separation, such as modern chromatographic tech-
niques, the use of compound class distributions is gradually
diminishing. In its place we have the capability of detailed
determinations of the chemical composition of petroleum on a Petroleum: Chemistry and Occurrence, Fig. 2 Planar depictions of
compound-by-compound basis. Conventions for individual structural configurations of methane (left) and n-heptane (right). The
bonds shown for methane are intended to show its three dimensional
compound names are much more specific than those for
configuration, whereas the shorthand depiction of n-heptane requires the
compound classes and are largely specified by nomenclatural viewer to assume the presence of carbon and hydrogen atoms. More
rules of the International Union of Pure and Applied Chem- details are provided in the text
istry. IUPAC names as well as so-called “trivial” names are
currently in use for many of the components of petroleum, the behind (dashed line) and one in front of the page. In contrast,
simplest of which are listed in Table 2, for methane through the configuration shown for n-heptane is far simpler and most
n-decane. commonly encountered: each endpoint and apex of the figure
Each of the compounds shown in Table 2 – and indeed, are occupied by a carbon atom, and the bonded hydrogens
each chemical compound in petroleum – has a distinctive (not shown) necessary to account for each carbon’s valence
structural configuration, and multiple methods have been shell are assumed to be present but not shown. For example,
used to depict this configuration. Typical examples are three hydrogen atoms are present at each endpoint carbon,
shown in Fig. 2 for methane (left) and n-heptane (right). and two are present at each mid-chain carbon. In an analogous
Here, the three-dimensional existence of methane is depicted manner it is possible to depict all of petroleum’s molecular
in two dimensions by showing one hydrogen atom projecting constituents in a rapid and consistent manner.
4 Petroleum: Chemistry and Occurrence

Petroleum: Chemistry and Occurrence, Table 3 Examples of ter- The hydrocarbons of natural gases are commonly domi-
minological conventions for naming the complex hydrocarbon compo- nated by methane, although the total amount of ethane, pro-
nents of petroleum are shown here. This table shows a brief listing of
how Greek prefixes are used to name various hydrocarbons in petroleum, pane, butanes, and pentanes often exceeds 5% by molar
with examples given from the classes of biological markers volume. Olefinic hydrocarbons, such as ethene and propene,
Number Greek prefix Example also occur in a small number of gases. Natural gases that are
1 mono- Monocyclic terpene dominantly or exclusively methane, known as dry gases, can
2 di-(variant: bi-) Bicyclic terpane arise both from the action of microbial methanogenesis and
3 tri- Tricyclic diterpane (e.g., cheilanthane) from the high-temperature thermal degradation of sedimentary
4 tetra- Tetracyclic (e.g., sterane) organic matter or of other petroleums. Non-hydrocarbon com-
5 penta- Pentacyclic (e.g., hopane) ponents such as carbon dioxide, molecular hydrogen and nitro-
gen, helium, and hydrogen sulfide are also present in many
natural gases. With standardized analytical methods, it is pos-
In general, a Greek prefix along with accepted IUPAC sible to characterize, quickly and accurately, over 99% of the
nomenclature is also used for the more complex hydrocarbons gaseous components in petroleum.
in petroleum, examples of which are given in Table 3. Using The liquid components of petroleum are assayed using
accepted nomenclatures such as those in Tables 2 and 3 allows various chromatographic methods applied to whole oils and
petroleum geochemists to communicate effectively when their compound class fractions (e.g., aliphatic hydrocarbons,
discussing the compounds of petroleum and when assigning aromatic hydrocarbons). Because of the extraordinary diver-
names to newly discovered components of petroleum. sity in these compositions, this article will summarize them by
presenting median concentration ranges defined by chromato-
graphic class and/or compound type (Table 1). The broadest
Composition: Elemental compositional distinction for liquids is that of hydrocarbons
versus non-hydrocarbons, with the former constituting
The elemental composition of petroleum, with few excep- 75–90% by mass of most mid-range, non-biodegraded crude
tions, is dominated by carbon and hydrogen (90%+). The oils (Tissot and Welte 1984). Among the hydrocarbons, the
so-called heteroelements of sulfur, nitrogen, and oxygen con- aliphatic fraction (i.e., those hydrocarbons without an aro-
stitute almost all of the remainder (Hunt 1996). In addition, matic ring) accounts for 60–70% of the total in most unaltered
most of the remaining elements of the periodic table have petroleums (this excludes petroleums of extreme composi-
been identified in petroleum. This includes sub-percent con- tion). Compound class categories are used to subdivide the
centrations of vanadium, nickel, cobalt, manganese, and aliphatic hydrocarbon fraction even further, into n-alkanes,
numerous other organically bound transition metals, which isoalkanes, acyclic, and cyclic isoprenoids.
are present mostly in the asphaltene fraction. Trace levels of The remaining 30–40% of the hydrocarbon material in
other components, including (among others) mercury, arse- petroleum is commonly referred to as the aromatic fraction,
nic, and the noble gases, also occur as part of the inorganic which consists dominantly of aromatic hydrocarbons.
portion of petroleum, in both gases and liquids. Sensitive Because of the chromatographic processes commonly used,
high-precision analytical methods, including inductively however, this fraction also includes minor amounts of sulfur-
coupled plasma-mass spectrometry (ICP-MS), now make it and nitrogen-containing compounds. As with the aliphatic
possible to determine the concentrations of most elements of hydrocarbons, the aromatic hydrocarbons can also be sub-
the periodic table via a single chemical analysis of petroleum. divided into additional classes. For example, this fraction can
be segregated according to the number of aromatic rings per
molecule.
Composition: Molecular Although less studied by petroleum geochemists for both
analytical and commercial reasons, non-hydrocarbons in
Early workers quickly recognized that elemental distributions crude oil are far more compositionally diverse than the hydro-
within petroleum, while of interest from an economic and carbons and include nuclear, alkylated, and benzylated carba-
refining perspective, were limited in assessing origin and zoles, thiophenes, pyridines, quinolines, and many other
history. In the mid-twentieth century, chromatographic and compound types. Organometallic constituents of crude oil
mass spectrometric methods were developed, largely within are rarely speciated routinely, although research has indicated
the petroleum industry, as a way to identify the molecular that they are dominated by porphyrinic and other tetrapyrrolic
components of petroleum. This revolutionary development compounds, commonly metallated (chelated) with nickelous
led to our highly detailed current understanding of the molec- and vanadyl cations.
ular distribution of both hydrocarbons and non-hydrocarbons
in petroleum.
Petroleum: Chemistry and Occurrence 5

Speciation and identification of hydrocarbons and the non- Composition: Isotopic

hydrocarbon constituents of liquid oils have benefited from
chromatographic methods accompanied by sophisticated detec- Although elemental and molecular descriptions of a petro-
tion systems, most importantly gas chromatography-mass spec- leum provide an extensive assessment of its composition,
trometry/mass spectrometry, liquid chromatography-mass petroleums are also compositionally distinctive with respect
spectrometry, and multidimensional gas chromatography using to the distribution of their stable isotopes. Thus, stable isotope
time-of-flight mass spectrometric detection (Eiserbeck et al. geochemistry is widely used to define the composition of
2012). Additionally, preparative chromatographic methods gases, condensates, oils, and solid bitumens and to assist in
followed by infrared, nuclear magnetic resonance, Raman, and understanding the maturation and migration history of fluids.
other forms of spectroscopy have made absolute stereochemical Indeed, petroleum compositional assessment in the absence
structural identification possible in many instances. As a result, of isotopic data is properly recognized as incomplete. Each of
thousands of specific components have been identified conclu- the five most common elements of petroleum – carbon,
sively as constituents of petroleum. Among these, the homolo- hydrogen, sulfur, oxygen, and nitrogen – possesses multiple
gous series in highest concentration in most unaltered stable isotopes, and stable isotope ratios of all except oxygen
petroleums is the n-alkane series of hydrocarbons ranging are commonly used by petroleum geochemists. Of the ratios
from C1 (methane) to greater than C100 (n-decacontane), in regular use, average crustal values for the secondary stable
which can account for 10–30% by mass of the petroleum. In isotope range from less than 0.02% (2H, or deuterium, as a
unusually waxy liquid petroleums and in some solid bitumens, percentage of total hydrogen) to 4.21% (34S, as a percentage
n-alkanes can account for more than 80% of the mass of the oil. of total sulfur) The stable isotope ratio most commonly used
Additional homologous series present in petroleum include the in petroleum geochemistry is that of 13C to 12C, which has a
acyclic isoprenoids (usually dominated by the widely measured crustal abundance ratio of approximately 1:99. The propen-
and interpreted pristane and phytane components), the sity of stable isotopes to fractionate during processes such as
alkylbenzenes, and the (loosely defined) cyclic isoprenoids. biotic growth, thermal cracking, and microbial utilization,
This latter group includes the bi-, tri-, tetra-, and pentacyclic caused by diffusive and kinetic effects, makes them excellent
aliphatic and aromatic compounds (Table 1) commonly referred tools for discriminating petroleums.
to as biomarkers. Isotopic discrimination of the compounds in petroleum is
Molecular components in petroleum which show a struc- greatest for methane, largely because it is the only component
turally recognizable descendance from biochemical com- with a direct biochemical origin. The dual origins of methane
pounds that are present in living (or once-living) organisms in petroleum – as a microbial product and as a thermal
are called biomarkers. This term is a contraction of “biolog- product – are reflected in the stable isotopic ratios of carbon
ical marker” and refers to chemical compounds which are and hydrogen (Whiticar 1999). As an example, methane
molecular fossils. The separation and identification of bio- associated with petroleum in seeps and in the subsurface
markers in crude oils have yielded dozens of compound will exhibit carbon isotope ratios (d13C) ranging from less
classes which are now routinely used to track the origin and than 100 o/oo to greater than 20 o/oo depending on,
history of petroleums. A short list of these classes includes respectively, its microbial or thermal origin or mixtures
acyclic isoprenoids, cheilanthanes, phenanthrenes, steranes, thereof. Within this range, the d13C value of methane and
terpanes, and porphyrins (free base and chelated) (Peters et al. higher-mass natural gas components will vary extensively as
2005). Although usually present only at ppm levels and less, a function of microbial consortia effective in the system,
the C26–30 steranes and C19–35 terpanes have received the original organic matter in the source rock, thermal maturity
most attention, largely because these components were level, extent of biodegradation, and possibly length and tor-
among the first identified and because they are remarkably tuosity of the migration pathway. Similar interpretive avenues
useful for interpreting the origin and history of liquid and exist and are utilized for other isotopic ratios in natural gases,
solid petroleums. Modern gas chromatographic-mass spec- including d2H, d15N, and d34S.
trometric analyses that are used to quantify these components Stable isotope ratio distinctions also exist in liquid petro-
have evolved to the point where measurement is now rapid, leums and are caused by many of the same geological pro-
precise, and inexpensive. This capability for rapid and accu- cesses. For example, distinctions arise from the broad secular
rate data acquisition has led to the use of petroleum molecular variability of d13C in crude oils. Oils originating from organic
distributions, and particularly biomarker distributions, in a matter in source rocks older than 0.5 Ga are often isotopically
wide variety of applications. These include assessment of lighter than 33 o/oo, whereas those originating from organic
source-rock origin and character, thermal maturity at time of matter in source rocks younger than 20 Ma can be isotopically
generation, relative subsurface migration extent, and degree heavier than 20 o/oo. In addition, (i) thermal maturity extent
of thermal, microbial, and evaporative alteration after expul- is often deducible from carbon and hydrogen isotope ratio
sion from the source rock. data, (ii) depositional setting of the source unit (e.g., open
6 Petroleum: Chemistry and Occurrence

marine vs. fresh water lacustrine) can be apparent from hydro- Cross-References
gen isotope trends, and (iii) origin of sulfur-rich gas can be
deduced from the sulfur isotope ratio of hydrogen sulfide. ▶ Basin and Petroleum System Modeling
These are but a few of the uses for stable isotope measure- ▶ Hydrocarbons: Origin
ments as tools for assessing petroleum origin. The broad ▶ Petroleum Geochemistry
application of stable isotope ratios in petroleum geochemistry ▶ Petroleum: Physical Properties
has made these parameters a necessary adjunct to any robust
compositional analysis of petroleum.
Bibliography

Summary and Future Directions Curiale JA, Curtis JB (2016) Organic geochemical applications to the
exploration for source-rock reservoirs – a review. J Unconv Oil Gas
Res 13:1–31
Our compositional understanding of petroleum has evolved in Eiserbeck C, Nelson RK, Grice K, Curiale J, Reddy C (2012) Compar-
parallel with our analytical capabilities and has driven our ison of GC-MS, GC-MRM-MS, and GCxGC to characterize higher
knowledge of petroleum’s origin and fate. As analytical plant biomarkers in tertiary oils and rock extracts. Geochim
Cosmochim Acta 87:299–322
instrumentation becomes progressively more sophisticated,
Hunt JM (1996) Petroleum geochemistry and geology, 2nd edn.
the ability to deconvolve and speciate the thousands of petro- W.H. Freeman and Company, San Francisco. 743 p
leum components will be enhanced and, ultimately, com- Peters KE, Walters CC, Moldowan JM (2005) The biomarker guide,
pleted. Recent developments in compound-specific isotope volume 2: biomarkers and isotopes in petroleum systems and earth
history. Cambridge University Press, Cambridge, UK
ratio analysis (for carbon and, most recently, hydrogen and
Speers GC, Whitehead EV (1969) Crude petroleum. In: Eglinton G,
nitrogen) and whole-oil compositional analyses (achieved Murphy M (eds) Organic geochemistry – methods and results.
without prior compound class fractionation, using techniques Springer, New York, pp 638–675
such as Fourier transform ion cyclotron resonance mass spec- Tissot BP, Welte DH (1984) Petroleum formation and occurrence: a new
approach to oil and gas exploration. Springer, Berlin. 538 p
trometry) are representative approaches undergoing rapid
Whiticar MJ (1999) Carbon and hydrogen systematics of bacterial for-
advancement. Early results from these approaches are already mation and oxidation of methane. Chem Geol 161:291–314
being applied successfully to problems of petroleum geo- Yen TF (1974) Structure of petroleum asphaltene and its significance.
chemistry. These and numerous other new technological Energy Fuels 1:447–463
developments are inexorably moving us toward a complete
understanding of the composition of petroleum.
P

Petroleum Geochemistry Historical Development

Joseph A. Curiale The historical development of petroleum geochemistry as a

Geochemical Advisory Services, Sugar Land, TX, USA distinct discipline evolved from the convergence of several
prior sciences, including chemistry, geology, and biology, and
their sub-disciplines as depicted in Fig. 1. Following the
Definition Industrial Revolution, extensive observations of bedded
coals led to early theories which proposed that liquid and
Petroleum geochemistry is the science and application of solid crude oils originated from coal and its precursor peat
chemical concepts to understand the origin of deposits, and most treatises on the origin of oil dating from the
petroleum – natural gas, condensate, and crude oil – and its eighteenth and nineteenth centuries reflect these ideas (Hunt
occurrence and fate on the earth’s surface and within its crust 1996; Dott 1969). More detailed chemical studies during that
(adapted from Hunt 1996). period addressed compositional similarities between liquid
oil and animal or plant components, leading to theories pro-
posing that fish oil and plant pigments were starting materials
Introduction for oil. Although many of these early theories may be thought
fanciful today, they eventually led to the seminal work of
The most extensive development of petroleum geochemistry Alfred Treibs (Treibs 1934). Compositional analysis of plant
has been in an industrial sense, because petroleum geochem- pigments, including chlorophyll, led Treibs to posit a genetic
ical principles are applied widely in exploring for, develop- relationship between once-living organic matter and petro-
ing, and producing petroleum. Petroleum geochemical leum. Similarities evident in tetrapyrrolic chemical structures
concepts are also applied in such diverse areas as environ- identified in both substances ultimately led to a working
mental studies, forensic applications, archeological and hypothesis in which living organic matter is the starting
anthropological studies, and the search for present and past point in a chain of events that eventually leads to the occur-
evidence of extraterrestrial life. rence of natural gas, condensate, and crude oil.
This article focuses on the use of petroleum geochemistry Following the insights established by Treibs and the sub-
in understanding the source, maturation, migration, and alter- sequent widespread commercial exploitation of petroleum,
ation of petroleum in the earth’s upper crust, where petroleum progress in petroleum geochemistry was intermittent over
is considered to encompass a molecular continuum from the next few decades. Early understanding of the chemistry
natural gas to liquid and solid oil. More extensive discussions of petroleum came predominantly from refinery science and
are provided in several textbooks and technical reviews, in particular the need to understand input chemistry in order to
including Tissot and Welte (1984), Hunt (1996), Killops and “tailor” specific output products. These advances began with
Killops (2005), and Peters et al. (2005). methodical and painstaking compositional studies in indus-
trial or industry-supported organizations, most notably the
American Petroleum Institute, as outlined in chronological
detail in Hunt et al. (2002). Most importantly, however,
research efforts at this time were initiated following the
development of integrated laboratories within the petroleum

# Springer International Publishing AG 2017

R. Sorkhabi (ed.), Encyclopedia of Petroleum Geoscience,
DOI 10.1007/978-3-319-02330-4_2-1
2 Petroleum Geochemistry

Petroleum Geochemistry,
Fig. 1 Petroleum geochemistry is
an interdisciplinary science which
draws upon concepts and data
from numerous other disciplines

industry and governmental organizations worldwide, and it organic matter to petroleum (correlation science). By the
was within these laboratories that most advances were made mid-1990s, these concepts were firmly established (e.g.,
during the last half of the twentieth century and, in some Peters and Moldowan 1991; Curiale 1993; Whiticar 1996),
cases, continue to the present (Table 1). and developments since then have focused on enhanced ana-
In almost all instances, conceptual developments in petro- lytical capabilities accompanied by the incorporation of
leum geochemistry were preceded by, or coincident with, the petroleum geochemistry as a significant and invaluable com-
advent of instrumental techniques specifically suited to ponent of our understanding of petroleum systems.
unraveling the complex chemistry of petroleum. The most The key ongoing development in the field, from both a
critical techniques from this perspective were gas chromatog- conceptual and applied perspective, is the increasingly tight
raphy and coupled gas chromatography-mass spectrometry, interrelationship between petroleum geochemistry as a tool
isotope mass spectrometry, and simultaneous multi-elemental for understanding hydrocarbon charge in sedimentary basins
analysis of complex organic mixtures. Upon development of and the additional risk elements used to assess petroleum
these analytical methods, many organic chemists shifted their systems in these basins. These include reservoir quality, seal
research focus to the rapidly expanding field of petroleum quality, and structural configuration. Modern integration of
chemistry. Typical examples include early work by Silverman petroleum geochemistry with petroleum system science has
and Epstein (1958) on carbon isotope ratios of organic matter provided academic scientists as well as petroleum
and studies on early geochemical applications of gas chroma- explorationists with a powerful approach for understanding
tography (Cooper and Bray 1963). These early studies, the generation, migration, and entrapment of oils, conden-
including the strong emphasis on analytical chemistry, were sates, and gases. Continuing developments are chronicled in
summarized in the 1960s in volumes edited by Breger (1963) numerous technical journals and several international confer-
and Eglinton and Murphy (1969). The content of these com- ences. Among these, the most prominent are, respectively,
pilations is still relevant today. Detailed timelines and key Elsevier’s Organic Geochemistry journal and the European
contributors throughout the twentieth century are listed in Association of Organic Geochemistry’s International Meeting
Hunt et al. (2002) and Kvenvolden (2006). on Organic Geochemistry. Table 1 presents a condensed ver-
The instrumental developments that drove petroleum geo- sion of seminal contributions to the development of petro-
chemical research in its early days (Table 1) ultimately led to leum geochemistry in the twentieth and twenty-first centuries.
the concepts which now form the backbone of the discipline. An excellent timeline, a record of contributors to journals and
These include the natural generation of petroleum hydrocar- conferences, and related photographs are provided by
bons from source rock organic matter derived from plants Kvenvolden (2006).
containing structurally analogous non-hydrocarbon biochem-
ical components (now commonly referred to as biomarker
geoscience), the natural fractionation of carbon and hydrogen Major Sub-disciplines
isotopes from precursor organic matter during the origin of
petroleum (isotope geoscience), and the use of molecular The three major sub-disciplines of petroleum geochemistry
markers, isotopic ratios, and elemental distributions to link (Fig. 2) – elemental, molecular, and isotopic
components along the transformation route from living geochemistry – collectively identify and quantify the 104 to
Petroleum Geochemistry 3

Petroleum Geochemistry, Table 1 Key developments in petroleum geochemistry. For greater detail see Tissot and Welte (1984), Hunt (1996),
Hunt et al. (2002), and Kvenvolden (2006)
Year Historical development
1927 American Petroleum Institute Project 6 is initiated, methodically identifying the hydrocarbons in a single crude oil for the
first time and leading to new development in separation science
Early 1920s to early Petroleum geochemical analysis of soil gases in Europe, Asia, and North America, opening the era of petroleum
1930s exploration via analysis of near-surface hydrocarbons
Early 1930s Alfred Treibs and colleagues establish a relationship between metalloporphyrins in oils and chlorophyll in living organic
matter, anticipating the biological market concept
Early 1950s The first industry-based and causally defined oil-oil and oil-source rock correlations are conducted as early industry
geochemical laboratories begin petroleum geochemistry research programs
Late 1950s Early stable carbon isotope analyses are adapted for use in geochemical organic matter, including crude oils and organic-
rich rocks. Immediate uses are found in correlation studies
Early 1960s Gas chromatographic (GC) analyses are applied to analyze hydrocarbons in geochemical organic matter. Mass
spectrometry is utilized in the decade as a GC detector, resulting in an explosion of compound identifications in oils and
rock extracts, and the era of modern biological marker analysis in petroleum geochemistry begins
Late 1960s Organic petrography studies are conducted on organic matter in petroleum source rocks, and the first vitrinite reflectance
laboratory is established in the petroleum industry
1970s Most large energy companies establish in-house chemistry laboratories devoted to research on the origin of oil and gas.
For the first time, petroleum geochemical analyses and interpretations are widely applied to exploration, development,
and production problems
Late 1970s Automated pyrolysis methods are developed and become commercially available, providing rapid and reproducible
assessment of petroleum source rock potential
1980s to present New methods of chemical analysis are adopted by explorationists; numerical modeling is used to estimate petroleum
generation timing and products at the basin scale; petroleum geochemistry becomes a necessary discipline in all parts of
the industry value chain

105 hydrocarbon and non-hydrocarbon components present which focused on carbon isotope ratios of specific hydrocar-
in petroleum. bon classes in petroleum, evolved in the twenty-first century
Elemental compositional studies focus on the non- into the routinely applied present-day method of compound-
hydrocarbons present in petroleum fluids, including compo- specific isotopic analyses (CSIA) whereby carbon and hydro-
nents such as He and Hg in natural gases, and sulfur, nitrogen, gen stable isotope ratios of individual components are mea-
oxygen, and transition metals (e.g., vanadium, nickel, cobalt, sured. CSIA instrumentation, initially commercialized for
manganese) in liquid oil and solid bitumen. Raw elemental carbon and then for hydrogen and other elements
concentrations and specific elemental ratios are used as cor- (Schimmelmann et al. 2006), provides a highly specific tool
relative tools and as a means to evaluate the origin and history for distinguishing one petroleum from another.
of a specific petroleum. Taken together and used holistically, the petroleum geo-
Molecular geochemistry focuses on the speciation of these chemistry sub-disciplines of elemental, molecular, and isoto-
elements in petroleum. In a full-spectrum petroleum pic geochemistry are required tools for understanding the
consisting, at standard temperature and pressure, of natural origin and subsequent chemical alteration of petroleum.
gas, condensate, and crude oil, the molecular suites present in
the petroleum are wide-ranging. They extend from low
molecular-mass components such as molecular hydrogen Applications
and methane to acyclic and cyclic higher molecular-mass
hydrocarbons and non-hydrocarbons and ultimately to Because the discipline of petroleum geochemistry evolved
extremely high molecular-mass asphaltenes that are present over the last several decades largely as a tool used by the
in liquid oils as a colloid. Over the past two decades, devel- energy industry in petroleum exploration, the applications of
opment of ever higher-resolution separation methods accom- petroleum geochemistry focus on the relationship between
panied by highly specific detection techniques has made petroleum and its source rock and on chemical modifications
molecular analysis and interpretation the most commonly that occur to the petroleum after it migrates away from its
used sub-discipline of petroleum geochemistry (Peters source location. These applications can be classified as
et al. 2005). (i) genetic – i.e., compositional aspects imparted to the petro-
The third sub-discipline, isotopic geochemistry, presents leum by the organic matter in its source rock – and
the ideal complement to elemental and molecular evaluations. (ii) nongenetic. The latter includes applications of petroleum
Compound class isotopic analyses of the twentieth century, geochemistry to understand and, in some cases, quantify the
4 Petroleum Geochemistry

Petroleum Geochemistry, Fig. 2 Elemental, molecular and isotopic geochemistry comprise the three sub-disciplines of petroleum geochemistry.
Shown here are just a few of the many analytical approaches which contribute to the discipline

extent of in-source and post-source thermal maturation, fluid absolute temperature – at the time of generation and expul-
migration, and post-entrapment/in-reservoir compositional sion, (c) determination of a lacustrine versus a marine depo-
alteration. The conceptual underpinning of these applications sitional setting, and (d) if lacustrine, an inference of saline
arises from the understanding that a petroleum’s chemical versus freshwater conditions in the depositional water col-
composition contains a full complement of information umn. Evaluation of source rock character through petroleum
about its origin and its post-sourcing history. Based upon compositional analysis continues to be one of the most active
this fundamental precept, the petroleum geochemist attempts areas of petroleum geochemical applied research.
to interpret the compositional data of a petroleum in such a The compositional modifications that occur in petroleum
way that all genetic and nongenetic compositional changes after it is expelled from the source rock(s) can be assessed
are deciphered and the full history of the petroleum is through a combination of the elemental, molecular, and iso-
understood. topic sub-disciplines of petroleum geochemistry. Both the
Historically, the application of petroleum compositional specific pathway and the relative extent of the migration
analysis to our understanding of a petroleum’s origin, includ- journey from source rock to the entrapment volume may be
ing the identity and depositional conditions of its source estimated using molecular techniques. This occurs because of
unit(s) and the conditions of its generation (temperature, the progressive depletion of high molecular-mass compo-
pressure, composition of associated waters, etc.), is the most nents and the post-sourcing uptake of exogenous molecular
common use of petroleum geochemical techniques. Through species caused by, respectively, progressive migration dis-
combining elemental, molecular, and isotopic analyses of a tance and contact with specific and distinct organofacies
petroleum, it is now possible to retrodict the character of its during migration. Compositional changes in petroleum fol-
source rock with varying levels of success. For example, age lowing entrapment can be evaluated in order to determine
and lithology of the source unit can often be estimated, as can numerous features of petroleum history, including (a) extent
its depositional environment, organofacies, and thermal his- of light-end loss due to evaporation; (b) loss of specific
tory, from the composition of its expelled petroleum. Molec- (usually aromatic) components due to preferential dissolution
ular and isotopic analyses also provide tools for determining into the accompanying water phase; (c) decrease in overall
if multiple source units, or multiple organofacies within a molecular mass of the fluid, caused by thermal effects; and
single source unit, are responsible for a specific petroleum. (d) compositional modifications caused by microbial con-
Focused approaches have achieved impressive levels of suc- sumption (biodegradation) of selected molecular series.
cess. For example, crude oil compositional analysis and inter- Although petroleum geochemical applications have tradi-
pretation often allow (a) assignment of source age, in some tionally focused on the exploration for petroleum, both field
cases to within 20–30My (e.g., Holba et al. 1998), development and production efforts also benefit from the
(b) estimation of source rock maturity – and, in some cases, application of petroleum geochemical techniques. Indeed,
Petroleum Geochemistry 5

industrial applications for this purpose date from the 1970s and pressure in sedimentary basins utilize both chemical (e.g.,
and shortly thereafter (see Slentz 1981), preceding some phase distributions) and physical (e.g., API, pour point, etc.)
exploration-related geochemical applications. Many uses of parameters, both as input parameters and as model validation
petroleum geochemistry as a tool in field development and parameters. This often extends to the molecular composition
production have been established. Highly precise chromato- of petroleum, particularly when epimerization ratios and other
graphic analyses are commonly used to assess hydrocarbon maturity-induced molecular ratios are used to test and validate
fluid continuity in gas and liquid petroleum reservoirs, pri- model predictions (Hantschel and Kauerauf 2009).
marily to minimize the number of wells needed to drain an
accumulation efficiently. Related studies utilize knowledge of
petroleum composition within individual compartments in Frontier Developments
order to determine (i) fluid contact locations, (ii) the extent
of compositional gradation in oil and gas columns, and (iii) Because the application of petroleum geochemistry has been
the location within the accumulation which contains the driven strongly by the development of new analytical tools
highest-value product. Petroleum geochemical applications (Table 1), frontier developments in the field will undoubtedly
in gas, condensate, and oil fields that are already on produc- be modulated by the continued development of novel analyt-
tion include (i) the assessment of equity distribution in wells ical methods. Industrial needs are another major driver for the
producing from multiple horizons, (ii) the proper allocation of discipline and will also present new frontiers at the conceptual
multiple product streams carried within a single pipeline, and and applied levels.
(iii) evaluation and remediation of production impediments Recently developed molecular analytical methods allow
caused by a wide range of scale types. Although field devel- enhanced methods of achieving single-run whole-petroleum
opment and production applications of petroleum geochem- analyses (i.e., without the need for prior separation of petro-
istry are well defined and cost-effective, the discipline is leum compounds into chemical classes) as well as detailed
largely underutilized for these purposes (Slentz 1981; Kauf- evaluation of the non-hydrocarbon components of petroleum.
man et al. 1990). Ultra-high resolution mass spectrometric techniques such as
It is important to note that a single type of geochemical ion cyclotron resonance mass spectrometry enable rapid eval-
analysis of petroleum will rarely succeed in solving an indus- uation of most molecular components in liquid oils in a single
trial problem. Rather, it is the synergy that derives from analysis (Rodgers and Marshall 2007). Multidimensional
applying multiple analyses which provides a holistic interpre- chromatographic techniques such as two-dimensional gas
tation useful for understanding the origin and history of the chromatography coupled to rapid response mass spectromet-
fluid and its reservoir behavior. Furthermore, although petro- ric methods (e.g., GCxGC-TOFMS) are already yielding
leum encompasses multiple phases, from supercritical fluids molecular information previously masked by coelution and
present in situ at generation depths to vapor and liquid phases low concentration (Eiserbeck et al. 2012). Rapid progress in
at the surface, the elemental, molecular, and isotopic sub- compound-specific isotopic analysis will eventually make
disciplines of petroleum geochemistry each have distinctive hydrogen isotopic analysis (and ultimately nitrogen and sul-
applications. For example, elemental analyses applied to nat- fur isotopic analyses) of individual molecular components
ural gases address characteristic features of origin and migra- routine over the full range of compounds amenable to chro-
tion (e.g., mercury and arsenic concentrations), whereas matography, providing an additional important correlation
molecular and isotopic analyses of condensates address com- tool (Schimmelmann et al. 2006). These and other methods
positional change resulting from subsurface movement (e.g., currently under development promise to provide petroleum
instances of migration-contamination and migration- geochemists with critical new tools for assessing the origin
fractionation in moving fluids). In total, all sub-disciplines and history of petroleum.
are necessary to deduce the origin and history of petroleum. It Novel concepts and developments of the past several years
is the application of all three sub-disciplines and the holistic also allow us to forecast frontier developments in petroleum
interpretation of their analytical results that allow the petro- geochemistry. Continuing expansion of our knowledge of
leum geochemist to correlate an oil to its source rock by source rocks as reservoirs (referred to variously as resource
deducing the role of a specific petroleum system in generating plays or unconventional exploration) provides new opportu-
petroleum of a specific composition (Curiale 1993). nities for petroleum geochemists to understand the effects of
In addition to the use of petroleum geochemistry to solve ultra-maturity on organic matter in shales and the resulting
problems related directly to petroleum and its source rock, unusual compound-specific isotopic distributions (Curiale
data from this discipline are useful in other areas, including as and Curtis 2016). In liquids-rich resource plays, our under-
input parameters for numerical modeling of petroleum gen- standing of compositional changes arising from in situ matu-
eration in the subsurface. Modern algorithms for modeling the rity and micro-migration within shale units continues to
generation of petroleum with increasing time, temperature, expand as these plays become economically more well
6 Petroleum Geochemistry

defined. Renewed interest in the efficient production of high- Cross-References

viscosity petroleum will lead to continued research into the
speciation of high molecular-mass hydrocarbons and non- ▶ Hydrocarbons: Origin
hydrocarbons in heavy oils. In addition, continued efforts to ▶ Petroleum Chemistry and Occurrence
model the generation of petroleum as well as the continuing ▶ Petroleum Exploration
need to correlate petroleums to source units which have never ▶ Petroleum Geoscience
been drilled are leading, respectively, to novel understanding ▶ Petroleum: Physical Properties
of the importance of proper kinetics determinations and to
enhancement of age-diagnostic molecular assessment
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Cooper JE, Bray EE (1963) A postulated role of fatty acids in petroleum
has also been called upon to assist in understanding natural formation. Geochim Cosmochim Acta 27:1113–1127
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ronment, to map ancient trade routes via the commercial use studies. In: Engel M, Macko S (eds) Organic geochemistry. Topics
in geobiology, vol 11. Plenum Press, New York, pp 473–490
of tars and solid bitumens, to deconvolute ancient dietary
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patterns through molecular analysis of cooking vessels, to exploration for source-rock reservoirs: a review. J Unconv Oil Gas
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(Compilers) Sourcebook for petroleum geology. American Associa-
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ison of GC-MS, GC-MRM-MS, and GCxGC to characterise higher
earth, and beyond.
plant biomarkers in tertiary oils and rock extracts. Geochim
Cosmochim Acta 87:299–322
Hantschel T, Kauerauf AI (2009) Fundamentals of basin and petroleum
Summary systems modeling. Springer, New York. 476 p
Holba AG, Tegelaar EW, Huizinga BJ, Moldowan JM, Singletary MS,
McCaffrey MA, Dzou LIP (1998) 24-norcholestanes as age-sensitive
The science of petroleum geochemistry examines the origin, molecular fossils. Geology 26:783–786
occurrence, and fate of natural gas, condensate, and crude oil Hunt JM (1996) Petroleum geochemistry and geology, 2nd edn.
on the earth’s surface and within its crust. The history of the W.H. Freeman and Company, San Francisco. 743 p
Hunt JM, Philp RP, Kvenvolden KA (2002) Early developments in
discipline extends back to the eighteenth century, but rigorous
petroleum geochemistry. Org Geochem 33:1025–1052
scientific approaches began in earnest in the 1930s with the Kaufman RL, Ahmed AS, Elsinger RJ (1990) Gas chromatography as a
work of Alfred Treibs. Seminal developments in analytical development and production tool for fingerprinting oils from indi-
chemistry over the next several decades led to increased vidual reservoirs: applications in the Gulf of Mexico. In:
Schumaker D, Perkins BF (eds) Proceedings of the 9th annual
understanding of petroleum composition from the molecular
research conference of the society of economic paleontologists and
to the isotopic level, and petroleum geochemistry today mineralogists, New Orleans, 1 Oct 1990, pp 263–282
encompasses three broad sub-disciplines – elemental geo- Killops SD, Killops VJ (2005) Introduction to organic geochemistry,
chemistry, isotopic geochemistry, and molecular geochemis- 2nd edn. Wiley Blackwell, Oxford, UK. 280 p
Kvenvolden KA (2006) Organic geochemistry: a retrospective of its first
try. These sub-disciplines provide extensive datasets for
70 years. Org Geochem 37:1–11
multiple applications of petroleum geochemistry, conceptu- Peters KE, Moldowan JM (1991) Effects of source, thermal maturity, and
ally focused on extracting from each petroleum complete biodegradation on the distribution and isomerization of homo-
information about its origin and its post-sourcing history. hopanes in petroleum. Org Geochem 17:47–61
Peters KE, Walters CC, Moldowan JM (2005). The Biomarker Guide,
Today the discipline is widely applied in the exploration and
Volume 2: Biomarkers and Isotopes in Petroleum Systems and Earth
production of petroleum, both in conventional source- History. Cambridge University Press. Cambridge, UK
reservoir plays and in more recent source rock reservoir Rodgers RP, Marshall AG (2007) Petroleomics: advanced characteriza-
exploration and development efforts. As continued progress tion of petroleum-derived materials by fourier transform ion cyclo-
tron resonance mass spectrometry (FT-ICR MS). In: Asphaltenes,
is made in chemical analysis of organic mixtures and holistic
heavy oils, and petroleomics. Springer, New York, pp 63–93
interpretation of petroleum systems, our understanding of Schimmelmann A, Sessions AL, Masterlerz M (2006) Hydrogen isoto-
petroleum geochemistry and its applications to petroleum pic (D/H) composition of organic matter during diagenesis and
geoscience will continue to expand. thermal maturation. Annu Rev Earth Planet Sci 34:501–533
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Silverman SR, Epstein S (1958) Carbon isotope composition of petro- Tissot BP, Welte DH (1984) Petroleum formation and occurrence: a new
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Geol 42:998–1012 Treibs A (1934) Chlorophyll- und Haminderivate in bituminosen
Slentz LW (1981) Geochemistry of reservoir fluids as unique approach to Gesteinen, Erdolen, Erdwachsen und Asphalten. Ein Beitrag zur
optimum reservoir management. SPE #9582. Presented at middle Entstehung des Erdols. Justus Liebigs Ann Chem 510:42–62
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gens and related natural gases. Int J Coal Geol 32:191–215
T

Total Organic Carbon (TOC) (depositional) TOC, referred to as TOCo, are particularly
valuable when results can be validated at the regional scale
Joseph A. Curiale by comparing modeled values to measured values.
Geochemical Advisory Services, Sugar Land, TX, USA

Analytical Measurement
Definition
Our focus in this section will be on automated instrumental
Total organic carbon (TOC) content, as used in the petroleum methods for quantitative TOC measurement, as these have
geosciences, is a measure of the mass of organically bound largely replaced wet oxidation methods of TOC determina-
carbon in a geological sample relative to the mass of the tion in recent sediments and sedimentary rocks. Qualitative
sample. Most commonly abbreviated as TOC and expressed (e.g., infrared and other spectroscopic), semiquantitative
as a percentage value – for example, % organic carbon within (e.g., assessment by inference and calculation, such as TOC
a rock – total organic carbon measurements are fundamental deduction from organic matter volume estimates), and
to petroleum geochemistry and indispensable for source rock deconvolution (e.g., using electric logs) methods for TOC
analysis and interpretation. estimation are not considered here. Common high-throughput
approaches for quantitative measurement of TOC in the
starting sample involve either the combustion or the pyrolysis
Introduction of organic matter, which creates one or more carbon-
containing species that is then measured by specialized detec-
This article will discuss analytical and modeling methods for tion systems (Jarvie 1991). Various standard methods have
assessing total organic carbon in solid geological samples and been devised for TOC and total organic matter measurement
will briefly address applications and interpretation of TOC in recent and lithified sediments, including ASTM approaches
values in petroleum geoscience. TOC percentages in geolog- (e.g., Schumacher 2002 and references therein). This article
ical samples, and specifically in sedimentary rocks being will focus on the most common direct and indirect approaches
evaluated for their petroleum source rock potential, can be used in petroleum geoscience.
determined through laboratory measurement of individual Direct analysis of TOC involves the oxygen-mediated
samples or estimated through numerical modeling at the combustion of organic matter in approximately 0.1–0.3
regional scale. Analytical measurements are appropriate and grams of starting sample (Fig. 1). The sample is treated
necessary for samples which are physically available in suf- initially to remove inorganic carbon prior to instrumental
ficient amounts for laboratory assessment. Modeled TOC analysis. Various levels of treatment, usually involving
values can be developed from first principles of biological hydrochloric acid or phosphoric acid, are employed to remove
production, transport to the site of deposition, and long-term carbonate-bound carbon from the sample. The organic carbon
preservation in the sediment column. Although analytical remaining in the treated sample is then combusted quantita-
determinations are highly accurate, model values must be tively to carbon dioxide and carbon monoxide (the latter can
considered when samples are unavailable and/or when it is subsequently be converted catalytically to carbon dioxide
desired to determine the evolution of TOC through time. prior to detection) in a carbon analyzer at temperatures of
Numerical modeling assessments of TOC and initial 1200–1400  C. Generated total carbon dioxide is then

# Springer International Publishing AG 2017

R. Sorkhabi (ed.), Encyclopedia of Petroleum Geoscience,
DOI 10.1007/978-3-319-02330-4_3-1
2 Total Organic Carbon (TOC)

Total Organic Carbon (TOC),

Fig. 1 Total organic carbon is
measured on a small, powdered,
homogenous rock sample
following acid treatment to
remove the carbon bound as
carbonate. Values are commonly
reported as grams organic carbon
per gram rock, given as a
percentage

measured through thermal conductivity detection or non- oxidation method vary as a function of organic matter type,
dispersive infrared detection. Depending on the detection a concern not present in direct analysis. For this reason, many
system, the carbon dioxide-containing effluent may be subject interpreters prefer to use TOC data generated from the direct
to selective trapping prior to carbon measurement. TOC oxidation method. Nevertheless, the indirect methods elimi-
values are calculated through the use of external standards nate the need for prior removal of carbonate carbon, resulting
and are reported on a dry-weight basis as a carbonate-free in the ability to process a greater number of samples per unit
carbon mass percentage of starting material. For example, a time. Furthermore, whereas the direct method provides a
typical petroleum source rock might have 2%, 5%, or 10% single parameter – TOC – the indirect method, using current
total organic carbon. Modern instruments for direct carbon instrumentation, provides pyrolytic data in addition to TOC
measurement often possess the simultaneous ability to mea- data, including hydrocarbon yields from pyrolysis over pro-
sure other elements as well (e.g., sulfur, nitrogen). grammed temperature ranges. For this reason, the indirect
The most common indirect method of TOC analysis method is gradually surpassing the direct method and may
involves, prior to a final oxidation step, pyrolytic analysis of ultimately become the technique of choice.
the more labile component of organic matter in the starting The accuracies of analytical methods for TOC measure-
sample. Approximately 0.1 g of untreated sample is heated to ment are a function of instrument quality and known carbon
550  C or 600  C in the absence of oxygen and commonly in a standards in the case of both direct (full oxidative) and indi-
flow of helium (Jarvie 1991). The hydrocarbons and non- rect (pyrolytic/oxidative) measurements. As noted earlier, an
hydrocarbons volatilized in this step, along with those created additional influence to consider when assessing measurement
from pyrolysis of heavy hydrocarbons and kerogen, are quan- accuracy in the case of the fully oxidative method is the
tified with a flame ionization detector. After this initial efficiency of removal, prior to instrumental analysis, of the
oxidant-free heating episode, the sample is oxidized at ele- carbon bound as carbonates. In practice, commercially avail-
vated temperature, and the carbon-containing effluent is able standards are used to assess accuracy, and blanks are run
quantified. Suitable conversion coefficients are used to con- regularly. Analytical precision for both direct and indirect
vert pyrolysis yield to carbon mass, and these coefficients analysis types is usually less than 5–10% relative, as deter-
vary as a function of the type of organic matter in the sample mined through repeated analysis of homogenized aliquots.
(Fujine 2014). The calculated value for carbon derived from Given the wide lateral and stratigraphic variation in carbon
the pyrolysis yield – the so-called convertible fraction – is content within a sedimentary rock unit, this analytical preci-
then summed with the residual carbon amount from oxidation sion level is minor compared to the wide range of natural
to generate the TOC of the sample. Although multiple com- variation in TOC.
mercial instruments are available for assessing TOC indi-
rectly in this manner, the concepts used in the analyses and Computational Approaches for Determination of Initial
computations are similar. TOC (TOCo)
Indirect TOC determination as measured through com- Instrumental measurement of TOC is necessary for determin-
bined pyrolysis oxidation is a multistep process and therefore ing potential and effective source rock characteristics, as
is likely subject to greater error than purely oxidative (direct) noted previously, whereas numerical modeling of deposi-
determination of acid-treated samples. Additionally, as noted tional TOC is critical when samples are unavailable (see the
above, conversion coefficients in the combined pyrolysis- next section). However, it is often useful to compute initial, or
Total Organic Carbon (TOC) 3

depositional, TOC from the present-day TOC of petroleum Physical and chemical inputs controlling the deposition
source rocks. This value, commonly designated TOCo, can be and preservation of organic carbon in a marine setting have
computed with varying degrees of certainty. The techniques been known for decades, although appropriate use of these
for doing so generally utilize present-day TOC values modi- inputs for successful model predictions still remains under
fied according to various assumptions about the process and discussion. Fundamentally, initial production of organic mat-
rate of loss of organic carbon through time. Several authors ter, dominantly in the photic zone of the marine water column,
have proposed various methods (Tyson 2006; Jarvie 2012, must be preserved during transport through the water column
2014; Curiale and Curtis 2016), most of which back- and after taking up residence in unconsolidated sediments.
extrapolate (retrodict) TOCo from kerogen type and present- Dilution of sedimented organic matter with mineral matter
day level of thermal maturity. For example, present-day TOC and biogenic inorganic remains will reduce the proportion of
levels within a single source rock unit of 0.82 and 4.31 at organic carbon (on a mass of carbon to total mass of sediment
thermal maturity levels of Ro = 1.9% and 0.6%, respectively, basis) and, therefore, becomes a critical element in any
may both extrapolate back to a retrodicted TOCo value of numerical model. Thus, estimates of parameters such as pro-
5.0%. It is this value which would be used for this source unit duction rate, accumulation rate and burial efficiency, and the
in resource assessments and as input to, or validation of, the rate of change of these parameters through time are key inputs
numerical models discussed in the next section. to any numerical model for organic carbon accumulation
As reviewed in Curiale and Curtis (2016), estimates to (Tyson 1994). Parameterizing a numerical model with these
back-calculate TOCo by accounting for the effect of thermal inputs has been attempted by several workers (see Mann and
maturity are useful if organofacies or starting maceral distri- Zweigel 2008 and references therein), and it is now possible
butions (or general kerogen type) are known. Straightforward to retrodict regional TOC distributions at past geologic times
efforts include the use of a TOC-maturity relationship based with varying degrees of success.
on a representative set of source rock measurements within a These forward-directed (first principle) numerical models
single unit in a basin. In such an approach, an equation in may also be supplemented with modeled estimates of past
which maturity is the independent variable and TOC is the earth conditions – e.g., using paleogeographic and various
dependent variable is used to compute TOCo. Essentially, paleoenvironmental assumptions – and used in a concerted
TOCo is retrodicted as the TOC value occurring at deposi- fashion to retrodict temporal and spatial deposition of
tional levels of thermal maturity. More complex approaches organic-rich sediments. In this way, we can indirectly assess
include the use of additional parameters, such as initial hydro- TOC levels at time of deposition (Peters et al. 2008; Bohacs
gen index, fitted to various nomograms (Jarvie 2012). et al. 2010 and references therein). Retrodiction approaches of
Although methods for TOCo assessment are useful in this type are available within the petroleum industry and from
resource assessment, the geochemical community has not commercial vendors, although their routine use is inconsistent
yet centralized on a single, acceptable approach. Indeed, as from company to company and vendor to vendor. As with
noted by Curiale and Curtis (2016, p. 16), “. . .all approaches forward-directed numerical models, these too have met with
seeking to determine initial/depositional TOC. . ., while per- varying degrees of success.
haps comforting to the explorationist, are heavily laden with A common approach of paleogeographic-paleoclimate
assumptions, most of which are difficult or impossible to carbon depositional modeling begins by addressing a specific
validate.” Thus, caution is urged. geologic timeslice. A paleoclimate model is typically run
using landform distributions derived from a paleotectonic
Numerical Modeling Approaches model appropriate to the timeslice. Paleoclimate outputs
The importance of total organic carbon information in the (e.g., upwelling intermittence through time; seabottom cur-
petroleum geosciences has led to extra-analytical methods rent and intensity; monthly rainfall patterns) and paleogeo-
of assessment, most particularly those involving numerical graphic inferences (e.g., shore-to-shore distance as a proxy
modeling using various geologic, tectonic, and climatic for oxic conditions in the water column) are employed to infer
inputs. As petroleum exploration has moved to more and settings likely to promote organic matter production and
larger frontier areas, and particularly as the evaluation of preservation. Analytical methods of TOC assessment can be
organic matter in deepwater sediments became critical, the used when representative samples of the geologic unit are
absence of access to source rock material has made modeling available, and results of these analyses can be used to validate
of organic carbon, and organic matter deposition in general, the output of paleogeographic-paleoclimatic modeling.
critical to success. Established models for this purpose have
met with varying levels of success, although modeling accu- Origin and Applications
racy is expected to increase as knowledge of earth history and Total organic carbon values are used extensively in the petro-
general petroleum systems increases. leum geosciences, and the TOC concentration in recent sed-
iments and sedimentary rocks is a fundamental and primary
4 Total Organic Carbon (TOC)

Total Organic Carbon (TOC), Table 1 Source rock interpretation guidelines based on initial (depositional) total organic carbon – TOCo – are
shown here for various ranges. As noted in the text, TOCo alone is unable to assess source rock potential properly. As shown in this figure, kerogen
type and thermal maturity, among other parameters, are also necessary (Hunt 1996)
TOCo
range
(%) Potential interpretation Comments
0–1% Little to no petroleum-generative potential Some workers consider 0.5% as minimum TOCo for gas-prone effective source
rocks
1–5% Poor to fair petroleum-generative potential, if Minimal values for effective source rock occurrence in this range of TOCo depend
organic matter type is appropriate on kerogen type and lithology
>5% Good to excellent petroleum-generative An excellent range for marine and some lacustrine depositional environments;
potential, if organic matter type is appropriate greatly elevated TOCo values commonly encountered in terrigenous depositional
setting may show good gas-prone potential but poor oil-prone potential

parameter in organic matter assessment. This section will averages, and interpretations made by geochemists will vary
briefly describe the development and fate of total organic as a function of kerogen type, thermal maturity, geological
carbon concentration levels in recent sediments and petro- history, and several other factors (Hunt 1996). Indeed, it is
leum source rocks. More details may be found in other entries widely understood that the use of just the TOC value as a
of this encyclopedia. source rock assessment tool is foolhardy – at a minimum,
Organic matter (OM) in sedimentary systems, including its measures of organic matter quality and thermal maturity are
carbon content as well as secondary elements such as hydro- required for this purpose.
gen, oxygen, nitrogen, and sulfur, originates in living systems
native to the water column (autochthonous OM) and to sur-
rounding land surfaces (allochthonous OM). As noted in the Summary
previous section, this organic matter is scavenged as it settles
through the marine or lacustrine water column and often Total organic carbon concentration in recent sediments and
partially oxidized at the water-sediment interface. These phe- sedimentary rocks is a fundamental measurement used in
nomena, supplemented with sedimentary dilution by inor- petroleum geoscience. Its quantitative derivation through ana-
ganic material, yield the TOC levels observed in recent lytical measurement on a per-sample basis or numerical
sediments (Tissot and Welte 1984). modeling at the local and regional scale provides a starting
Once this recent sediment TOC content is established, it point (TOCo) for the assessment of petroleum source rock
then becomes the baseline level – i.e., initial TOC, or capacity, thermal maturity evolution, and surface adsorption
TOCo – from which petroleum source rock potential is characteristics of sedimentary rocks. These applications make
assessed. accurate determination of TOC a key requirement of all
Diagenetic and catagenetic changes which occur during petroleum system evaluations.
sediment burial, including microbial utilization of organic
carbon and loss of organic carbon due to generation of petro-
leum and its expulsion from the sediment, gradually reduce Cross-References
the organic carbon content. (Exceptions can also occur. For
example, TOC of coarse-grained reservoir rocks can increase ▶ Basin and Petroleum System Modeling
when petroleum accumulates in the pore space of these ▶ Hydrocarbons: Origin
rocks.) Knowledge of this reduction is useful in assessing ▶ Petroleum Exploration
past and present capacity of a sedimentary rock to generate ▶ Petroleum Geochemistry
and expel petroleum and thus has extensive application in ▶ Petroleum Source Rocks
petroleum geoscience (Hunt 1996). ▶ Petroleum System
Total organic carbon levels necessary for the generation of ▶ Programmed Pyrolysis
petroleum are a continuing subject of discussion, and several ▶ Total Organic Carbon: Calculations from Well Logs
workers have proposed ranges useful for source rock assess- ▶ Total Organic Carbon: Estimation of Initial TOC
ment. Interpretations based on these ranges require several
factors to be considered, including postdepositional loss of
TOC due to generation and expulsion of petroleum. Table 1
provides guidelines for interpretation of present-day TOC as a
determinant of present-day petroleum source rock potential. It
is important to consider that these ranges are only broad
Total Organic Carbon (TOC) 5

Bibliography resources for the 21st century. AAPG Memoir, 97. American Asso-
ciation of Petroleum Geologists. Tulsa, Oklahoma. pp 69–87
Bohacs KM, West BP, Grabowski GJ (2010) Retrodicting source-rock Jarvie DM (2014) Components and processes affecting producibility and
quality and paleoenvironmental conditions. US Patent Application commerciality of shale resource systems. Geol Acta 12:307–325
Publication No. US 2010/0175886, 15 July 2010 Mann U, Zweigel J (2008) Modelling source-rock distribution and
Curiale JA, Curtis JB (2016) Organic geochemical applications to the quality variations: the organic facies modelling approach. Spec
exploration for source-rock reservoirs – a review. J Unconv Oil Gas Publ Int Assoc Sedimentol 40:239–274
Resour 13:1–31 Peters KE, Ramos LS, Zumberge JE, Valin ZC, Scotese CR (2008) Res-
Fujine K (2014) IODP source rock (SR) analyzer: user guide. https:// toration of Circum-Arctic upper Jurassic source rock paleolatitude
rosetta.iodp.tamu.edu/A/TechDoc/14?encoding=UTF-8 based on crude oil geochemistry. Org Geochem 39:1189–1196
Hunt JM (1996) Petroleum geochemistry and geology, 2nd edn. Schumacher BA (2002) Methods for the determination of total organic
W.H. Freeman and Company, San Francisco. 743 p carbon (TOC) in soils and sediments, NCEA-C-1281, EMASC-001.
Jarvie DM (1991) Total organic carbon (TOC) analysis. In: Geochemical United States Environmental Protection Agency. Washington, D.C.
methods and exploration, Chapter 11. In: Source and migration Tissot BP, Welte DH (1984) Petroleum formation and occurrence: a new
processes and evaluation techniques. American Association of Petro- approach to oil and gas exploration. Springer, Berlin. 538 p
leum Geologists Treatise, Tulsa, Oklahoma. pp 113–118 Tyson RV (1994) Sedimentary organic matter. Springer, New York
Jarvie DM (2012) Shale resource systems for oil and gas: part 1 – shale- Tyson RV (2006) Calibration of hydrogen indices with microscopy: a
gas resource systems. In: Breyer JA (ed) Shale reservoirs – giant review, reanalysis and new results using the fluorescence scale. Org
Geochem 37:45–63
M

Microfossils: Calcareous Nannoplankton Introduction

(Nannofossils)
Microscopic investigations of nannofossils have important
Sudeep Kanungo1, Jeremy Young2 and Gosia Skowron1 applications in petroleum geology as they provide critical
1
University of Utah, Energy & Geoscience Institute (EGI), information and data on geologic age (biostratigraphy) and
Salt Lake City, UT, USA sedimentary facies of petroleum source and reservoir rocks
2
Department of Earth Sciences, University College London that have been deposited since the Late Triassic. In the fossil
(UCL), London, UK record, nannofossils are found in fine-grained pelagic and
hemipelagic sediments and can also occur in rock-forming
proportions in facies such as the Upper Cretaceous chalk. The
Definition calcite in chalk is derived primarily from nannofossils, and
other calcareous microfossils such as foraminifera and
Calcareous nannoplankton or nannofossils are a heteroge- calcispheres. The Late Cretaceous is unusual in having wide-
neous group of marine living organisms and calcareous fossil spread chalk deposition in shelf environments, but similar
structures, generally smaller than 30 mm in size. These uni- facies have accumulated since the Jurassic in deep-sea envi-
cellular, planktonic organisms are the most abundant calcify- ronments. Nannoconids, a distinctive group of Mesozoic
ing organisms on our planet. The term “nannoplankton” was nannofossils, were carbonate rock-forming organisms in
coined by the German scientist H. Lohmann in 1902 for Upper Jurassic–Lower Cretaceous pelagic limestones, and
plankton capable of passing through the finest nets with a in Lower Cretaceous chalks of the North Sea.
mesh size < 63 mm. This is a diverse group of organisms, but Oil and gas is produced from chalk reservoirs successfully
the only ones which are fossilized to any great extent are in the North Sea and the Middle East. In the US Gulf Coast,
coccoliths, the calcareous plates of coccolithophores. significant discoveries have been made from the Austin
Group, which are, predominantly, low-porosity lime mud-
stones packed with nannofossils and foraminifera. However,
Synonyms oil production in the Austin Group is derived from fracture
porosity, not inter-coccolith pores. In the US Western Interior,
Calcareous nannofossils; Coccolithophores; Coccoliths; unconventional hydrocarbons (oil shale) are being actively
Nannofossils; Nannoplankton explored from the Upper Cretaceous Niobrara chalk fractures.
Overviews of different microfossil groups, including cal-
careous nannofossils, have been provided by several authors,
These terms, however, have somewhat different meanings:
notably Haq and Boersma (1978) and Armstrong and Brasier
“nannoplankton” and “coccolithophore” refer to the whole
(2005). Plankton Stratigraphy, edited by Bolli, Saunders and
organism, while “nannofossil” and “coccolith” refer to the
Perch-Nielsen (1989), in two volumes, is a treatise on micro-
calcareous plates. Similarly, coccolithophores and coccoliths
fossil disciplines and their biostratigraphic applications. Cal-
refer to one taxonomic group, whereas nannofossil and nanno-
careous Nannofossil Biostratigraphy, edited by Bown (1998)
plankton are broader terms. In practice, however, these differ-
is a practical textbook and atlas exclusively on nannofossils.
ences are largely ignored outside academic circles, and the
terms are often used interchangeably.

# Springer International Publishing AG 2017

R. Sorkhabi (ed.), Encyclopedia of Petroleum Geoscience,
DOI 10.1007/978-3-319-02330-4_4-1
2 Microfossils: Calcareous Nannoplankton (Nannofossils)

Biology of Coccolithophores: Haptophyte Algae Morphology

Coccolithophores, the dominant group of calcareous nanno- Hard-part morphology is the main basis for classifying living
plankton, are unicellular planktonic algae with photosynthetic and fossil members of the group. Coccoliths are divided into
pigments. Coccolithophores are important primary producers two principal groups: heterococcoliths and holococcoliths.
in the marine ecosystem. They belong to the division A third informal group of nannoliths exists, whose origins
Haptophyta and like most haptophytes, possess two flagella are uncertain with regards to Haptophyte algal affinities
of equal length and a third whiplike, coiled structure called the (Young et al. 1999). The three groups are briefly described
“haptonema.” Within the Haptophyta, the coccolithophores below.
are distinguished by their ability to produce calcareous scales,
called coccoliths, to form an exoskeleton, known as the (i) Heterococcoliths are formed of a radial array of
coccosphere (Fig. 1). complex-shaped intergrown calcite crystals. Growth
The classification of coccolithophores follows the rules of starts from a proto-coccolith ring of calcite nuclei,
the International Code of Botanical Nomenclature (ICBN) which results in a rather characteristic division into a
with the following hierarchy: rim, with strongly radial structure, and a central area,
which may be empty, crossed by bars, filled with a plate
Kingdom, Protoctista; Division, Haptophyta; Class, or lattice, and sometimes preserved with a spine (Fig. 1b,
Prymnesiophyceae coccolith rim and central area). The inward or proximal
face of the coccolith which faces toward the cell is
As illustrated in Fig. 1a, a coccolithophore cell shows typically flat or concave.
straightforward organization for eukaryotic phytoplankton, Heterococcoliths vary considerably in form and con-
dominated by two large chloroplasts and a nucleus, along struction, and some special descriptive terms are used for
with mitochondria and the Golgi body. While the chloroplast heterococcolith rim morphology, the two most important
and nucleus serve as sites of photosynthesis and genetic being murolith and placolith. Muroliths have elevated
material, the mitochondria is associated with energy storage. rims without distinguishable proximal and distal shields
The Golgi body, a stack of interlinked vesicles, serves various (Fig. 2), e.g., Zeugrhabdotus (Mesozoic genus) and
biosynthesis functions and, in coccolithophores, is modified Pontosphaera (Cenozoic genus). These typically abut
as the site of coccolith formation. The coccoliths are formed against one another on the coccosphere forming a single
inside Golgi vesicles, and then extruded to the cell surface via continuous cover. Placoliths have rims with two or more
a process, which has been studied by both transmission elec- well-developed shields (Fig. 2), e.g., Coccolithus
tron microscopy (Probert et al. 2007) and video microscopy (Cenozoic genus; Fig. 3-1), Emiliania (living genus;
(Taylor et al. 2007). Fig. 3-2), and Watznaueria (Mesozoic genus; Fig. 3-3).
These typically interlock and overlap on the
coccosphere, forming a robust shell (Fig. 3-1).
Fossilization of Coccoliths (ii) Holococcoliths are made of uniformly shaped calcite
crystals, commonly about 0.1 mm across, held together
Tiny coccoliths constitute an exoskeleton around by an organic matrix. These crystals are typically
coccolithophore cells, forming a coccosphere. After death, euhedral calcite rhombohedrons showing uniform align-
coccospheres sink through the water column at rates of a ment over large surfaces. Unlike heterococcoliths,
few meters per day (Young 1994) and tend to disintegrate holococcoliths often do not show a clear distinction
into individual coccoliths, which sink even slower. However, between the rim and the central area and exhibit more
sinking is accelerated by incorporation into fecal pellets and homogeneity in construction. The fossil record of
by aggregation as “marine snow.” The smallest and most holococcoliths is sparse and sporadic due to their low
delicate coccoliths have low preservation potential, but iden- preservation potential, both during transport through the
tifiable coccoliths can be preserved up to the calcite compen- water column and during diagenesis in sediments.
sation depth (CCD). Bioturbation on the seafloor further Examples include Lucianorhabdus (Mesozoic genus;
disaggregates coccospheres, so, in the marine fossil record, Fig. 3-9) and Holodiscolithus (Cenozoic genus).
individual coccoliths are much more common (over 99%) (iii) Nannoliths are an informal group of variably shaped
than complete coccospheres. As they are abundant and rela- (starlike, rod-shaped, florets, etc.,) calcareous structures
tively easy to extract from marine calcareous sediments, with unknown origins (Fig. 4). Nannoliths can be the
nannofossils are a prime means of dating post-Triassic same size or larger than coccoliths and co-occur with
sediments. them in the stratigraphic record. It is possible that some
nannoliths are formed by different biomineralization
Microfossils: Calcareous Nannoplankton (Nannofossils) 3

b COCCOLITH
outer rim
cycle
rim
inner rim
cycle

central area

central area
structure
element

haptonema

cytoplasm flagella

a cross-section
Golgi body
cross-section

chloroplast

nucleolus
nucleus

mitochondria
storage vesicle

Microfossils: Calcareous Nannoplankton (Nannofossils), coccolith in plan (top) view under the microscope (Source: Bown and
Fig. 1 (a) Schematic diagram (not to scale) of the structure and com- Young (1998a))
ponents of a coccolithophore cell covered with coccoliths. (b) Single

processes to either hetero- or holococcoliths (Young crystals thicker than 0.1 mm, the following terms are used to
et al. 1999). Examples include Braarudosphaera describe calcite c-axis orientation:
(living genus; Fig. 4a) and Discoaster (Cenozoic
genus; Fig. 4b). V-unit: crystal unit with subvertical orientation of c-axis;
when the coccolith is lying in plan (top) view, these appear
dark in all orientations under xpl.
Crystallography R-unit: crystal unit with sub-radial orientation of c-axis; when
the coccolith is lying in plan view, these appear bright
Calcite crystallographic orientation is precisely controlled under xpl, and the cycle of unit shows a pseudo-extinction
during coccolith growth and provides a key for understanding cross.
phylogenetic relationships. It also controls the appearance of T-unit: crystal unit with sub-tangential orientation of c-axis,
nannofossils in cross-polarized light microscopy (xpl). The and like R-units, these are bright in xpl and exhibit a
brightness or birefringence of a calcite crystal unit under xpl is pseudo-extinction cross. The two (R- and T-units) can be
a function of its thickness and orientation. Very thin calcite distinguished by using an accessory plate, such as a gyp-
crystals usually appear dark, irrespective of orientation. For sum plate. T-units are virtually absent in the rims of
heterococcoliths but are common in nannoliths, for
4 Microfossils: Calcareous Nannoplankton (Nannofossils)

PLACOLITH MUROLITH
LIFE DISTAL
POSITION DISTAL

cell wall
PROXIMAL cell wall
PROXIMAL
tube cycle outer,
VERTICAL distal cycle
SECTION rim
distal shield inner,
rim proximal cycle
proximal shield

LATERAL
VIEW
dextrally-imbricate distal-shield
elements, sutures displaying radially-arranged
anticlockwise obliquity butting elements vertically-oriented
dextrally-imbricate outer rim cycle
outer rim cycle (Protolith)
monocyclic (Loxolith)
suture shield
obliquity
DISTAL
VIEW

bicyclic shield

clockwise anticlockwise
obliquity of sutures imbrication of elements

Microfossils: Calcareous Nannoplankton (Nannofossils), Fig. 2 Schematic diagram (not to scale) of heterococcolith (placolith and murolith)
structures and rim morphologies (Source: Bown and Young (1998a))

example, in the families Polycyclolithaceae, significant part of the phytoplankton community, along with
Nannoconaceae, and Braarudosphaeraceae (Bown and diatoms, dinoflagellates, and cyanobacteria. As a photo-
Young 1998a). synthesizing group, they live in the photic zone of the water
column. They reach maximum diversity in tropical and sub-
tropical latitudes and are less diverse, though more abundant
Taxonomy in temperate and sub-Arctic waters, but tend to be very rare or
absent at latitudes higher than 70 . The majority of species
Detailed taxonomy of the group is outside the scope of this have broad ecological tolerances for a wide range of temper-
entry. Perch-Nielsen (1985a, b) and Bown (1998) are two ature and salinities.
comprehensive references on nannofossil taxonomy covering Nannoplankton distribution patterns are strongly related to
their entire evolutionary history. Since then, there has not surface water temperature and macronutrient availability
been a major published review, and the most comprehensive (nitrate and phosphate), which, in turn, are linked to oceano-
data is now available online. In particular, the Nannotax graphic features such as circulation and water masses. Sea-
project (mikrotax.org/Nannotax3) which started in 2007 at sonally stable, oligotrophic (low-nutrient), tropical and
University College London, UK, has been instrumental in the subtropical ocean gyre environments support the highest
online documentation of nannofossil taxonomy (Young et al. diversities, but standing populations tend to be very low,
2017). A large database including more than 2,500 taxa and reflecting nutrient limitation. Eutrophic (nutrient-rich) condi-
20,000 images on Nannotax are widely used by nannofossil tions, associated with the continental shelf, or in upwelling
workers globally. zones, support high-standing populations dominated by a
distinctive assemblage of one or a few species. There are
strong contrasts between eutrophic and oligotrophic assem-
Ecology and Distribution blages in terms of taxonomic composition of the plankton
assemblages. These contrasts are not as strong in sediments
Calcareous nannoplankton have a widespread marine distri- due to effects of seasonal averaging of assemblages and
bution, from the shelf to the open ocean, and constitute a differential preservation (Andruleit et al. 2004). That being
Microfossils: Calcareous Nannoplankton (Nannofossils) 5

Microfossils: Calcareous Nannoplankton (Nannofossils), embergeri. 8. SEM of Poricalyptra aurisinae coccosphere. 9. SEM of
Fig. 3 Comparative micrographs of some Cenozoic and Mesozoic Lucianorhabdus cayeuxii (Mesozoic holococcolith). 10. LM (XPL, left;
nannofossil species. 1. SEM (Scanning Electron Micrograph) of PC, right) of Lucianorhabdus cayeuxii. 11. SEM of Braarudosphaera
Coccolithus pelagicus coccosphere (living species). 2. SEM of bigelowii (living nannolith). 12. SEM of Eprolithus floralis, side view of
Emiliania huxleyi (living species). 3. SEM of Watznaueria barnesiae broken specimen (Mesozoic nannolith). 13. SEM of Eprolithus floralis,
(Mesozoic placolith). 4. LM (Light microscope), cross-polarized light plan view. 14. LM (XPL, left and PC, right) of Eprolithus floralis (plan
(XPL, left) and phase contrast view (PC, right) of same specimen of view). 15. LM (XPL, left and PC, right) of Eprolithus floralis (side
Watznaueria barnesiae. 5. SEM of Pontosphaera syracusana view). Note: All individual scale bars on the plate are 1 mm (Source:
coccosphere. 6. SEM of Zeugrhabdotus embergeri (Mesozoic murolith). Authorsrsquo; archive)
7. LM (XPL, left; PC, right) of same specimen of Zeugrhabdotus

said, the differentiation is still noticeable, especially in source chlorophyll maximum) and deep photic zone
rock-related oceanic anoxic events (OAEs), where eutrophic (sub-thermocline) assemblages (Winter and Siesser 1994).
assemblage abundances have been used as a proxy to pick The deep photic zone species, Florisphaera profunda, is
high total organic carbon (TOC) intervals. well represented in the Quaternary and Pliocene fossil record
In addition, there is clear evidence for vertical stratification and has proven to be an invaluable proxy for surface water
of nannoplankton in the water column, especially in stably oligotrophy (Molfino and McIntyre 1990; Beaufort
stratified subtropical environments, via a well-developed et al. 1997).
upper photic zone, middle photic zone (thermocline/deep
6 Microfossils: Calcareous Nannoplankton (Nannofossils)

Microfossils: Calcareous
Nannoplankton
(Nannofossils), a b c
Fig. 4 Schematic diagram (not to
scale) showing morphology of
three nannolith genera. (a) Genus
Braarudosphaera (living genus).
(b) Genus Discoaster (Cenozoic).
(c) Genus Ceratolithus (Neogene)
(Source: www.mikrotax.org/
Nannotax3)

not to scale

Modern nannoplankton biogeography is defined by broad Major Events in Nannoplankton Evolution

latitudinal zones and is distinguished by variations in assem-
blage composition rather than high endemicity. The majority Bown et al. (2004) synthesized nannofossil evolution and
of species show a cosmopolitan distribution. By analogy with diversity using speciation and extinction rates to delineate
living nannoplankton, Mesozoic and Cenozoic paleobiogeo- major events in the history of the group, which have signifi-
graphical distributions also reflect temperature controls and cant implications in biostratigraphy. A summary of major
are broadly recognized as paleolatitudinal, with low-, mid-, nannofossil evolutionary events is given in a chronological
and high-latitude assemblage patterns (Lees 2002; see order in Table 1. Photomicrographs of some of the important
“Applications of Calcareous Nannofossils in Petroleum Mesozoic and Cenozoic taxa are illustrated in Fig. 3.
Exploration” section).
(i) Late Triassic (Carnian) first appearance: The earliest
records of nannofossils are from Carnian sediments in
Reproduction and Life Cycle the Southern Alps of Italy. Only a few other surviving
pelagic sections are known from the Upper Triassic
Reproduction in coccolithophores is predominantly asexual (NW Australia, Canada, and Timor) that document the
and occurs via binary fission. Asexual reproduction allows first appearance of nannofossils. These earliest forms
rapid proliferation forming coccolith “blooms” (e.g., were nannoliths (e.g., Prinsiosphaera), coccoliths
Emiliania huxleyi bloom) under optimal environmental con- (e.g., Crucirhabdus), and calcispheres (e.g., Ortho-
ditions. In addition, coccolithophores have a sexual life cycle pithonella). Triassic assemblages are characterized by
with alternation of haploid and diploid phases. Somewhat very low diversity and are only seen in low
unusually, both the haploid and diploid life cycle phases are paleolatitude sites.
capable of indefinite binary fission. (ii) Triassic–Jurassic boundary extinction: A major extinc-
The best documented example of a single species produc- tion episode where the majority of the Late Triassic
ing both heterococcoliths and holococcoliths is provided by nannofossil species became extinct at, or close to the
the living species Coccolithus pelagicus. The typical phase of boundary, coinciding with mass extinctions
C. pelagicus is non-motile and bears large placolith hetero- documented in invertebrate and vertebrate faunas.
coccoliths (Fig. 5). Monoclonal cultures of C. pelagicus occa- One coccolith species, Crucirhabdus primulus, sur-
sionally undergo a phase change, giving rise to quite different vived into the Jurassic.
motile cells bearing holococcoliths. In addition, combination (iii) Early Jurassic evolutionary radiation: One of the most
coccospheres showing both coccolith types are occasionally significant diversification events in the group’s history
seen in living plankton communities (Fig. 5, center). In many was in the Early Jurassic. More than half of the
other species, these combination coccospheres have allowed 16 Mesozoic families originated in the Early Jurassic,
life cycle pairings to be established without any laboratory and much of the modern high-level molecular genetic
cultures (Cros et al. 2000). diversity can be related to this event (Medlin et al.
Life cycle phases are a fascinating phenomenon which has 2008). Coccoliths became the dominant nannofossil
greatly changed our knowledge of coccolithophore biology group with the appearance of placoliths by the latter
and ecology. However, for paleontologists, reconstruction of half of the Early Jurassic (Pliensbachian–Toarcian).
life cycle pairings is almost impossible, so the different phases Holococcoliths also appeared for the first time in the
are, in effect, treated as separate species. stratigraphic record with the genus Anfractus.
Microfossils: Calcareous Nannoplankton (Nannofossils) 7

Microfossils: Calcareous Nannoplankton (Nannofossils), heterococcoliths (center), and of the heterococcolith-bearing diploid
Fig. 5 Life cycle phases in the living species, Calcidiscus leptoporus phase (right). The arrows indicate how the transition from haploid to
ssp. quadriperforatus. The images (from left) are of the holococcolith diploid phase can occur, with the fusion of two haploid cells giving rise
bearing, haploid phase (formerly called Syracolithus quadriperforatus), to the diploid cell, which initially has a covering of holococcoliths,
of a combination coccosphere with both holococcoliths and inherited from the haploid phase (Source: Authors’ archive)

Microfossils: Calcareous Nannoplankton (Nannofossils), Table 1 Timeline of major evolutionary events in nannofossils (Based on Bown et al.
2004)
Geologic time Associated nannofossil evolutionary events and changes
Late Triassic (Carnian) First appearance of nannofossils in the fossil record; low diversity; rare occurrences in low paleolatitude sites
Triassic–Jurassic Major extinction; almost all the Triassic species except the coccolith species, C. primulus, went extinct
boundary
Early Jurassic Major diversification with new Mesozoic families; holococcoliths appeared for the first time; coccoliths became the
dominant group
Jurassic–Cretaceous Large turnover with extinctions and originations; 3 new nannolith families appeared (e.g., Nannoconus); steady
boundary diversity increase
Mid-Cretaceous Broadly cosmopolitan nannofossils with well-known high-fertility index species (e.g., B. constans, Z. erectus/
noeliae)
Late Cretaceous Acme in diversity (~150 species); widespread chalk and marl deposition; marked endemism in the Campanian
K–Pg boundary Nannofossil mass extinction event; ~90% of the species went extinct
Paleogene Rapid diversification in the Late Paleocene with several new lineages; ~120 species in the Eocene; diversity drop in
the Oligocene
Neogene and Quaternary Miocene recovery and diversification in the Discoaster family; overall diversity loss and size reduction in the
Quaternary

(iv) Jurassic–Cretaceous boundary turnover: The is particularly important because their role in primary
Tithonian–Berriasian boundary was a time of large turn- productivity is useful in understanding the causal mech-
over at the species and family level. There were approx- anisms of OAEs. Elevated phytoplankton productivity is
imately 17 extinctions and 15 originations at the species cited as a major component of mid-Cretaceous OAEs,
level, with the appearance of 3 nannolith families. Three especially OAE 1a and OAE 2, contributing to a signif-
nannolith genera, Nannoconus, Braarudosphaera, and icant proportion of global source rocks (Leckie et al.
Micrantholithus evolved at or close to the boundary, of 2002). Characteristic marker species of the mid-
which Braarudosphaera still survives in the modern Cretaceous include, among others, Corollithion
oceans. Under certain conditions, nannoconids contrib- kennedyi, Lithraphidites acutus (Cenomanian markers),
uted to the deposition of pelagic limestones during this Axopodorhabdus albianus (Albian–Cenomanian), and
time. Following the boundary, nannofossil diversity Hayesites albiensis (Albian).
appears to have steadily increased through the Early (vi) Late Cretaceous acme in diversity: The Late Creta-
Cretaceous. ceous saw the pinnacle of nannofossil diversity, with
(v) Mid-Cretaceous: The Aptian–Cenomanian interval, a the Campanian–Maastrichtian interval (marker species
time of high-diversity and cosmopolitan nannofossils, include Arkhangelskiella cymbiformis, Reinhardtites
8 Microfossils: Calcareous Nannoplankton (Nannofossils)

levis, Lithraphidites quadratus, etc.) recording the Discoaster surculus in the Pliocene. The overall trend
highest diversity in the history of the group with more from the Pliocene to Holocene is one of diversity loss
than 150 species. Nannofossil chalk and marl deposi- and size reduction, which is evident in the genera
tion was geographically widespread in the Upper Cre- Gephyrocapsa, Pseudoemiliania, and Emiliania. Neo-
taceous. High atmospheric CO2 concentrations gene marine sediments are extensively recovered
supported a greenhouse climate along with high sea through offshore commercial drilling in the US Gulf
levels and extensive epicontinental seas. Furthermore, Coast and SE Asia, where nannofossil biostratigraphy
modern ocean pathways had opened, promoting global plays a major role in exploration and production studies
dispersal of the majority of phytoplankton. However, (see “Applications of Calcareous Nannofossils in
the Campanian, and to some extent the Maastrichtian, Petroleum Exploration” section).
witnessed significant endemism, related to enhanced
paleobiogeographic differentiation within
nannofossils. Research Workflow
(vii) Cretaceous–Paleogene (K–Pg) boundary: The cata-
strophic extinction at the K–Pg boundary represented The workflow begins with sample collection and preparation,
a species extinction rate of around 90%, making it the followed by microscopic observation and sample data docu-
most dramatic event in the group’s evolutionary his- mentation, leading to data presentation and report generation
tory. Available evidence indicates that the nannofossil (Fig. 6). These steps are summarized in this section.
mass extinction event was abrupt and therefore tends to
support the meteorite impact hypothesis (Schulte et al. Sample Collection and Design
2010). A range of taxa, most of which were only Chalks, marls, muddy sands, and silts, including glauconitic
present in very low numbers prior to the boundary, sands, can all yield well-preserved nannofossil assemblages.
did survive the event (e.g., Markalius inversus, Poor preservation or complete absence is common in coarse
Zeugrhabdotus sigmoides) and went on into Paleocene clastic rocks or indurated limestones, where the fine carbonate
assemblages for a short time. Some of them gave rise to fraction has been recrystallized or etched.
new Cenozoic lineages. Most paleontological data in industry wells is derived from
(viii) Paleocene radiation: A period of rapid radiation ditch-cutting samples (also called well cuttings). These sam-
followed in the Paleocene (around 60 new species ples are taken from the rig’s “shale shaker” and consist of rock
were added) that resulted in diverse coccolith morphol- fragments produced by the rotary drill bit from a known depth
ogies, often significantly different from those seen in interval (e.g., 500–510 m), but also dislodged rock fragments
the Mesozoic. In addition, new nannolith groups such from shallower well depths. The dislodged rock fragments
as Sphenolithus and Discoaster arose that characterized become a dangerous source of downhole contamination or
Paleogene and Neogene assemblages. “cavings.” The microfossils found in well cuttings are a
(ix) Eocene diversity: A diversity peak (~120 species) is mixture of those that come from the in situ section interval
noted in the Late Paleocene–Early Eocene time, which drilled, and microfossils that originated at shallower well
is associated with a global warming and ocean acidifi- depths, but then got “caved” into the drilled interval
cation event, followed by a slow diversity decline to a (Fig. 7a). Because of this contamination problem, biostrati-
minimum of around 40 species in the Oligocene. The graphic analyses using well cuttings emphasize using the top
recovery of hydrocarbons in post-Paleocene sediments or first downhole occurrence of a microfossil. Conversely, the
and the application of seismic and sequence stratigra- base or last downhole occurrence of a microfossil cannot be
phy to explore the nature and geometry of stratigraphic reliably defined using well cuttings because a microfossil can
traps have led to a demand for high-resolution biostra- continue to be recovered below its true base, due to contam-
tigraphy for the Eocene and Oligocene. Important ination from downhole cavings. Hence bases are rarely, if at
Eocene–Oligocene genera include Chiasmolithus, all, used in the industry. The opposite problem of reworking,
Discoaster, Helicosphaera, Sphenolithus, and or recycling of older material that causes the upper strati-
Reticulofenestra. graphic limit (or top) of the microfossil to be overextended,
(x) Neogene and Quaternary: The Miocene was marked by can also be a common source of error in biostratigraphic
recovery and diversification, especially among the studies, if it goes unrecognized (Fig. 7b).
Discoaster family (D. hamatus, D. berggrenii, In contrast to ditch-cutting samples, core samples
D. quinqueramus, etc.). Other marker species include (conventional and side wall cores) are taken from discrete
Triquetrorhabdulus carinatus, Sphenolithus hetero- well depths and do not represent a mixture of rock fragments
morphus, and Helicosphaera ampliaperta in the Mio- from shallower depths. Microfossils recovered from core
cene, and Reticulofenestra pseudoumbilicus and
Microfossils: Calcareous Nannoplankton (Nannofossils) 9

50 m or more), depending on the thickness of the stratigraphic

I. Sample Collection interval that is analyzed. For high-resolution biostratigraphy,
1. Cuttings
such as identifying biohorizons, finely tuned samples (about
2. Core 1 m intervals or less) are recommended to identify changes in
3. Outcrop
biostratigraphic character within the assemblages.

Sample Preparation
Nannofossils are viewed in sediment smear slides because it is
II. Sample Preparation impossible to extract individual specimens due to their minute
size. The standard technique for preparing smear slides for
1. Smear slide light microscopy (LM), involves four basic steps: (a) scraping
2. Pipette straw a little rock powder onto a cover slip, (b) dispersing the
sample in a drop of buffered distilled water, (c) mixing with
a toothpick and smearing the resulting suspension across the
cover slip, and (d) drying the cover slip before affixing it on a
slide, using an optical mounting medium. The aim is to obtain
III. Optical Observation
a uniform concentration of nannofossils per field of view
Light microscope (FOV) during microscopic examination so that statistical
1. Leitz, Nikon, Olympus, Zeiss
2. Essentials
variability is minimized.
- x100 oil immersion objective lens A variation from this technique is the pipette strew slide,
- good condenser
- rotating stage which involves preparing the sediment suspension in a beaker
- binocular head with distilled water and flooding the coverslip with the sus-
- XPL and PC illumination
- gypsum plate pension, using a pipette. Some smearing of the suspension is
often necessary even with this method. An advantage of the
pipette strew method is that a deflocculant (e.g., Calgon) can
be added to the sediment suspension to aid disintegration of
IV. Data Acquisition the clay particles (Bown and Young 1998b).
Because of their small, dust-sized nature, chances of con-
1. Semi-quantitative counting tamination during nannofossil preparation is considerably
2. Relative abundance counting
3. Fixed FOV and extended counting higher than for other fossils, therefore special care should be
4. Preservation analysis taken by avoiding rock dust in the preparation area,
5. Diagenesis/overgrowth recognition
6. Reworking/caving recognition maintaining highly clean surfaces, and using disposable
7. Photography equipment.

Observation under the Light Microscope (LM)

Routine study is carried out on the LM, which allows an
accurate determination of calcite crystallography and identi-
V. Data Presentation
fication to the species level. The essential requirements for a
microscope include (a) high-quality 63 or 100 oil-
1. Range charts (biostratigraphy) immersion objective lens (b) high-quality condenser matched
- spreadsheet
- StrataBugsTM to the objective, (c) binocular head and rotating stage, and
(industry software) (d) cross-polarized illumination (xpl). Leitz, Nikon, Olym-
2. Report
pus, and Zeiss are the major suppliers of microscopes. Scan-
ning electron microscopy is invaluable for research on
Microfossils: Calcareous Nannoplankton (Nannofossils), nannofossil taxonomy, but it is much slower than light
Fig. 6 Workflow of nannofossil research from sample collection to microscopy and can only be used on clay-free sediments.
data presentation So, for biostratigraphy, light microscopy is almost
always used.
samples are likely in situ, allowing both tops and bases to be
used in biostratigraphic analyses. LM Photography
Sample design varies according to the needs of the project. Digital cameras fitted to microscopes capture high-quality
In expanded sections and for broad age control, sampling is LM images. The resolution achieved is excellent and allows
usually designed at relatively coarse intervals (about every for faster generation of LM photographs or plates.
10 Microfossils: Calcareous Nannoplankton (Nannofossils)

Microfossils: Calcareous
Nannoplankton
a b
(Nannofossils), Fig. 7
(a) Potential problem of “cavings”
in well cuttings causing false false
bases; (b) reworking causing true false range
range range

reworking
false top
false tops
true
range

caving
Legend

Base
Top
false base Nannofossil

well bore well bore

Photography is a good practice and comes in handy, espe- method helps in achieving statistically significant counts
cially in identifying doubtful specimens. Furthermore, an LM without being overly time consuming. A series of abundance
photograph constitutes a valid holotype (primary specimen) categories ranging from “rare” (1–5 specimens) to “extra
on the basis of which a new species is created under the rules abundant” (>9999 specimens) can be assigned to each iden-
of the ICBN. tified taxon. However, even with using this accurate method,
rare marker species can be missed, so most workers perform
Data Documentation the cascading count on one traverse, and then look for rare
This involves counting nannofossils in a sample using the markers over several more traverses.
semiquantitative or quantitative method.
The semiquantitative counting technique is used to record Data Presentation
the relative abundance of each taxon, in terms of specimens Stratigraphic range charts (or distribution charts)
per FOV, using a logarithmic scale. Usually four or more documenting the occurrence of identified species on a
traverses are performed across the length of the coverslip to sample-by-sample basis are the most effective way of pre-
arrive at relative abundance categories, such as present (P), senting biostratigraphic data. Data such as sample depth/
rare (R), few or frequent (F), common (C), and abundant (A). height, lithologic units, comments on overgrowth/preserva-
These are mnemonic terms, to a large degree, and there is no tion, inferred nannofossil zone, and age assignment are usu-
universal agreement among nannofossil experts on these ally recorded along with the relative abundances of species.
categories. Spreadsheets offer the simplest tool to create range charts
The quantitative cascading count method (Styzen 1997) is (Fig. 8), although software applications such as StrataBugsTM
used in the industry for counting individuals of each taxon in a and BugwareTM are well established in the industry. Strati-
limited number of FOVs, sometimes as low as 5–10 FOVs, graphic range charts are an integral component of reports and
and then multiplying that count number by an integer to publications.
estimate the number of specimens per traverse (e.g., number
of individuals with a double digit count are multiplied by
12 after counting 10 FOVs), in order to relate it to a full
traverse. Usually after a quarter traverse, all but taxa with
the lowest abundances are assigned an abundance count. At
this point, the remaining taxa can be counted for the rest of the
traverse without generating excessively high counts. This
Microfossils: Calcareous Nannoplankton (Nannofossils) 11

Microfossils: Calcareous Nannoplankton (Nannofossils), Fig. 8 An example of stratigraphic range chart (nannofossil) from an industry well
showing sample depth on the vertical axis and logged species on the horizontal axis. Semiquantitative counting technique is demonstrated via the
species abundance scale (P, R, C, etc.)

Applications of Calcareous Nannofossils in chalk (Mutterlose and Bottini 2013), plus a nearly cosmo-
Petroleum Exploration politan distribution across marine habitats
• Inexpensive and quick preparation technique that can be
Biostratigraphy applied even on drilling rigs
Nannofossils are primarily employed to determine the age of
marine sedimentary rocks, including petroleum source and However, nannofossils also suffer from major disadvan-
reservoir rocks, and to correlate rock sections from one well to tages, namely:
another well and from one basin to another basin. Their utility
as global biostratigraphic tools is attributed to the following • Compromised preservation in certain environments, e.g.,
factors: Miocene prodelta environments in the Gulf of Mexico
(Everett 1982)
• Rapid evolutionary changes within the group, associated • Vulnerability to destruction by diagenetic processes due to
with high diversity and varied morphologies their minuscule size
• Small size that protects them from mechanical damage and • Greater susceptibility to reworking, downhole caving, and
allows them to be studied in well cuttings or small rock laboratory contamination, compared to other microfossils,
chips (only a toothpick sample is sufficient) again due to their minute size
• Exceptional abundance in calcareous sediments (e.g.,
2.4  109 specimens per gram of Barremian–Aptian Nannofossils are applied to industrial biostratigraphy in
one or more of the following ways:
12 Microfossils: Calcareous Nannoplankton (Nannofossils)

Microfossils: Calcareous Nannoplankton (Nannofossils), biostratigraphers in response to increased deep-sea explora-

Table 2 Bioevents used in industry for high-resolution correlation of tion and production activities in the Gulf of Mexico, North
well sections (Modified after Bowman et al. 2008)
Sea, North and West Africa basins, southeast Asia,
Bioevent acronym Meaning etc. However, industrial zonation schemes are usually kept
“Top” or FDO (first Extinction level of a taxon confidential due to competition between companies and/or
downhole occurrence)
biostratigraphers. Some examples of published industry
FDI/FDAI First downhole abundance increase
nannofossil zonation schemes include those for the Paleocene
FDCO First downhole common and
consistent occurrence of the North Sea (Varol 1989), Upper Cretaceous of the
Acme (not an acronym) Abundance increase or spike, usually Norwegian North Sea (Bergen and Sikora 1999), Paleogene
a dramatic increase of the Gulf of Mexico (Denne 2007), Miocene of the Gulf of
LDCO Last downhole common and Mexico (Bowman et al. 2009), and Cretaceous of the Pelotas
consistent occurrence Basin (Guerra et al. 2012). These schemes place more empha-
“Base” or LDO (last Evolutionary appearance of a taxon sis on bioevents (tops, acme, FDI, FDCO), rather than zones,
downhole occurrence)
and tops, instead of bases, due to the problem of cavings in
well cuttings. In summary, academic zonation schemes are
Bioevents (Biostratigraphic Events) global in their applicability, whereas industrial zonation
A bioevent is identified by the presence of a taxon in its time schemes are better suited for basin or regional use, usually
context derived from its position in a sediment sequence to provide higher resolution within a given stratigraphic
(Gradstein et al. 2008). The first occurrence (base) and the interval.
last occurrence (top) of nannofossil species are unique
bioevents that can be correlated between stratigraphic sec- Sequence Biostratigraphy and Biohorizons
tions to establish synchroneity. These bioevents delimit the The relationship between microfossil bioevents and sequence
range of a species and are regarded as geologically instanta- stratigraphy is used in industry subsurface geology
neous events. In addition to tops and bases, there are several (Armentrout 1996). Although biozones work well in con-
other useful bioevents, as listed in Table 2. densed, fossiliferous, deep-sea sections, expanded continental
Biostratigraphers tend to have different ideas and methods margin sections drilled for hydrocarbons usually have lower
on how to define bioevents. Therefore it is important to agree microfossil/nannofossil abundances with uneven distribution.
on stratigraphic and taxonomic rules when defining words Microfossils tend to be concentrated within condensed sec-
like “common,” “consistent,” and “acme” during the process tions or maximum flooding surfaces (MFSs) in expanded
of documenting bioevents. Figure 9 illustrates the terminol- sections (Denne 2003). For example, most bioevents in the
ogy of bioevents in relation to the stratigraphic range of a Neogene Gulf of Mexico are associated with MFSs. Upon
taxon. detailed examination, microfossil assemblages within MFSs
often exhibit distinctive assemblage changes and extinction
Biozones (Biostratigraphic Zones) events that can be used to characterize MFSs. Such assem-
The biostratigraphic potential of nannofossils is derived from blage changes can be denoted as “biohorizons.” A biohorizon
their utility and prominence as primary age markers (index is defined as a stratigraphic boundary, surface, or interface,
fossils) in scientific and commercial drilling programs. These across which there is a significant change in biostratigraphic
age markers have been employed to develop global character, e.g., a downhole increase, acme, size or morpho-
nannofossil biozones (a stratigraphic unit defined by its logic change, or coiling direction change in planktonic
nannofossil content, irrespective of thickness or geographic foraminifera.
extent). Some of the important nannofossil zonation schemes A good example of biohorizons is demonstrated by the
for the Cenozoic and the Mesozoic that were developed nannofossil lineage of the Miocene marker, Discoaster
largely by academia are listed in Table 3. Nannofossil zona- quinqueramus–D. berggrenii–D. bergenii, whose morphotypes
tion schemes, along with those for planktonic foraminifera (e.g., size-related changes) were used to define ten biohorizons
and dinoflagellate cysts, provide standard biochronological within the Upper Miocene Zone, NN11, of Martini (1971).
references for the marine stratigraphic record. The chronostra- By identifying such unique morphologic shifts within the
tigraphic resolution of nannofossil zones is higher in the MFS, the number of biohorizons and bioevents was increased
Cenozoic (1 million years to 60,000 years) than in the Meso- to improve the precision and correlation potential of the Upper
zoic (1–3 million years) due to better preservation and recov- Miocene (Denne 2009). Using this methodology, high-
ery from Cenozoic sediments and, arguably, to slower resolution nannofossil zonation schemes, at resolution as high
evolutionary turnover rates within Mesozoic lineages. as 100 ka, have been constructed for the Pleistocene of the Gulf
Using these global biozones as a foundation, industrial of Mexico (Denne 2003). Sequence biostratigraphic studies are
nannofossil zonation schemes have been developed by applied more easily to Neogene and Quaternary sediments,
Microfossils: Calcareous Nannoplankton (Nannofossils) 13

Microfossils: Calcareous
Nannoplankton
(Nannofossils),
Fig. 9 Terminology of
biostratigraphic events within the FDI = First Downhole Abundance Increase
stratigraphic range of a single
taxon in well cuttings (Modified
after Gradstein (2005) and FDCO = First Downhole Common and Consistent Occurrence
Bowman et al. (2008))

TOTAL RANGE
Acme

LDCO = Last Downhole Common and Consistent Occurrence

Base/LDO = Last Downhole Occurrence => Appearance

In addition to providing a tight age control, nannofossils,

Microfossils: Calcareous Nannoplankton (Nannofossils), like other planktonic microfossils, assist in calculating sedi-
Table 3 Examples of Mesozoic (Triassic, Jurassic, and Cretaceous)
and Cenozoic (Paleogene, Neogene, and Quaternary) nannofossil ment/rock accumulation rates (sediment thickness divided by
(NF) zonation schemes time interval) of marine sections. The duration of unconfor-
Mesozoic NF zonation mities can also be estimated by calibrating missing
schemes Cenozoic NF zonation schemes nannofossil markers or zones in a stratigraphic section. This
Barnard and Hay (1974): Martini (1971): gives an estimate of the missing time interval (expressing
Triassic–Jurassic Paleogene–Quaternary erosion or nondeposition) in the rock record. Information on
Sissingh (1977): Cretaceous Gartner (1977): Quaternary accumulation rates and unconformities, portrayed via age-
Perch-Nielsen (1985b): Okada and Bukry (1980): depth plots (Fig. 11), have a direct application in basin model-
Cretaceous Paleogene–Quaternary
ing, a fundamental analytical tool for exploring frontier and
Bown (1998): Backman et al. (2012):
Triassic–Cretaceous Miocene–Quaternary mature sedimentary basins.

Well Site Biostratigraphy and Biosteering

compared to older Mesozoic sections, because the superior To facilitate real-time stratigraphic monitoring of drilling,
preservation of nannofossils in younger sections allows well site biostratigraphy is used to determine the stratigraphic
biohorizons to be identified reliably. Figure 10 illustrates the position of the drill bit and to pick coring and casing points,
concept of biohorizons in a hypothetical Miocene section, based and total depth (TD) of an exploration or production well.
on acmes of three species (adapted from Denne 2009). Ditch cuttings and side wall core samples are prepared and
analyzed on the drilling rig to gauge the stratigraphic posi-
Age-Depth Plots and Numerical (Absolute) Age Determination tioning with accuracy, usually through biostratigraphic zona-
The majority of nannofossil markers (tops and bases) have tion schemes developed prior to drilling. Nannofossils are an
been calibrated to the geologic time scale in million years excellent group in providing real-time data, due to minimal
(Ma) to facilitate absolute age correlation. Nannofossils them- set-up required for their preparation and observation. As an
selves do not give absolute ages; the absolute ages in the example, they have been used for well site biostratigraphy
geologic time scale are determined by radiometric dating of extensively in offshore deep water Nigeria to aid exploration
certain lithologic units (e.g., volcanic ash beds) within the and production (Fadiya 2014).
sedimentary succession. Nannofossil tops and bases are then In relation to reservoir characterization, nannofossils can
calibrated to those radiometrically dated tie-points, based on be used in biosteering horizontal and high-angle wells that are
relative stratigraphic positioning. increasingly being drilled nowadays for shale-related
14 Microfossils: Calcareous Nannoplankton (Nannofossils)

Microfossils: Calcareous
Nannoplankton Depth Species 1 Species 2 Species 3 Global Miocene
Nannofossil Zone
(Nannofossils),
Fig. 10 Schematic diagram Top Top
showing three nannofossil species Top
NN12
in a hypothetical Upper Miocene
section. As an example, two Acme
biohorizons (Biohorizon 1 and 2) Biohorizon 1
Acme
are identified, based on acmes of Biohorizon 2 NN11
Acme
species 1, 2, and 3, within the Base
Upper Miocene Nannofossil Zone
NN11 (Modified after Denne NN10
2009) Base Base

exploration. Supporting data, such as lithology obtained distribution patterns, have been used to characterize short-
through wireline logs, are combined with paleontological term environmental fluctuations in the marine rock record.
data to maximize the effectiveness of biosteering. The pri- Paleoecological affiliations of nannofossils are linked to one
mary goal of biosteering, a subset of geosteering, is to max- or both of the following factors:
imize reservoir penetration by biostratigraphically
“fingerprinting” the reservoir-enveloping, non-pay packages Cool/Warm Surface Water Temperature
that are encountered during drilling. If the well bore encoun- Particular associations of living nannoplankton have been
ters a non-pay horizon by passing up through the top or the used to define latitude-related zones in the Atlantic and Pacific
base of the reservoir, or by hitting upon a normal fault, oceans (McIntyre and Bé 1967; Okada and Honjo 1973) and
microfossils can be utilized to determine the stratigraphic extended to extinct species of the Cretaceous by defining
position and steer the well bore back into the reservoir. paleobiogeographic zones (Lees 2002). Studies have demon-
Biosteering through microfossils for optimal reservoir place- strated that the paleobiogeographic patterns of certain Meso-
ment has saved tens of millions of dollars in drilling costs and zoic species were governed by surface water temperature. For
added to tens of thousands of barrels per day of production in example, the distribution of at least four high-latitude Creta-
many producing fields, including those in Colombia (Cusiana ceous species, e.g., Stradnerlithus silvaradius, Crucibiscutum
Field, Llanos Basin, Upper Cretaceous sandstones), United salebrosum, Repagulum parvidentatum, and Seribiscutum
Arab Emirates (Sajaa Field, Oman Mountains, Lower Creta- primitivum, in paleolatitudes greater than 50 N and S,
ceous marine carbonates), and the North Sea (Valhall Field, suggested that temperature gradients between low and high
Norwegian Sector, Upper Cretaceous chalky turbidites) paleolatitudes were smaller during the Early and mid-
(Jones et al. 2005). Cretaceous times than present day. A broad tropical belt,
ranging approximately from 50 N to 50 S, on the other
Paleoenvironmental Analysis hand, was characterized by weak latitudinal, but stronger
Factors which make nannofossils supremely useful as bio- neritic-oceanic gradients (Street and Bown 2000). Also, the
stratigraphic markers also tend to reduce their utility as progressive paleolatitudinal migration and/or expansion of
paleoenvironmental indicators. As planktonic organisms, cold-water species (e.g., Nephrolithus frequens) from higher
nannofossils are widely distributed and transportable after to lower latitudes during the terminal Cretaceous has con-
death, so individual species can occur in very diverse marine firmed the role of surface water temperature in the distribution
environments with broad geographical and environmental of nannofossils (Pospichal and Wise 1990).
tolerances. Also, many species evolve rapidly, so it can be
perilous to extrapolate the knowledge of the ecological pref- Oligotrophic (Oceanic) Versus Eutrophic (Neritic) Environment
erences of a particular taxon back through geologic time. Living species (and their fossil counterparts) that prefer
Finally, unlike diatoms or dinoflagellates, the majority of neritic environments experience a broader range of tempera-
species are oceanic. Therefore, in some ways, neritic commu- ture and salinity variations than species that inhabit centers of
nities can be considered as a restricted subset of oceanic subtropical ocean gyres. This is because nutrients tend to be
assemblages. more abundant and replenished in neritic, polar, and upwell-
However, the continuous high-resolution record of ing areas, whereas at the centers of ocean gyres, quieter
nannofossils compensates for many of these problems, permit- climatic conditions and greater distance from land contribute
ting them to be utilized for understanding paleoceanographic to nutrient depletion in the surface waters. Hence a “nutrient
and/or paleoclimatic changes. The paleoecological preferences gradient” exists from eutrophic neritic habitats to oligotrophic
of particular taxa, inferred from their biogeographic subtropical ocean gyres.
Microfossils: Calcareous Nannoplankton (Nannofossils) 15

Gephyrocapsa spp. small-acme

R. ampla

D. asymmetricus

Nannofossil
Marker Datums
Unconformity
490m
Depth of Section (meters)

P. acostaensis

D. decorus Period
of Rock
Accumulation
Line of
Correlation
S. abies influx
700m

R. haqii Unconformity

Geologic Age (million years)

Microfossils: Calcareous Nannoplankton (Nannofossils), (Pliocene–Pleistocene), via the line of correlation, which consists of
Fig. 11 An example of an age-depth plot (depth vertical, geologic age two parts: (i) periods of rock accumulation (slopes) and
horizontal), demonstrating the utility of nannofossil marker/datums (ii) unconformities (horizontal terraces) (Source: Authors’ archive)
(green) to determine the age of the stratigraphic section
16 Microfossils: Calcareous Nannoplankton (Nannofossils)

Microfossils: Calcareous Nannoplankton (Nannofossils), Microfossils: Calcareous Nannoplankton (Nannofossils),

Table 4 Some Cenozoic nannofossil genera and their suggested paleo- Table 5 Selected Mesozoic nannofossil species and their suggested
ecological affinities paleoecological affinities can be utilized for understanding surface
water conditions (temperature and nutrients) during source rock deposi-
Selected Cenozoic
tional intervals in the Cretaceous
genera Paleoecological affinities
Braarudosphaera, Low salinity, shallow coastal to brackish? Selected Cretaceous species Paleoecological affinities
Micrantholithus Biscutum constans, Discorhabdus High fertility indicators (e.g.,
Pontosphaera Neritic ignotus, Zeugrhabdotus erectus/ increased upwelling)
Helicosphaera Increased nutrient availability, warm to noeliae
temperate waters Nannoconus spp. Low-latitude, warm water,
neritic, deep photic zone
dweller
Particular taxa demonstrate such nutrient gradients Braarudosphaera, Micrantholithus Low salinity, eutrophic, neritic
(Table 4). In the Cenozoic, a few species of Pontosphaera, spp.
e.g., P. discopora and P. multipora, are generally described as Repagulum parvidentatum, High-latitude distribution
Seribiscutum primitivum,
preferring neritic environments, while being uncommon in Crucibiscutum salebrosum,
open-ocean settings (Perch-Nielsen 1985a). The living spe- Stradnerlithus silvaradius
cies Braarudosphaera bigelowii, and the closely related
Micrantholithus vesper, tend to be abundant in eutrophic
to phytoplankton-derived organic matter in high-productivity
conditions in low salinity, or even brackish conditions in
marine environments. In such settings, a high contribution of
coastal areas, in addition to their presence in the open-ocean
coccoliths to sediments produces organic-rich marls, which
environment. Additionally, Braarudosphaera blooms in lower
can become effective source rocks.
Oligocene chalks on both margins of the South Atlantic have
been linked to paleoceanographic changes caused by rhythmic-
ity in the configuration and vigor of gyre circulation (Peleo-
Summary
Alampay et al. 1999; Kelly et al. 2003). In their study, two
braarudosphaerid depositional events within the lower Oligo-
Calcareous nannoplankton are a heterogeneous group of liv-
cene were interpreted to be either related to (a) subsurface
ing marine planktonic organisms and calcareous fossil struc-
blooms that took place in the lower part of the euphotic zone
tures, comprising the most abundant calcifying organisms on
or, alternatively, (b) seasonality, reflecting spring upwelling.
our planet. Their fossil record is particularly remarkable,
The termination of the braarudosphaerid blooms near the end
providing one of the most complete stratigraphic records
of the early Oligocene was speculated to be related to
among any group of organisms. Nannofossils first appear in
the opening of the Drake Passage and the development of the
the rock record in the Upper Triassic and can be found in
Antarctic Circumpolar Current. Helicosphaerids (H. euphratis,
staggering abundances in fine-grained pelagic sediments,
H. ampliaperta, H. mediterranea), which can be common in
with rock-forming proportions in facies like the Upper Creta-
Paleogene and Neogene assemblages, are generally considered
ceous chalk. Coccolithophores, the dominant group of calcar-
to prefer warm to temperate waters and increased nutrient
eous nannoplankton, and associated calcareous
availability (Auer et al. 2014).
phytoplankton are important primary producers in the marine
In the Mesozoic, nannoconids have been known to be
ecosystem, whose record is intimately linked to the
dominant in warmer, tropical latitudes, indicating continental
climate–ocean system influencing biodiversity and the global
margin, shallow plateau, and epicontinental sea affiliations
carbon cycle.
(Erba 1994). Continental margin assemblages enriched
Nannofossils are primarily employed in petroleum geol-
with Biscutum constans, Discorhabdus ignotus, and
ogy to determine the age of marine sediments
Zeugrhabdotus erectus/noeliae are correlated with higher
(biostratigraphy), including source and reservoir rocks. As
nutrient concentrations, caused by upwelling along the east-
global correlation tools, they enable high-resolution correla-
ern margin of the North and South Atlantic oceans and in the
tion of stratigraphic sections from one well to another well
paleo-equatorial divergence zone (related to upwelling) in the
and from one basin to another basin. This is achieved by
western Pacific Ocean (Erba 1992). These three species are
recognizing (i) bioevents (e.g., bases, tops, acme),
prominently used as high-fertility indices, particularly in the
(ii) biozones (stratigraphic units delimited by age markers
mid-Cretaceous (Table 5).
and defined by their nannofossil content), and/or (iii)
As mentioned above, selected nannofossil taxa can be
biohorizons (distinctive assemblage changes within maxi-
utilized to estimate the surface water fertility/nutrient levels
mum flooding surfaces in expanded sections), based on
in relation to mid-Cretaceous anoxic intervals and source rock
nannofossil assemblages recovered from stratigraphic
depositional environments, as they are important contributors
Microfossils: Calcareous Nannoplankton (Nannofossils) 17

sections. Through absolute age calibration of bioevents in Beaufort L, Lancelot Y, Camberlin P, Cayre O, Vincent E, Bassinot F,
million years (Ma), nannofossils, like other planktonic micro- Labeyrie L (1997) Insolation cycles as a major control of Equatorial
Indian Ocean primary production. Science 278:1451–1454
fossils, can be utilized in calculating sediment/rock accumu- Bergen JA, Sikora PJ (1999) Microfossil diachronism in southern Nor-
lation rates and duration of unconformities. In addition to wegian North Sea chalks: Valhall and Hod fields. In: Jones RW,
real-time stratigraphic monitoring of well site drilling, Simmons MD (eds) Biostratigraphy in production and development
nannofossils are also used in biosteering horizontal and geology, Special publications, vol 152. Geological Society, London,
pp 85–111
high-angle wells that are popular for shale exploration. Bolli HM, Saunders JB, Perch-Nielsen K (1989) Plankton Stratigraphy,
The continuous stratigraphic record of nannofossils volume 1: Planktonic foraminifera, calcareous nannofossils and
coupled with a cosmopolitan distribution permits their utili- calpionellids. Cambridge University Press, Cambridge
zation in understanding paleoceanographic and paleoclimatic Bowman A, Gradstein FM, Lugowski A, Hammer O (2008) Increasing
resolution in exploration biostratigraphy – part II. Nat Resour Res
changes in the geological past. The ecological affinities of 17(3):129–134
certain species are closely linked to surface water temperature Bowman, A., Jones, G.D. (deceased), Witmer, R.J., Gary, A. C., 2009.
(cool vs. warm water species) and nutrient/fertility gradients, Application of a statistically derived, integrated biozonation to a
ranging from eutrophic neritic habitats to oligotrophic sub- deepwater Miocene Gulf of Mexico Field. In: Demchuk, T. D.,
Gary, A.C., Geologic problem solving with microfossils: a volume
tropical ocean gyres. Selected species that demonstrate tem- in honor of Garry D. Jones, SEPM Tulsa Special publication
perature and/or elevated fertility levels are therefore 93, 337–342.
employed to characterize source rock depositional environ- Bown PR (1998) Calcareous nannofossil biostratigraphy, British Micro-
ments, especially in Mesozoic anoxic intervals, as significant palaeontological Society publication series. Kluwer, Dordrecht
Bown PR, Young JR (1998a) Introduction. In: Bown PR (ed) Calcareous
contributors to phytoplankton-derived organic matter. nannofossil biostratigraphy. Kluwer, Dordrecht, pp 1–15
Bown PR, Young JR (1998b) Techniques. In: Bown PR (ed) Calcareous
Acknowledgments We sincerely thank Dr. Richard Denne and nannofossil biostratigraphy. Kluwer, Dordrecht, pp 16–28
Dr. Eiichi Setoyama for improving the manuscript with their constructive Bown PR, Lees JA, Young JR (2004) Calcareous nannoplankton evolu-
suggestions. tion and diversity through time. In: Thierstein HR, Young JR (eds)
Coccolithophores from molecular processes to global impact,
vol 4. Springer, Berlin, pp 481–508
Cros L, Kleijne A, Zeltner A, Billard C, Young JR (2000) New examples
of holococcolith-heterococcolith combination coccospheres and their
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▶ Palynology Denne RA (2007) Paleogene calcareous nannofossil bioevents from the
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H

Hydrous Pyrolysis (Ruble et al. 2001; Lewan et al. 2002), timing of petroleum
generation from a source rock within a sedimentary basin
Michael D. Lewan (Lewan et al. 2006), utility of organic components in oils
U.S. Geological Survey, Emeritus, Denver, CO, USA and source rocks as indicators of thermal maturity (Lewan
1983; and Lewan et al. 1986), and parameters to use in oil-to-
oil and oil-to-source rock correlations for defining petroleum
Definition systems (Curtis et al. 2004).
Experiments have shown that the liquid water in hydrous
Hydrous pyrolysis is a laboratory method for simulating pyrolysis is essential to oil generation in and expulsion from a
natural petroleum formation, which involves pyrolysis (i.e., source rock. The added water surrounding the source rock
heating in the absence of oxygen) of petroleum source rocks during pyrolysis only ensures that organic matter within the
or their isolated organic matter in the presence of liquid water rock contains dissolved water. It is the dissolved water within
as originally defined by Lewan et al. (1979). the organic matter that provides hydrogen for thermal crack-
ing reactions and expulsion of immiscible oil from the rock
(Lewan 1997). Hydrous pyrolysis experiments using D2O
Methodology instead of H2O show that water dissolved in the organic
matter is a source of hydrogen (Lewan 1997; Schimmelmann
Hydrous pyrolysis is a closed reactor system that generates et al. 1999) that reacts with hydrocarbon radicals during
expelled oil between 280  C and 365  C after durations of thermal decomposition of the organic matter (Hoering 1984;
24–72 h. The generated oil accumulates on the water surface and Leif and Simoneit 2000). Oxygen from the reacted
within the reactor and is similar in composition to natural dissolved water occurs as excess CO2 through a proposed
crude oils. The oil is expelled from the rock by processes reaction with carbonyl groups in the organic matter (Lewan
considered similar to those operative during natural thermal 1997). The lack of high CO2 in natural gases is attributed to its
maturation of source rocks subsiding in sedimentary basins. high solubility in subsurface pore waters and reactivity to
Collection of subsurface data from petroleum wells drilled in form carbonate cements (Kotarba and Lewan 2013).
sedimentary basins is critical to developing a quantitative The surrounding liquid water only serves as a reservoir to
understanding of the natural processes responsible for petro- maintain dissolved water in the organic matter (i.e., bitumen)
leum generation, expulsion, migration, and accumulation. of the source rock. As a result, the ratio of added water to
However, the vastness of sedimentary basins, limited subsur- source rock is not important as long as there is sufficient water
face well data, regional variations in source-rock facies, and to maintain liquid water in contact with the source rock during
migration of petroleum away from its sources requires pyrolysis (Lewan 1993). This condition exists in natural
researchers to use hydrous pyrolysis to more fully understand thermal maturation with water being ubiquitous within the
the natural processes. The simplest schemes for overall reac- subsurface of sedimentary basins. Voids, fractures, and pores
tions responsible for the processes of petroleum formation are within buried sedimentary rocks are filled with liquid water.
multifaceted (Fig. 1), which further limits their recognition The ubiquity of subsurface water is demonstrated in its abun-
and understanding with only natural subsurface data. In this dance in crystalline basement rocks at depths greater than
capacity, hydrous pyrolysis is also used to determine the 8 km (Kerr 1994) and its required presence in deep crustal
amount and type of petroleum a source rock can generate

# Springer International Publishing AG 2017

R. Sorkhabi (ed.), Encyclopedia of Petroleum Geoscience,
DOI 10.1007/978-3-319-02330-4_5-1
2 Hydrous Pyrolysis

Hydrous Pyrolysis, Fig. 1 Overall reactions involved with the gener- thermally decomposing bitumen to form char (i.e., pyrobitumen). Reac-
ation of petroleum with increasing thermal maturity (time and tempera- tion 5 involves cracking reactions within thermally decomposing bitu-
ture). Reaction 1 involves the partial thermal breaking of weak non- men to form hydrocarbon gas (i.e., natural gas). Reaction 7 involves
covalent bonds in solid insoluble kerogen to a high-molecular-weight cross-linking reactions within thermally decomposing crude oil to form
tarry-soluble bitumen. Reaction 3 involves cross-linking reactions char (i.e., pyrobitumen). Reaction 8 involves cracking reactions within
within thermally decomposing kerogen to form char (i.e., pyrobitumen). thermally decomposing crude oil to form hydrocarbon gas (i.e., natural
Reaction 4 involves cracking reactions within thermally decomposing gas). Reaction 9 involves continued cross-linking and aromatization to
kerogen to form hydrocarbon gas (i.e., natural gas). Reaction 2 involves form graphitic carbon (i.e., graphitization). Reaction 10 is the thermal
thermal cracking of covalent bonds in bitumen to hydrocarbon-rich oil cracking of light gaseous hydrocarbons (i.e., ethane, propane, and
(i.e., crude oil). Reaction 5 involves cross-linking reactions within butanes) to form pure methane

metamorphic reactions (Ferry 1983) and magma generation pressures are those of water vapor pressure plus generated gas
(Wyllie 1977). pressure at the intended experimental temperatures and dura-
A typical hydrous pyrolysis setup is shown in Fig. 2 with a tions. Typical experimental conditions used to achieve a full
1-liter, stainless steel reactor and gravel-sized (0.5–2.0 cm) range of oil formation are 280–365  C for 72 h. Longer and
source rock. The method can be scaled to various sized high- shorter durations within this temperature range are typically
pressure reactors provided the proportions of source rock and used in determining isothermal kinetics of expelled oil gen-
water are appropriate for the reactor volume to ensure that the eration (e.g., Lewan and Ruble 2002; Lewan et al. 2006).
rock is submerged in liquid water before, during, and after Other experiments that use steam, supercritical water, or
pyrolysis (Fig. 2). In addition, it is also imperative for safety mixtures of H2O phases in contact with the source rocks or
that the reactor volume is not exceeded by the thermal expan- their isolated organic matter are not hydrous pyrolysis but
sion of the liquid water. This requires prior knowledge of the may be referred to as steam, supercritical, or hydrothermal
rock density and the reactor volume to determine the amount pyrolysis, respectively (Lewan 1992). Hydrous pyrolysis
of added water needed for a given experimental temperature. focused on the thermal stability or reactivity of organic com-
The liquid water prerequisite limits the upper experimental pounds dissolved in water (e.g., Seewald 1994; Reeves et al.
temperature to 374  C, which is the critical point for distilled 2012; McCollom et al. 2001) may be more specifically
water, but addition of NaCl to the water can extend this referred to as aqueous pyrolysis or aquathermolysis (Siskin
temperature limit beyond 400  C (Lewan 1993). Maximum et al. 1990; Fekete et al. 2012).
Hydrous Pyrolysis 3

Hydrous Pyrolysis,
Fig. 2 General schematic of
hydrous pyrolysis of a petroleum
source rock before, during, and
after an experiment, with range of
temperatures and pressures given
above schematic reactors

Applications and depositional setting of petroleum source rocks. These

studies may involve precursory living organic matter
Natural thermal decomposition of sedimentary organic matter (vascular plants, algae, or bacteria; e.g., Jaeschke et al.
to form petroleum occurs at temperatures less than 200  C 2008) or thermally immature sediments and rocks (e.g.,
over tens of thousands to millions of years as a source rock is Koopmans et al. 1997; and Zárate-del Valle et al. 2006).
buried in sedimentary basins. This kinetically controlled pro- Hydrous pyrolysis has been used to determine the effects of
cess depends on time of heating as well as temperature, which thermal maturity on stable isotopes of organic matter and
collectively is referred to as thermal maturation. Obviously, petroleum (d13C, Lewan 1983; d2H, Schimmelmann et al.
these long natural durations cannot be applied in laboratory 1999; and dS34, Arami et al. 2005). It has also been used to
pyrolysis. Therefore, higher temperatures must be applied to determine the effects of thermal maturity on biomarkers
shorten the pyrolysis durations. The relationship between (Lewan et al. 1986; Peters et al. 1990; Curiale et al. 1992;
time and temperature for 50% oil generation based on kinetic and Koopmans et al. 1997) and diamondoids (Wei et al.
parameters determined by hydrous pyrolysis is plotted in 2007), which are used for genetic correlations among oils
Fig. 3. This relationship indicates that pyrolysis temperatures and their source rocks.
greater than 271  C are needed to obtain timely results in less Gases generated during hydrous pyrolysis have been used
than 1 year. This substitution of higher temperatures for to define timing of natural gas formation from oil cracking
longer times assumes that the mechanisms involved in natural (Tsuzuki et al. 1999; Shuai et al. 2012) and thermal decom-
petroleum formation remain similar to those during labora- position of source-rock organic matter (Knauss et al. 1997;
tory pyrolysis. This assumption is in part affirmed by hydrous Seewald et al. 1998). In addition, these generated gases have
pyrolysis in that it operates at the lowest possible tempera- been used for gas-to-source rock correlations (Kotarba and
tures and generates petroleum products that are composition- Lewan 2013), thermal maturity limits of gas generation from
ally similar to natural petroleum. Hydrous pyrolysis studies humic coals (Lewan and Kotarba 2014), prediction of gas/oil
have shown that the time-temperature relationship in Fig. 3 ratios (Lewan and Henry 1999), and determining potential
varies significantly with the organic sulfur content of organic H2S generation from different types of organic matter
matter in petroleum source rocks (Lewan 1985, 1998). Low- (Kotarba et al. 2009; Spigolon et al. 2015). Water-derived
sulfur contents require higher levels of thermal maturity, hydrogen reacting with radicals during methane generation in
which moves the relationship above that shown in Fig. 3. hydrous pyrolysis has provided a means of determining pre-
Conversely, high-sulfur contents require lower levels of ther- viously generated and trapped methane in a source rock from
mal maturity, which moves the relationship below that shown methane generation potential of a source rock (Dias et al.
in Fig. 3. 2014; and Lewan and Kotarba 2014).
In addition to understanding processes and reactions Expelled oils generated by hydrous pyrolysis reside on the
responsible for petroleum formation, hydrous pyrolysis pro- surface of the liquid water within the reactor. These oils
vides information on the stability or alteration pathways of typically have API gravities similar to natural crude oils
specific organic compounds used to evaluate precursor input between 20 and 38 (Lillis et al. 1999; and Spigolon et al.
4 Hydrous Pyrolysis

Hydrous Pyrolysis, Fig. 3 Time

and temperature needed for a
typical petroleum source rock to
generate and expel 50% of its oil
based on hydrous pyrolysis kinetic
parameters for Woodford Shale
(Lewan 1985)

2015). Gas chromatograms of these expelled oils have similar Recovered waters from hydrous pyrolysis provide infor-
alkane distributions to those of natural crude oils with no mation on aqueous-organic and aqueous-inorganic constitu-
alkenes, which commonly do not occur in natural crude oils ents released from a petroleum source rock during thermal
(Winters et al. 1983). Column chromatography of the gener- maturation. Hydrous pyrolysis has helped evaluate the timing
ated expelled oils falls within the enriched saturate and and extent of organic acids and CO2 in the formation of
enriched aromatic hydrocarbon field for most natural crude secondary porosity in the development of petroleum reser-
oils and is distinctly different than the enriched polar field for voirs (e.g., Barth et al. 1987; Eglinton et al. 1987; Lundegard
bitumen retained in source rocks (Lewan 1997; Ruble et al. and Senftle, 1987; Lewan and Fisher 1994; and Dias et al.
2001). As first recognized (Lewan et al. 1979), the ability to 2002). Hydrous pyrolysis has also been used to evaluate
generate an expelled oil similar to natural crude oils with the release of metals during thermal maturation. These metals
mere presence of water gave this pyrolysis method a major may be of environmental concern with respect to oil shale
advantage over previously used pyrolysis methods that retorting (Hill and Lewan 2006) or the source of metallic ores
require products by vaporization or organic solvent extrac- (Grauch et al. 2004). The catalytic effect of transition metals
tions, which do not occur in the subsurface of sedimentary on natural gas generation was evaluated with hydrous pyrol-
basins. ysis of metal-rich shales (Lewan et al. 2008).
Hydrous Pyrolysis 5

Recovered rocks from hydrous pyrolysis have been used to Cross-References

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(Clauer et al. 2014). Re-Os age determinations of source
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been studied (Rooney et al. 2012; and Cumming et al. 2014). References
Seewald et al. (1990) used hydrous pyrolysis to simulate
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Cosmochim Acta 69:5317–5331
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mineralogy and organic matter are the same throughout a acids produced during kerogen maturation-amounts, composition
hydrous pyrolysis-induced maturation series. Cores are and role in migration of oil. Org Geochem 13:461–465
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placed in a uniaxial confinement clamp during hydrous pyrol-
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alogical, chemical, and K-Ar isotopic changes in Kreyenhagen Shale
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to extract organic compounds from meteorites (Sephton et al. hydrous-pyrolysis experimental maturation. Geochim Cosmochim
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formation at submarine hydrothermal vents (Simoneit 1992; Basin, USA. Geochim Cosmochim Acta 138:32–56
Kvenvolden et al. 1994; and Zárate-del Valle et al. 2006). Curiale JA, Lundegrad PD, Kharaka YK (1992) Hydrous pyrolysis of
crude oil in gold- plated reactors. Org Geochem 18:745–756
Hydrous pyrolysis has also been used to study thermal stabil-
Curtis JB, Kotarba MJ, Lewan MD, Więcław D (2004) Oil/source rock
ity, solubility, and reactivity of organic compounds dissolved correlations in the Polish Flysch Carpathians and Mesozoic basement
in water to evaluate recycling of plastics (Siskin et al. 1991) and organic facies of the Oligocene Menilite Shales: insights from
and generate abiotic organics related to the origin of life hydrous pyrolysis experiments. Org Geochem 35:1573–1596
Dias RF, Freeman KH, Lewan MD, Franks SG (2002) d13C of low-
(McCollom et al. 1999b; Rushdi and Simoneit 2001).
molecular weight organic acids generated by hydrous pyrolysis of
oil-prone source rocks. Geochim Cosmochim Acta 66:2755–2769
Dias RF, Lewan MD, Birdwell JE, Kotarba MJ (2014) Differentiation of
Summary pre-existing trapped methane from thermogenic methane in an
igneous-intruded coal by hydrous pyrolysis. Org Geochem 67:1–7
Eglinton TI, Curtis CD, Rowland SJ (1987) Generation of water-soluble
Hydrous pyrolysis simulates natural petroleum formation in organic acids from kerogen during hydrous pyrolysis: implications
the laboratory. It is conducted on petroleum source rocks or for porosity development. Mineral Mag 51:495–503
their isolated organic matter in the presence of liquid water, Elliott DC (2007) Historical developments in hydroprocessing bio-oils.
Energy Fuel 21:1792–1815
which allows dissolved water in the organic matter to act as a
Fekete J, Sajgó C, Kramarics Á, Eke Z, Kovács K, Kárpáti Z (2012)
source of hydrogen and facilitates immiscibility for separa- Aquathermolysis of humic and fulvic acids: simulation of organic
tion and expulsion of hydrocarbon-rich oil from polar-rich matter in hot thermal waters. Org Geochem 53:109–118
organic matter (bitumen) in a closed system. Hydrous pyrol- Ferry JM (1983) Regional metamorphism of the Vassalboro formation,
ysis requires higher temperatures (280–365  C) to offset the south-central Maine, USA: a case study of the role of fluid in
metamorphic petrogenesis. J Geol Soc Lond 140:551–576
longer durations (hundreds of thousands to millions of years) Grauch RI, Lewan MD, Lamothe PJ, Landis GP, Emsbo P (2004) Ele-
experienced in natural petroleum formation, which occurs at ment partitioning into generated petroleum and hydrothermal fluids
lower temperatures (<200  C). The generated and expelled as determined by hydrous pyrolysis of Retort Shale: Geological
petroleum is physically and chemically similar to natural Society of America annual meeting, Denver, 7–10 Nov, Abstracts
and Programs, vol 36. no. 5, pp 199–200
petroleum. Hill RJ, Lewan MD (2006) Evaluating oil-shale byproducts of environ-
mental concern by hydrous pyrolysis: 26th Oil Shale Symposium,
Golden, 17 Oct
6 Hydrous Pyrolysis

Hoering TC (1984) Thermal reactions of kerogen with added water, Lewan MD, Winters JC, McDonald JH (1979) Generation of oil-like
heavy water and pure organic substances. Org Geochem 5:267–278 pyrolyzates from organic-rich shales. Science 203:897–899
Jaeschke A, Lewan MD, Hopmans EC, Schouten S, Sinninghe Damsté Lewan MD, Bjorøy M, Dolcater DL (1986) Effects of thermal matura-
JS (2008) Thermal stability of ladderane lipids as determined by tion on steroid hydrocarbons as determined by hydrous pyrolysis of
hydrous pyrolysis. Org Geochem 39:1735–1741 Phosphoria Retort Shale. Geochim Cosmochim Acta 50:1977–1987
Kerr RA (1994) German super-deep hole hits bottom. Science 266:545 Lewan MD, Henry ME, Higley DK, Pitman JK (2002) Material balance
Knauss KG, Copenhaver SA, Braum RL, Burnham AK (1997) Hydrous assessment of the New Albany-Chesterian petroleum system of the
pyrolysis of New Albany and Phosphoria shales: production kinetics Illinois basin. Am Assoc Pet Geol Bull 86:745–777
of carboxylic acids and light hydrocarbons and interactions between Lewan MD, Kotarba MJ, Curtis JB, Więcław D, Kosakowski P (2006)
inorganic and organic systems. Org Geochem 27:477–496 Oil- generation kinetics for organic facies with type-II and -II kero-
Koopmans, M. P., de Leeuw, J. W., Lewan, M. D., and Sinninghe- gen in the Menilite Shales of the Polish Carpathians. Geochim
Damste, J.S., (1997), Impact of dia- and catagenesis on sulfur and Cosmochim Acta 70:3351–3368
oxygen sequestration of biomarkers as revealed by artificial matura- Lewan MD, Kotarba MJ, Wieclaw D, Piestrznski A (2008) Evaluating
tion of an immature sedimentary rock: Org Geochem v. 25, transition-metal catalysis in gas generation from Permian
pp. 391–426. Kupferschiefer by hydrous pyrolysis. Geochim Cosmochim Acta
Kotarba MJ, Lewan MD (2013) Sources of natural gases in Middle 72:4069–4093
Cambrian reservoirs in Polish and Lithuanian Baltic Basin as deter- Lewan MD, Dolan MP, Curtis JB (2014) Effects of smectite on oil-
mined by stable isotopes and hydrous pyrolysis of lower Paleozoic expulsion efficiency of the Kreyenhagen Shale based on hydrous
source rocks. Chem Geol 345:62–76 pyrolysis experiments. Am Assoc Pet Geol Bull 98:1091–1109
Kotarba MJ, Curtis JB, Lewan MD (2009) Comparison of natural gases Lillis PG, Lewan MD, Warden A, Monk MS, King JD (1999) Identifica-
accumulated in Oligocene strata with hydrous pyrolysis gases from tion and characterization of oil types and their source rocks. In: Bird
Menilite Shales of the Polish Outer Carpathians. Org Geochem KJ, Nelson PH, Takahashi KI (eds) The oil and gas resource potential
40:769–783 of the Arctic National Wildlife Refuge 1002 Area, Alaska, G.S. Open
Kvenvolden KA, Rapp JB, Hostettler FD, Rosenbauer RJ (1994) Labo- file report 98-34, OA1- OA101. [CD-ROM]. http://pubs.usgs.gov/of/
ratory simulation of hydrothermal petroleum formation from sedi- 1998/ofr-98-0034/OA.pdf
ment in Escanaba Trough, offshore from northern California. Org Lundegard PD, Senftle JT (1987) Hydrous pyrolysis: a tool for the study
Geochem 22:935–945 of organic acid synthesis. Appl Geochem 2:605–612
Leif RN, Simoneit BRT (2000) The role of alkenes produced during McCollom TM, Ritter G, Simoneit BRT (1999a) Lipid synthesis under
hydrous pyrolysis of a shale. Org Geochem 31:1189–1208 hydrothermal conditions by Fischer-Tropsch-type reactions. Orig
Lewan MD (1983) Effects of thermal maturation on stable organic Life Evol Biosph 29:153–166
carbon isotopes as determined by hydrous pyrolysis of Woodford McCollom TM, Simoneit BRT, Shock EL (1999b) Hydrous pyrolysis of
Shale. Geochim Cosmochim Acta 47(8):1471–1479 polycyclic aromatic hydrocarbons and implications for origin of PAH
Lewan MD (1985) Evaluation of petroleum generation by hydrous in hydrothermal petroleum. Energy Fuel 13:401–410
pyrolysis experimentation. Philosophical Transactions of the Royal McCollom TM, Seewald JS, Simoneit BRT (2001) Reactivity of mono-
Society, London, Series A315:123–134 cyclic aromatic compounds under hydrothermal conditions.
Lewan MD (1992) Nomenclature for pyrolysis experiments involving Geochim Cosmochim Acta 65:455–468
H2O. Am Chem Soc Fuel Chem Div Preprints 37(4):1545–1547 Peters KE, Moldowan JM, Sundararaman P (1990) Effects of hydrous
Lewan MD (1993) Laboratory simulation of petroleum formation: pyrolysis on biomarker thermal maturity parameters: Monterey Phos-
hydrous pyrolysis. In: Engle MH, Macko SA (eds) Organic phatic and Siliceous members. Org Geochem 15:249–265
Gerochemistry: Principles and Applications. Plenum, New York, Reeves EP, Seewald JS, Sylva SP (2012) Hydrogen isotope exchange
pp 419–442 between n-alkanes and water under hydrothermal conditions.
Lewan MD (1997) Experiments on the role of water in petroleum Geochim Cosmochim Acta 77:582–599
formation. Geochim Cosmochim Acta 61:3691–3723 Roaldset EH, Wei H, Grimstad S (1998) Smectite to illite conversion by
Lewan MD (1998) Sulfur-radical control on petroleum formation rates. hydrous pyrolysis. Clay Miner 33:147–158
Nature 391:164–166 Rooney AD, Selby D, Lewan MD, Lillis PG, Houzay J-P (2012) Evalu-
Lewan MD, Birdwell JE (2013) Application of uniaxial confining-core ating Re–Os systematics in organic-rich sedimentary rocks in
clamp with hydrous pyrolysis in petrophysical and geochemical response to petroleum generation using hydrous pyrolysis experi-
studies of source rocks at various thermal maturities. In: Unconven- ments. Geochim Cosmochim Acta 77:275–291
tional Resource Technology Conference proceedings, Denver, 12–14 Ruble TE, Lewan MD, Philp RP (2001) New insights on the Green River
Aug, Paper No. 1571475 petroleum system in the Uinta basin from hydrous pyrolysis exper-
Lewan MD, Buchardt B (1989) Irradiation of organic matter by uranium iments. Am Assoc Pet Geol Bull 85:1333–1371
decay in the Alum Shale, Sweden. Geochim Cosmochim Acta Rushdi AI, Simoneit BRT (2001) Lipid formation by aqueous Fischer-
53:1307–1322 Tropsch-type synthesis over a temperature range of 100 to 400  C.
Lewan MD, Fisher JB (1994) Organic acids from petroleum source Orig Life Evol Biosph 31:103–118
rocks, Chapter 4. In: Pittman ED, Lewan MD (eds) Organic acids Schimmelmann A, Lewan MD, Wintsch RP (1999) D/H isotope ratios of
in geological processes. Springer, Heidelberg, pp 70–114 kerogen, bitumen, oil, and water in hydrous pyrolysis of source rocks
Lewan MD, Henry AA (1999) Gas: oil ratios for source rocks containing containing type-I, -II, -IIS, and -III kerogen. Geochim Cosmochim
type-I, -II, -IIS, and -III kerogen as determined by hydrous pyrolysis: Acta 63:3751–3766
USGS Open-File Report No. 99-327, 34p; also USGS DDS-67, Seewald JS (1994) Evidence for metastable equilibrium between hydro-
Chapter E (2001) carbons under hydrothermal conditions. Nature 370:285–287
Lewan MD, Kotarba MJ (2014) Thermal maturity limit for primary Seewald JS, Seyfried WE, Thornton EC (1990) Organic-rich sediment
thermogenic gas generation from humic coals as determined by alteration: an experimental and theoretical study at elevated temper-
hydrous pyrolysis. Am Assoc Pet Geol Bull 98:2581–2610 ature and pressures. Appl Geochem 5:193–209
Lewan MD, Ruble TE (2002) Comparison of petroleum generation Seewald JS, Benitez-Nelson BC, Whelan JK (1998) Laboratory and
kinetics by isothermal hydrous and nonisothermal open-system theoretical constraints on the generation and composition of natural
pyrolysis. Org Geochem 33:1457–1475 gas. Geochim Cosmochim Acta 62:1599–1617
Hydrous Pyrolysis 7

Sephton MA, Pillinger CT, Gilmour I (1999) Small-scale hydrous pyrol- pyrolysis: case study using a Brazilian source rock with type-I
ysis of macromolecular material in meteorites. Planet Space Sci kerogen. Org Geochem 83(84):27–53
47:181–187 Tannenbaum E, Huizinga BJ, Kaplan IR (1986) Role of minerals in
Shuai YH, Zhang SC, Luo P, Liu JZ, Hu GY (2012) Experimental thermal alteration of organic matter–II: a material balance. Am
evidence for formation water promoting crude oil cracking to gas. Assoc Pet Geol Bull 70:1156–1165
Chin Sci Bull 57:4587–4593 Tsuzuki N, Takeda N, Suzuki M, Yokoi K (1999) The kinetic modeling
Simoneit BRT (1992) Natural hydrous pyrolysis: petroleum generation of oil cracking by hydrothermal pyrolysis experiments. Int J Coal
in submarine hydrothermal systems. In: Whelan JK, Farrington JW Geol 39:227–250
(eds) Organic matter: productivity, accumulation, and preservation in Wei Z, Moldowan JM, Paytan A (2007) Diamonoids and molecular
recent and ancient sediments. Columbia University Press, New York, biomarkers generated from modern sediments in the absence and
pp 368–402 presence of minerals during hydrous pyrolysis. Org Geochem
Siskin M, Brons G, Katrizky AR, Balasubramanian M (1990) Aqueous 37:891–911
organic chemistry. Coments1. Aquathermolysis: comparison with Winters JC, Williams, JA, and Lewan MD (1983) A laboratory study of
thermolysis in the reactivity of aliphatic compounds. Energy Fuel petroleum generation by hydrous pyrolysis. In: Bjoröy, M. (ed),
4:475–482 Advances in Organic Geochemistry 1981. John Wiley & Sons Ltd.,
Siskin M, Brons G, Katrizky AR (1991) Reactivity of organic com- New York, pp 524–533.
pounds in hot water: geochemical and technological applications. Wyllie PJ (1977) Effects of H2O and CO2 on magma generation in the
Science 254:231–237 crust and mantle. J Geol Soc Lond 134:215–234
Spigolon ALD, Lewan MD, de Barros Penteado HL, Coutinho LFC, Zárate-del Valle PF, Rushdi AI, Simoneit BRT (2006) Hydrothermal
Filho JGM (2015) Evaluation of the petroleum composition and petroleum of Lake Chapala, Citala Rift, western Mexico: bitumen
quality with increasing thermal maturity as simulated by hydrous compositions from source sediments and application of hydrous
pyrolysis. Appl Geochem 21:701–712
B

Biostratigraphy assemblages changed over time, leading to the construction

of the geologic time scale. As additional information on
Richard A. Denne stratigraphy and paleontology became available, further
School of Geology, Energy, & the Environment, Texas applications of paleontologic data, such as paleoenvir-
Christian University, Fort Worth, TX, USA onmental analyses, were devised.
Prior to the 1920s, applications of biostratigraphy within
the oil and gas industry were concentrated on the surface
Synonyms mapping of anticlinal structures using larger invertebrate fos-
sils (macrofossils) such as ammonites. With the advent of
Paleontology; Applied paleontology; Economic rotary drilling and the availability of cutting samples pro-
micropaleontology. duced by this process, subsurface correlation supplanted
Paleontology is the study of ancient life and their fossilized field mapping during the 1920s (Howe 1943). Macrofossils
remains and therefore is a much broader term than either are typically destroyed by the rotary drilling process, which
biostratigraphy or applied paleontology. Applied paleontol- necessitated a shift by industry paleontologists to the use of
ogy denotes the geological applications of paleontology, fossils too small to be damaged by the rotary drill bit (Howe
which biostratigraphy as well as other applications such as 1959). The new field of economic micropaleontology was
paleoenvironmental interpretation. Economic micropaleon- established by paleontologists working in the US Gulf Coast
tology refers specifically to the industrial application of and California during the early 1920s (Croneis 1941). These
microfossils. early workers specialized in benthic foraminifera, but utiliza-
tion of other microfossil groups, such as palynomorphs
(organic-walled microfossils), calcareous nannofossils, and
Definition planktic foraminifera, also became widespread as paleontol-
ogists developed a better understanding of their identification
Biostratigraphy is the application of paleontology for the and age distribution.
correlation and age determination of sedimentary rocks. The
term biostratigraphy is often used in a broader sense to
encompass all applications of paleontology to solve geolog- Fossil Types
ical problems.
As noted above, the destructive nature of the drilling process
precludes the use of fossils either too big or too fragile to
Introduction survive the drill bit. Thus, the focus of industry
paleontologists is on so-called microfossils. Most industry
Fossils have been used by geologists to correlate sedimentary biostratigraphers are specialists in foraminifera, calcareous
rocks since the founding of the science of stratigraphy by nannofossils, or palynology. Larger fossils (macrofossils) or
William Smith during the early 1800s and remain the focus of fragments thereof are sometimes noted in thin sections or in
biostratigraphy. Early stratigraphers recognized that strata conventional cores, or are used in outcrop studies, so the
could be grouped by their fossil content and that fossil geologic ranges of some useful types are also shown (Fig. 1).

# Springer International Publishing AG 2017

R. Sorkhabi (ed.), Encyclopedia of Petroleum Geoscience,
DOI 10.1007/978-3-319-02330-4_6-1
2 Biostratigraphy

Foraminifera Calcareous Nannofossils

Foraminifera are single-celled, amoeba-like protozoans with Although the term “calcareous nannofossil” is a catch-all for
tests (i.e., shells) composed of either calcite, agglutinated any calcareous fossil less than 63 mm in size, most calcareous
particles, or organic material. Historically, the term “micro- nannofossils are coccoliths, the disaggregated plates of
paleontology” in industry literature referred to the study of marine planktic algae with calcitic tests that are typically
foraminifera. Foraminifera are typically sand grain-sized smaller than 30 mm. Calcareous nannofossils evolved during
(63–200 mm), although so-called larger foraminifera could the Carnian (Late Triassic) and were widespread by the Early
be much as big as 14 cm across (Grell 1973). Most forami- Jurassic (Bown et al. 2004). Nannoconids, a relatively large
nifera are benthic, inhabiting environments ranging from nannofossil that evolved during the Tithonian (Late Jurassic)
marginal marine (coastal marshes, estuaries, lagoons, etc.) and became extinct during the Campanian (Late Cretaceous),
to the deep abyss, whereas a much smaller number of species are a major constituent of some Early Cretaceous Tethyan
are planktic. limestones, whereas coccoliths are the dominant component
The oldest known foraminifera are agglutinated of Cretaceous chalks. As calcareous nannofossils are abun-
(a.k.a. arenaceous) benthic forms found in Early Cambrian dant in most neritic to bathyal deposits, and only a few grams
rocks (Fig. 1) that formed their tests by cementing together of rock are needed to study them, they play an important role
sedimentary particles. Agglutinated foraminifera are found in in correlating Mesozoic and Cenozoic marine rocks.
nearly every marine to marginal marine environment, includ-
ing low-oxygen waters and below the carbonate compensa- Palynomorphs
tion depth (CCD). They are the dominant type of foraminifera Palynology is the study of palynomorphs – the organic-walled
in brackish waters and the deepwater “flysch facies” and are microfossils such as pollen, spores, dinoflagellates,
usually the only foraminifera found in the Paleocene-Eocene chitinozoans, and acritarchs. Palynomorphs are grouped
sand-prone intervals of the North Sea and the Gulf of Mexico together by their common method of preparation
(Anisgard 1970; Gradstein and Berggren 1981). (maceration), which traditionally involves the use of both
Fusulinids are an extinct group of calcareous-walled ben- HCl and HF to remove calcite and silica, and not by a
thic foraminifera that evolved during the Silurian and became common lineage. The oldest palynomorphs are acritarchs,
extinct at the end of the Permian (Fig. 1). Fusulinids are up to small (20–150 mm) organic-walled microorganisms of uncer-
10 cm in length and are typically associated with tropical tain origin, which include forms dating from the
Permo-Carboniferous reefs. Although species can be identi- Proterozoic. Acritarchs range throughout the Phanerozoic
fied from whole specimens, fusulinids are more readily (Fig. 1), but they are generally only used for biostratigraphy
speciated using thin sections (Ross and Ross 1987; Vachard in Paleozoic rocks (Evitt 1963; Fensome et al. 1990).
et al. 2010). Chitinozoans share a common flask-shaped morphology and
Smaller calcareous benthic foraminifera are most often are typically larger (50–2000 mm, with an average of
used to estimate paleobathymetry and bottom-water oxygen 150–250 mm) than acritarchs. They range from the Early
levels but are also utilized in some local zonation schemes, Ordovician to the Mississippian (Early Carboniferous)
particularly in neritic sections that contain few planktics. (Wilson and Clarke 1960; Paris et al. 1999) (Fig. 1).
Some deepwater forms have also been found to be useful Spores are the reproductive units of asexually reproducing
for global correlations (Van Morkhoven et al. 1986). plants, algae, and fungi. The oldest spore fossils are from
The larger foraminifera are a polyphyletic (i.e., multiple Middle Ordovician rocks (Wellman et al. 2003). Pollen is
lineages) group that includes both calcareous and aggluti- derived from sexually reproducing plants (angiosperms and
nated benthic species that grew to be larger than 200 mm in gymnosperms); the oldest known gymnosperms occur in
size. They are most commonly found in warm, shallow Fammenian (Late Devonian) rocks (Hilton 2006) and the
waters, particularly in tropical to subtropical reefal environ- earliest angiosperms in Barremian (Early Cretaceous) strata
ments during greenhouse periods (middle Cretaceous, Paleo- (Hickey and Doyle 1977) (Fig. 1). Spores and pollen are
gene), and in some regions were abundant enough to form important biostratigraphic markers in nonmarine and mar-
limestones. Larger foraminifera are used in a number of local ginal marine environments, including fluvio-deltaic, lacus-
zonation schemes and are best identified in thin sections trine, rift valley, and pre-salt sections. Although they are
(BouDagher-Fadel 2008). primarily derived from land plants, they can be transported
The oldest definitive planktic foraminifera were identified into marine environments by wind or deltaic outflow, provid-
in Toarcian (Early Jurassic) rocks (Fig. 1), although question- ing a biostratigraphic link between marine and terrestrial
able forms have been found in Triassic rocks (Hudson sections.
et al. 2009). In general, their occurrences are more widespread Fossilized dinoflagellates (or dinocysts) are the organic-
than those of benthic foraminifera, so they have become a key walled cysts of single-celled phytoplankton. They are primar-
tool in correlating Late Jurassic to Quaternary rocks. ily marine organisms, but freshwater cysts are known from
Biostratigraphy 3

Biostratigraphy, Fig. 1 Geologic ranges of fossil groups utilized by industry biostratigraphers

the modern (Mertens et al. 2012). The oldest dinoflagellate Calpionellids

remains are from the Ladinian (Middle Triassic) (Riding Calpionellids are an extinct group of marine, planktic pro-
et al. 2010) (Fig. 1). They are important markers in marine tozoa with a calcitic test (lorica) ranging in size from 100 to
sections where calcareous microfossils are poorly preserved 200 mm. They are generally found in Tethyan limestones
(e.g., Paleocene-Eocene of the North Sea and Gulf of Mex- deposited during the Tithonian (Late Jurassic) to the
ico). They may also be preserved in carbonate rocks where Valanginian (Early Cretaceous) (Fig. 1). They are primarily
recrystallization has destroyed calcareous fossils (Westphal identified in thin sections (Remane 1985).
et al. 2000).
Radiolarians
Ostracods Radiolarians are marine, planktic, amoeba-like organisms
Ostracods are small crustaceans (“seed shrimp”) protected by related to foraminifera, most of which had opaline silica
a pair of hinged valves typically made of calcite that are tests 10–1000 mm in size. Fossil radiolarians generally fall
usually from 100 to 2000 mm in length (Vannier and Abe into two major groups: the spherical spumellarians and the
1995). The earliest definitive ostracods occur in rocks from conical nasselarians. The oldest recorded occurrences of radi-
the Early Ordovician; analysis of specimens reported as ostra- olarians are from the earliest Cambrian (Braun et al. 2007).
cods from the Cambrian suggest that they belong to another Radiolarian cherts are common in Paleozoic and Mesozoic
group (Williams et al. 2008) (Fig. 1). They are found in most black shales and ophiolite deposits; modern radiolarians are
aquatic environments, from humid soils to the abyss, and can most abundant in areas of upwelling, so their presence in high
be benthic, planktic, or nektic. Ostracods are most common in numbers suggests upwelling of nutrient-rich waters (Jones
lacustrine, marginal marine, and inner neritic environments and Murchey 1986). Their utilization in biostratigraphic
but are rare elsewhere, so they are most often used in local zonations is typically limited to rocks with few calcareous
zonation schemes in these environments, and are critical in microfossils.
correlating Cretaceous lacustrine pre-salt sections in Brazil
and West Africa (Poropat and Colin 2012).
4 Biostratigraphy

Diatoms conventional core provide the highest resolution and have a

Diatoms are single-celled benthic or planktic algae with opal- much lower risk of contamination. There are drawbacks,
ine silica skeletons (frustules) that are typically 10–100 mm in however, as the plugs used to sample cores are smaller than
size, although forms up to 1000 mm are known (Barron 1985). the optimal sample size for most microfossil groups (Table 1),
The oldest conclusive diatom fossils are from the Toarcian and cores are typically taken in the fossil-poor reservoir
(Early Jurassic). Modern forms inhabit nearly all environ- section in conventional fields. Cuttings also provide a more
ments where water and sunlight are present, from the open continuous set of samples than cores. Occasionally, sidewall
ocean to soils; freshwater diatoms are known only from rocks cores are taken specifically for biostratigraphy, usually in
younger than the Middle Eocene (Sims et al. 2006), with one stratigraphically or structurally complex fields. Conventional
record from the Late Cretaceous in lacustrine rocks (Chacon- and sidewall cores have the added advantage of the availabil-
Baca et al. 2002). Diatoms have their highest abundances in ity of thin sections, although thin sections can be made from
areas of upwelling and are the dominant source of biogenic cuttings if necessary.
sediments in polar regions (Barron 1985). Diatomite/
porcelanite deposits such as the Monterey Formation of Cal-
ifornia are products of upwelling and can act as both a hydro- Biostratigraphic Zonations
carbon source rock and conventional reservoir (Pisciotto and
Garrison 1981; Reid and McIntyre 2001). Diatoms are nor- Biostratigraphic zonations are based on the top and base
mally used in industry biostratigraphy in sections with poor occurrences and acmes (periods of high abundance) of marker
preservation of calcareous microfossils, which includes the species (Fig. 2). There are separate, sometimes multiple,
Monterey Formation (Barron 1986), and the Paleogene of the standard zonation schemes for each fossil group and age
North Sea (Bidgood et al. 1999). constructed with samples from outcrops and cores (Figs. 3,
4, 5). The cutting samples utilized by industry can be con-
Silicoflagellates taminated by caved rock chips, thus base occurrences, which
Silicoflagellates are single-celled, planktic algae with a sim- form the backbone of many academic zonations, are used
ple skeleton composed of opaline silica. They are relatively sparingly in industry (Varol 1989). Conventional industry
small, ranging from 20 to 100 mm. They evolved during the wells are often drilled in expanded sections, requiring a higher
Early Cretaceous and are still present in modern oceans resolution than standard zonations provide. To provide the
(Fig. 1). They are only found in open marine waters, primarily additional resolution, industry paleontologists split species
in areas of upwelling. A biostratigraphic zonation has been into multiple forms, use the top occurrences of nonstandard
developed for them, which is typically only used in the markers and benthic species, and exploit assemblage changes,
absence of calcareous microfossils (Perch-Nielsen 1985). including downhole increases and acmes, dominance shifts,
planktic foraminifera coiling direction ratios, and changes in
Conodonts morphologic trends (size and shape) (Riley et al. 1989; Payne
Conodont elements are phosphatic, toothlike apparatus from a et al. 1999; Denne 2009) (Fig. 6). Some industry schemes
nektic (swimming), soft-bodied animal. These elements range simply note the marker species, whereas other schemes utilize
in size from 100 to 5000 mm. Conodonts lived in marine nomenclature systems to identify horizons. There are too
environments from the Late Cambrian to the Triassic many basin-specific industry zonation schemes to be
(Fig. 1) and are one of the primary groups used in Paleozoic discussed here; the reader is encouraged to seek out the
biostratigraphy (Sweet and Donoghue 2001). The color of appropriate microfossil or regional geology journals for
conodont elements can also be used to estimate burial tem- more details.
perature, a method known as the conodont alteration index
(Epstein et al. 1977).
Applications

Sampling Correlations
The primary purpose of biostratigraphy is to correlate one
The optimal sample size and preparation methods differ for section/well to another. Standard zonation schemes are gen-
each microfossil group (Table 1). The standard samples used erally sufficient for regional correlations, whereas reservoir-
in industry for biostratigraphy are cuttings retrieved from scale field correlations may require a higher resolution, often
the shale shaker, typically at 30’ (9 m) intervals. The use of localized, scheme (Payne et al. 1999; Crux et al. 2010)
cuttings has disadvantages, including their relatively (Figs. 6 and 7). Regional correlations are used to identify
large sampling interval, mixture of lithologies, and the possi- reservoir fairways, regional unconformities, and structural
bility of downhole contamination. Samples taken from trends. Field correlations can be used to identify stratigraphic
Biostratigraphy 5

Biostratigraphy, Table 1 Optimal sample size, preparation method, microscope type, thin section use, and well-site requirements for the
microfossil groups used by industry
Optimal
Microfossil sample Preparation Microscope Well-site
Group Size Preparation methods type Thin-section use requirements Remarks
Foraminifera .25–.5 kg Washed Samples are Stereo Preferred for the Requires
(1–2 residue washed over a binocular identification of availability of a
cups) sieve, often after fusulinids and sink with a
soaking in a larger sediment trap
surfactant or foraminifera. (usually found in
kerosene to break May be used for the mud-logging
down the shales. planktics and unit) and space
At well-site a hot smaller benthics for a hot plate if
plate and a blender in carbonates and utilized
may also be used highly indurated
rocks
Calcareous 10–30 g Smear slide Samples are Compound Occasionally Requires only Samples are
Nannofossils (.3–1 oz) crushed, soaked in under identifiable in access to water easily
water, and then polarized, ultra-thin or and a clean space contaminated
smeared onto a transmitted wedged thin- for slide due to
slide. A centrifuge light with sections preparation nannfossil’s
is sometimes used rotating very
stage, 63 small size
or 100 oil
immersion
objectives
Palynomorphs .25–.5 kg Palynology Maceration: Compound Identifiable in Non-acid
(1–2 (or strewn) samples are under thin-section. May preparation
cups) slide crushed, soaked in transmitted be utilized in techniques are
HCl and HF light, 40 or samples that do preferable at well-
(separately) 63 (oil not break down site due to the
leaving only immersion) using standard toxicity of HF. If
organic material, objectives maceration acids are to be
and then mounted techniques used, a separate
on a slide. palynology unit
A separate with proper
kerogen slide may ventilation is
also be prepared. needed
Non-acid
preparation
techniques are
often utilized at
well-site
Ostracods .25–.5 kg Washed Samples are Stereo Visible in thin- Requires Ostracods are
(1–2 residue washed over a binocular section, but availability of a usually
cups) sieve, often after usually cannot be sink with a studied from
soaking in a identified beyond sediment trap the
surfactant or the generic level (usually found in foraminifera
kerosene to break the mud-logging residue.
down the shales unit) and space
for a hot plate if
utilized
Calpionellids NA Thin- Typical thin- Compound Identifiable only NA
section section under in thin-section.
preparation polarized,
transmitted
light with
rotating
stage,
10-20
objective
(continued)
6 Biostratigraphy

Biostratigraphy, Table 1 (continued)

Optimal
Microfossil sample Preparation Microscope Well-site
Group Size Preparation methods type Thin-section use requirements Remarks
Radiolarians 50–100 g Radiolaria Samples are Stereo Identifiable in NA Occasionally
(2–5 oz) residue washed over a binocular thin-section, noted in the
sieve, often after although cathode- foraminifera
having been luminescence residue
soaked in HCl or may be necessary
acetic acid to
remove carbonate
material
Diatoms 10–50 g Smear slide Samples are Compound Identifiable in NA May be
(.3–2 oz) / washed usually soaked in under thin-section present in
residue H2O2 and HCl transmitted nannofossil
(separately) to light, 40 or smear slides
remove organic 63 (oil
and carbonate immersion)
material, and then objectives
smeared onto a
slide. A separate
washed residue
may also be
prepared
Silicoflagellates 10–50 g Smear slide Samples are Compound Identifiable in NA May be
(.3–2 oz) usually soaked in under thin-section present in
H2O2 and HCl transmitted nannofossil
(separately) to light, 40 or smear slides
remove organic 63 (oil
and carbonate immersion)
material, and then objectives
smeared onto a
slide
Conodonts .5 kg Conodont Limestone Stereo May be NA May be found
(2 cups) residue samples are binocular recognizable as a on shale
soaked in either conodont in thin- partings in
acetic or formic section, but likely cores from
acid and then not identifiable to black shales
sieved a useful level

Biostratigraphy, Fig. 2 Types of biostratigraphic zones (zones noted base (left) or top (right) occurrences. (d) Partial range zone, defined by
in gray): (a) Taxon range zone, defined by the total range of a taxon the interval between two nonoverlapping species, delineated by the base
(species). (b) Concurrent range zone, defined by the overlapping ranges of the younger species and the top of the older species, named after a
of two species, delineated by the top of one species and the base of third species that occurs throughout the zone. (e) Abundance or acme
another. (c) Interval range zone, defined by the range of one species that zone, defined by the interval of high abundance (acme) of a species
extends beyond the range of another species, delineated either by their
Biostratigraphy 7

Biostratigraphy, Fig. 3 Standard biostratigraphic zonation schemes calcareous nannofossil zones; boreal dinocyst zones (Lourens et al.
for the Neogene: Subtropical (Wade et al. 2011) and N (Berggren 2004); North Pacific diatom zones (Maruyama 2000); low-latitude radi-
et al. 1995) planktic foraminiferal zones; NN (Martini 1971), CN olarian zones (Sanfilippo and Nigrini 1998) (Age model is from Ogg
(Okada and Bukry 1980), and revised CN (Backman et al. 2012) et al. 2016)
8 Biostratigraphy

Biostratigraphy, Fig. 4 Standard biostratigraphic zonation schemes zones; boreal dinocyst zones (Luterbacher et al. 2004); mid-latitude
for the Paleogene: Subtropical (Wade et al. 2011) and P (Berggren et al. diatom zones (Hardenbol et al. 1998); low-latitude radiolarian zones
1995) planktic foraminiferal zones; NP (Martini 1971), CP (Okada and (Sanfilippo and Nigrini 1998) (Age model is from Ogg et al. 2016)
Bukry 1980), and revised CP (Agnini et al. 2014) calcareous nannofossil
Biostratigraphy 9

Biostratigraphy, Fig. 5 Standard biostratigraphic zonation schemes and UC (Burnett 1998) calcareous nannofossil zones; dinocyst zones
for the Late Cretaceous: Subtropical planktic foraminiferal zones (Hardenbol et al. 1998); radiolarian zones (Sanfilippo and Riedel 1985)
(Robaszynski and Caron 1995); CC (Sissingh 1977) NC (Roth 1978), (Age model is from Ogg et al. 2016)

thinning and pinch-out of reservoir units, potential barriers Chronostratigraphy

and baffles for reservoir connectivity, and faults, repeat sec- Most geochronologic units are defined by biostratigraphic
tion, and other local structures (O’Neill et al. 1999; Payne events, so using fossils to determine the relative age of
et al. 1999). Quantitative methods have been developed to rocks originated with the founders of stratigraphy. With the
increase the resolution and reliability of biostratigraphic cor- advent of radiometric dating and techniques such as orbital
relations (see discussion below). tuning, the ages of many biostratigraphic events are now well
10 Biostratigraphy

Biostratigraphy, Fig. 6 Numeric nannofossil zonation scheme for create a scheme with a higher resolution than the standard scheme of
portions of the Middle-Lower Miocene of the Gulf of Mexico demon- Martini (1971) (Modified from Denne 2009)
strating use of nonstandard marker tops and assemblage changes to

constrained (Ogg et al. 2016). Numeric ages derived from When drilling out of a salt sheet, they can also determine the
biostratigraphy are used in basin models, to determine rock age and depth of in situ section (Crux et al. 2010).
accumulation rates, to build age-depth plots and Wheeler Biosteering was developed as horizontal drilling became
diagrams (Figs. 8 and 9), and to tie to sequence stratigraphic commonplace in the North Sea and the Middle East. As a
cycles. form of geosteering, the objective is to keep a horizontally
drilled well within the target interval. A detailed biostrati-
Well-Site Biostratigraphy graphic zonation for the target zone and adjacent section is
Prior to the advent of logging while drilling (LWD) and 3D required. A key aspect of this technique is the ability to
seismic, paleontologists were routinely present at well-site, determine the vertical direction (upward or downward) in
particularly in the repetitive sand-shale sequences of the off- which the horizontal well exited the target interval in order
shore Gulf of Mexico (LeRoy 1977). The number of paleon- to steer the drill bit back into the target zone. This method can
tologists at well-site dropped off as the use of LWD and 3D also aid in identifying faults and their amount of throw (Payne
seismic became routine in the offshore realm. As industry et al. 1999).
began to drill wells where the seismic signal was attenuated, It is vital to plan ahead for on-site biostratigraphy to
and deepwater drilling costs began to escalate, the need for provide space for sample preparation and examination, and
paleontologists at well-site increased. Paleontologists are typ- documentation for any chemicals that may be needed
ically used at well-site to estimate the proximity to target (Table 1). In most cases, the well-site team will consist of a
intervals, pick coring, and casing points, and determine if sample technician and a paleontologist, preferably two of
the well has met the predetermined TD (total depth) criteria. each for 24-h coverage. The technology for remotely moni-
toring wells is under development, which would require that
Biostratigraphy 11

Biostratigraphy, Fig. 7 Biostratigraphic correlations between two local MFSs are marked by increases in abundance (total count) and
northern Gulf of Mexico wells approximately 5 km (3 mi) apart based diversity of calcareous nannofossils and foraminifera (planktic and
on standard nannofossil (NN) zones, Gulf of Mexico numeric bioevents, benthic)
and local maximum flooding surfaces (MFS). Regional (bioevents) and

only sample technicians would be needed at well-site (Gard by water depth per se but by the environmental parameters
et al. 2016). If acid-based palynology processing is to be that are often related to water depth. Paleobathymetric models
utilized, space for a processing unit is needed. Safer, non- utilized within industry are based on the assumption that
acid processing techniques are now an option for well-site modern species lived in similar environments during the
palynology (Williams et al. 2005). past (Bandy and Arnal 1960; Fleisher and Lane 1999). Ben-
thic foraminifera models based on modern distributions are
Paleoenvironmental Interpretations thought to be useful to the Middle Miocene (Poag 1977),
Paleobathymetry: Information on depositional environments although some bathyal species inhabit shallower waters due
became essential when the oil industry began to exploit strat- to upwelling (Moreno-Vasquez 1995), deltaic outflow (Pflum
igraphic traps during the 1930–1940s (Johnson 1944), pro- and Frerichs 1976), and changes in water mass configuration
mpting research on the distribution of modern benthic (Denne and Sen Gupta 2003), or they migrated from neritic to
foraminifera (e.g., Natland 1933; Phleger 1951a) and apply- bathyal waters over time (Lagoe 1988). Interpretations of pre-
ing it to the study of ancient assemblages (Lowman 1949). Miocene rocks are based on generic or morphologic associa-
The distribution of benthic microorganisms is not controlled tions (Poag 1981) or ancient distribution patterns (Sliter and
12 Biostratigraphy

Biostratigraphy, Fig. 8 Age-depth plot for a well in the deepwater northern Gulf of Mexico. Steep portions of the curve represent expanded
sections, low-angle portions are condensed sections, and flat portions represent missing section due to unconformities (hiatus) or faults

Biostratigraphy, Fig. 9 (a) Wheeler diagram (chronostratigraphic cross section) of selected Cenomanian-Turonian Eagle Ford Group outcrops in
Texas. Hiatuses are shown in white. Based on diagrams from Denne et al. (2016). (b) Map showing outcrop locations in magenta

Baker 1972; Olsson and Nyong 1984). Ratios of planktic to bottom-waters (Gebhardt 2006), and in Cretaceous rocks,
benthic foraminifera have also been used to estimate when planktic foraminifera thrived in shelfal waters (Leckie
paleobathymetry based on the assumption that planktic fora- et al. 1998).
minifera are more abundant away from the coastline (Gibson The Gulf Coast has been a focus for studies of modern
1989), although they can be misleading in areas of high benthic foraminiferal distribution patterns that have been used
planktic productivity (Berger and Diester-Haass 1988), in to build several iterations of bathymetric models (Phleger
areas with few to no benthic foraminifera due to anoxic 1951a; Crouch 1955a; Tipsword et al. 1966; Pflum and
Biostratigraphy 13

Biostratigraphy, Fig. 10 Paleobathymetric model for the northern Gulf of Mexico based on the bathymetric scheme from Picou et al. (1999)

Frerichs 1976; Picou et al. 1999) (Fig. 10). Other models have triserial planktic foraminifera in the Cretaceous (Leckie
been developed for carbonate reefs (Reiss and et al. 1998). Siliceous plankton (radiolarians, diatoms,
Hottinger 1984), the Cenozoic of the California coast silicoflagellates) may reflect eutrophic conditions produced
(Lagoe 1988), and the Cretaceous of the US East Coast by upwelling (Jones and Murchey 1986).
(Olsson and Nyong 1984). Bottom-water oxygen (redox) and/or sediment nutrient
Initially, paleobathymetric models were used to construct levels can be estimated based on benthic microfossil content.
depositional environment (facies) maps, with emphasis on the Strata deposited under highly oxygenated bottom-waters con-
shoreline, deltas, and the shelf edge (Lowman 1949; tain an abundant and diverse benthic assemblage, whereas
Tipsword et al. 1966). Prior to significant discoveries in few species are adapted to low-oxygen conditions. Studies of
deep water, it was thought that sands were rare and over- benthic foraminifera have indicated that their morphologies
pressured in bathyal environments (Crouch 1955a; Tipsword and test composition are related to habitat adaptations and
et al. 1966). After sands were identified in deep water, these thus may reflect oxygen and nutrient levels (Bernhard 1986).
maps were used to identify sources for deepwater sands and to In situ benthic fossils are rare to absent under extremely low-
predict sand geometries (LeRoy 1977). Industry paleontolo- oxygen conditions with the possible exception of the
gists also used paleobathymetry for correlation (Crouch so-called paper pectens (posidoniids, inoceramids) (Allison
1955b; Stude 1970), and paleotectonics (Bandy and Arnal et al. 1995).
1960; Stude 1970). Stude (1970) also suggested that a rapid
downhole paleobathymetric deepening indicated a fault or Sequence Biostratigraphy
unconformity; another option is that the rapid deepening Sequence stratigraphy is a methodology utilized by geologists
represents progradation of the shelf margin over the area within the industry to predict the presence and geometries of
(Fig. 11). Paleobathymetric interpretations are also utilized reservoir, seal, and source facies. The focus is on correlations
in geohistory and basin models (Van Hinte 1978; Célérier using chronostratigraphic, rather than lithostratigraphic, sur-
1988). faces, primarily the unconformable sequence boundary and
Paleoceanography: Planktic microfossil indicators the maximum flooding surface (MFS). These surfaces are
(proxies) for high surface-water fertility (eutrophic) condi- generated by changes in base level driven by sea level, stim-
tions were typically established based on their abundance in ulating the construction of eustatic cycle charts (e.g.,
organic-rich rocks: the algal cyst Tasmanites throughout Hardenbol et al. 1998).
much of the Paleozoic and Mesozoic (Hackley and Cardott The primary applications of biostratigraphic data in
2016), calcareous dinocysts (calcispheres) in the Cretaceous sequence stratigraphy are to aid in the identification of
(Wendler et al. 2002), small forms of the calcareous MFSs, condensed sections, and hiatal surfaces, and to tie
nannofossil genera Zeugrhabdotus and Biscutum during the wells to the global cycle chart. As mentioned above, biostra-
Late Jurassic and Cretaceous (Watkins 1989), and biserial/ tigraphy can be used to construct age-depth plots and Wheeler
14 Biostratigraphy

Biostratigraphy, Fig. 11 Abundances of benthic foraminifera upward shallowing at 4500 m is the result of the shelf margin prograding
grouped using the paleobathymetric model shown in Fig. 9 from a well over the location
drilled on the Louisiana shelf (northern Gulf of Mexico). The dramatic

diagrams to detect hiatal surfaces, condensed sections, and by increasing temperature, producing either a change in color
regional unconformities (Figs. 8, 9). Condensed sections and or reflectance. The most common and accepted technique is
MFSs can also be recognized by microfossil accumulations vitrinite reflectance, which is measured as the percentage of
and paleobathymetric deepening as indicated by benthic light reflected from woody tissue (VRo); the higher the reflec-
water-depth proxies (Loutit et al. 1988) (Figs. 7 and 11). tance, the higher the maturity. Land plants did not evolve until
Paleoenvironmental interpretations are also used to aid in the Silurian and woody material is not always present in
the identification of sequence boundaries (abrupt shallowing sufficient amounts to measure, so other indices have been
upward) and the interpretation of systems tracts (depositional formulated. Those based on color changes (darker=hotter)
models based upon their position within a sequence) (Fleisher include the conodont alteration index (CAI), thermal alter-
and Lane 1999). ation index (TAI) and spore coloration index (SCI) using
palynomorphs (a.k.a. exinite), foraminiferal coloration index
Thermal Maturity (FCI) using agglutinated foraminifera, and acritarch alteration
Although the estimation of thermal maturity is not usually index (AAI) (Epstein et al. 1977; Staplin 1969; Marshall
performed by paleontologists, most methods utilize fossil 1991; McNeil et al. 1996; Legall et al. 1981). Indices based
material. In general, organic matter and phosphate are altered on reflectance use graptolites, chitinozoa, and scolecodonts
(Bertrand and Heroux 1987).
Biostratigraphy 15

Limitations and Complications Frerichs 1976). Fossils found within sands are usually
discounted due to the possibility of downslope transport.
Preservation and Recovery
Even though industry paleontologists concentrate on micro- Diachroneity
organisms that are readily fossilized, there are still numerous It is commonly assumed that biostratigraphic horizons are
impediments to an organism becoming a fossil. Digestion, generally isochronous (time synchronous) within a reason-
dissolution, transport and abrasion, oxidation, diagenesis, able limit, but horizons are sometimes diachronous. Locally,
compaction, meteoric waters, and high burial temperatures in situ fossils may be relatively rare within sand-rich reservoir
can all negatively impact the preservation of a fossil. Simi- intervals. Therefore, suboptimal sampling/examination pro-
larly, a fossil must survive grinding by the drill bit, mud cedures may produce apparent diachroneity at the reservoir
system chemicals, and the sample preparation process before scale which may be resolvable by higher resolution sampling.
being examined by a paleontologist. Therefore, the fossils “Climbing” is a well-documented phenomenon in mar-
examined by the paleontologist are likely not representative ginal marine to neritic paleoenvironments that affects
of the original assemblage. Recovery of fossils from lime- environmentally restricted species, primarily benthic forami-
stones, calcareous shales, and other indurated rocks can be nifera. A species that “climbs” has a diachronous top occur-
challenging and may yield few, if any, fossils. When practical, rence produced by paleoenvironment; typically their top
thin sections or alternative processing techniques have been occurrence appears within successively younger sediments
used for indurated rocks with some success (Karaminia going from proximal to distal locations (Fig. 12) (Lowman
2004). 1949; Martin 2013).
Biostratigraphic datums may also be diachronous on a
Downhole Contamination (Caving) global scale. The speed at which species have populated the
During the drilling process, it is not unusual for pieces of rock world’s oceans has varied considerably; some have done so
from shallower portions of the well to fall down the hole and nearly instantaneously, whereas others have base occurrences
contaminate the cuttings, a process known as caving. There- that are clearly diachronous (Loutit et al. 1988). Conversely,
fore, industry zonation schemes do not typically utilize base environmental conditions may cause a species to become
occurrences due to the possibility that specimens may have locally extinct while the species continues to live elsewhere.
fallen downhole (Varol 1989). Caving can also make it diffi- For example, the extant benthic foraminifer Hyalinea
cult to recognize repeat sections, as the younger fossils are balthica is used as a Pleistocene marker in the Gulf Coast
likely to be interpreted as downhole contaminants if the rocks (Poag and Valentine 1976) but is found living in the Atlantic
are not too dissimilar in age. The abundance of caved fossils Ocean and Mediterranean Sea (Ross 1984).
usually drops off considerably below casing points.
Species Identification and Nomenclature (Taxonomy)
Reworking and Downslope Transport As long as there are multiple paleontologists working on a
Reworking (a.k.a. recycling) is the erosion and subsequent particular fossil group, there will be differences in opinion on
deposition of older fossils into younger sediments. Reworked how species are subdivided, identified, and named. Species
microfossils are sometimes more abundant than the in situ terminology has also changed over time as new species and
assemblage and have been used as locally correlatable hori- genera are added. Therefore, biostratigraphic datasets from
zons (Jiang 1993). Most standard zonation schemes empha- different paleontology groups often differ considerably in
size base occurrences to minimize problems with reworking, terminology, particularly in the usage of informal taxonomic
but this is not possible for industry zonations which rely on names (e.g., Textularia “W”). Industry paleontologists are
tops due to downhole contamination in cuttings. In some often obliged to continue using obsolete terms for well-
instances, reworked fossils are obvious due to differences in known marker species to avoid confusion after changes in
preservation and coloration or are significantly older than the generic assignment (Howe 1959). Attempts have been made
overall assemblage (Brett 1990), but this is not always the with some success to develop taxonomic equivalencies for
case. Denne (2009) suggested using assemblage-based Cenozoic foraminifera of the Gulf Coast (Picou et al. 1999),
biohorizons in sections where reworking is an issue. but work on other microfossil groups and basins is still
Downslope transport via turbidity currents or mass needed.
wasting carries organisms from shallower environments into
deeper ones (Phleger 1951b), potentially causing problems
with paleoenvironmental interpretations. Therefore, many Quantitative Data Analysis
industry paleobathymetric schemes rely on the upper depth
limits of species, limiting the problems associated with During the early days of biostratigraphy, the focus was on
downslope transport (Bandy and Arnal 1960; Pflum and rapid sample examination to provide “tops” for correlations,
16 Biostratigraphy

Biostratigraphy, Fig. 12 Diagrammatic dip section of a prograding at age C. In the updip well (#1), the top occurrence of the marker
margin demonstrating the concept of “climbing.” Colored units represent coincides with the highest penetration of middle neritic environments
depositional environments (marginal marine to upper bathyal), solid at age E. The downdip well (#2) penetrated middle neritic environments
black lines represent time lines (ages A–G), and the magenta lines in rocks younger (age B) than the extinction point of the marker (age C),
represent the highest occurrence (top) of a hypothetical marker species so the marker top in well #2 coincides with its extinction point. There-
that lived in middle neritic and deeper environments that became extinct fore, the marker appears to “climb” in time in a downdip direction

so the data collected was minimal (Martin 2013). As the need Ranking and Scaling (RASC)
for paleoenvironmental interpretations and higher biostrati- RASC is used to determine the optimal sequence of strati-
graphic resolution became necessary, data quality improved, graphic events identified in a number of wells, by first calcu-
enabling the use of quantitative analytical techniques. Several lating the most likely order of events (ranking) and then
techniques have been employed for paleoenvironmental inter- determining the inter-event distances (scaling). RASC differs
pretations, including cluster analysis, fuzzy c-means cluster from graphic correlation in that it runs on all of the data
analysis, polytopic vector analysis (PVA), and correspon- simultaneously and attempts to determine the average range
dence analysis (CA) (Crux et al. 2010). of an event and not its maximum range. When used in com-
bination with correlation and standard error calculation
Graphic Correlation (CASC), this method can also be used for correlation
Graphic correlation is a technique that plots datums (events), (Agterberg et al. 2013).
typically biostratigraphic or other correlatable events (e.g.,
bentonites), from one section or well against either another
section or a composite standard section. Datums are plotted High-Resolution Biostratigraphy
either as tops or bases with corresponding symbols. A line of
correlation is drawn through the points, attempting to keep all The term “high-resolution biostratigraphy” is frequently used
of the bases above the line and the tops below the line. If a by industry paleontologists, although not all biostratigraphic
datum violates this rule, it is either out of place (reworked or studies are truly high resolution. To qualify, a study must
caved) or the composite standard is revised to accommodate have:
the datum. When a well is plotted against a composite stan-
dard, a flat line implies either a hiatus or a fault in the well (a) High-resolution zonation scheme. As discussed above,
(Shaw 1964) (Fig. 13). The construction of a composite most standard zonation schemes are not considered to be
standard section is an iterative, time-intensive process and high resolution by industry standards, necessitating the
can contain errors if reworked specimens are inadvertently construction of in-house schemes with higher resolutions
included within the composite standard (Agterberg et al. using assemblage changes and nonstandard or local
2013). An automated adaptation of graphic correlation termed markers. The resolution is somewhat age dependent;
constrained optimization (CONOP) determines the best fit schemes for younger sections (e.g., Pleistocene) typically
line for each section simultaneously (Kemple et al. 1995). can attain higher resolutions than schemes for older
sections.
Biostratigraphy 17

Biostratigraphy, Fig. 13 Graphic correlation of an onshore Louisiana ignored, leaving the line of correlation (green line) poorly constrained.
well (well A) plotted against a local composite standard for the Three tops (cyan crosses) are higher in well A than in the composite
Berriasian-Oxfordian (basal Cretaceous-Late Jurassic) section. The standard, suggesting that they need to be revised upward (magenta
data from well A are from cuttings; the base occurrences (red circles) arrows) in the composite standard
are much lower than expected due to downhole contamination and so are

(b) Detailed, quantitative sample data. To provide the appro- sequence stratigraphy, and thermal maturity, some of which
priate data to recognize assemblage changes or difficult to are done at well-site. Due to the small size of individual
identify species, a significant amount of sample examina- cutting pieces from drill wells, industry biostratigraphers
tion time using quantitative counting methods is usually utilize microscope fossils, particularly foraminifera, calcare-
needed. ous nannofossils, and palynomorphs. Modern biostrati-
(c) High-density sampling. There is no set rule on sampling graphic techniques, including quantitative data analyses and
density; a condensed section will require a higher sample high-resolution biostratigraphy, were developed to aid in
density than an expanded section to provide the same resolving problems with biostratigraphy, which include fossil
resolution. In general practice, the sample density must preservation and recovery, downhole contamination and
be sufficient to differentiate all likely biohorizons to be reworking, diachroneity, and species identification.
“high resolution.”

Cross-References
Summary
▶ Calcareous Nannoplankton
Biostratigraphy is the application of paleontology to solve ▶ Foraminifera
geologic problems. Within industry, uses include determining ▶ Palynology
relative age, correlations, paleoenvironmental interpretations,
18 Biostratigraphy

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P

Programmed Temperature Pyrolysis samples of drill cuttings or core from wells under an inert
atmosphere using a single programmed ramp of increasing
Kenneth E. Peters1,2 and Leonardo Briceño Rodriguez3 temperature, typically 25
C/min (Espitalié et al. 1977; Peters
1
Schlumberger, Mill Valley, CA, USA 1986; Peters and Cassa 1994).
2
Department of Geological Sciences, Stanford University, Specialized programmed pyrolysis instrumentation is used
Stanford, CA, USA for item 3 to obtain accurate temperatures for the thermal
3
Schlumberger, Mexico City, Mexico decomposition of organic matter used in kinetic determina-
tions. Early work summarized by Tissot and Espitalié (1975)
showed that the laboratory maturation of organic matter in
Definition source-rock samples can be described by parallel series of
independent first-order reactions. The recommended method
Programmed pyrolysis is a laboratory method commonly for kinetic analysis of pyrolysis results generates a discrete
used to characterize organic matter in sedimentary rocks; it activation energy distribution and corresponding frequency
involves heating of a rock sample at progressively higher factor for thermally immature equivalents of the source rock
temperatures in the absence of oxygen in order to evaluate it and requires at least three pyrolysis temperature ramps on
as a petroleum source or reservoir rock or to determine kinetic aliquots of each sample (~3–10 mg) that span a 20-fold
paramaters that describe the thermal decomposition of the variation of comparatively low rates, such as 1, 5, and
organic matter to petroleum. 25
C/min (Peters et al., 2015b). Instrument design, thermo-
couple orientation and size, and sample weight are key fac-
tors that influence the quality of the resulting kinetic
Introduction parameters. Several commercial instruments that can be
used to measure kinetic parameters include Pyromat II™,
Open-system programmed temperature pyrolysis is used in Hawk™, SR Analyzer™, and Rock-Eval 6 ®.
exploration for conventional and unconventional petroleum Although this paper focuses on pyrolysis and discrete
resources to (1) rapidly and inexpensively measure properties sampling as described above, these data can be complemented
of organic matter that can be used to evaluate the quantity, by direct and indirect wireline measurements of total organic
quality, and thermal maturity of large numbers of candidate carbon (TOC; Peters et al. 2016a) and by downhole fluid
source-rock samples from wellbores, (2) identify petroleum analysis (DFA). For example, neutron-induced capture and
reservoir intervals and thermal maturity gradients with depth, inelastic gamma ray spectroscopy using a high-resolution
and (3) provide kinetic parameters for source rocks that can be scintillator differentiates complex lithologies and provides
used in computerized basin and petroleum system modeling quantitative TOC values at typical well logging speeds
(BPSM) to simulate the transformation of organic matter to (Gonzalez et al. 2013). DFA employs near-infrared, visible,
petroleum during burial in sedimentary basins. Commercial and fluorescence spectroscopy for continuous measurements
programmed pyrolysis instruments that address items 1 and 2, of fluid properties that are especially useful to evaluate reser-
such as Rock-Eval ® or SR Analyzer™, heat ~100-mg voir fluid gradients and connectivity (Mullins et al. 2014).

# Springer International Publishing AG 2017

R. Sorkhabi (ed.), Encyclopedia of Petroleum Geoscience,
DOI 10.1007/978-3-319-02330-4_7-1
2 Programmed Temperature Pyrolysis

Quality, Quantity, and Thermal Maturity of Rock Issler and Snowdon 1990). The method assumes that thermal
Samples alteration of organic matter can be described by independent,
parallel first-order reactions that conform to the Arrhenius
Most petroleum industry or service laboratories use Rock- equation (e.g., Ungerer and Pelet 1987). This assumption
Eval pyroanalyzers, so the following discussion will empha- may be oversimplified because petroleum generation com-
size the development and use of these systems. However, the prises multiple cracking reactions, including initiation, prop-
methods and results obtained by other systems, such as the SR agation, and termination steps (Stainforth 2009) that involve
Analyzer, are similar. Various generations of Rock-Eval free radicals, acid thermolysis, and carbonium ion reactions
pyroanalyzers are currently used (Espitalié et al. 1977; with a-olefins (Kissin 1987). In addition, Stainforth (2009)
Lafargue et al. 1998). Rock-Eval pyrograms and calculated infers that primary migration of petroleum through the
parameters for large numbers of closely spaced samples in source-rock kerogen network rather than kerogen cracking
wells can be used to identify petroleum source rocks as well as is the rate-limiting step in petroleum expulsion. Kerogen
petroleum reservoir rocks (Peters 1986; Peters and Cassa consists of particulate organic matter in sedimentary rocks
1994). The method is best used as a screening tool to identify that is insoluble in organic solvents. Despite these issues,
a few key samples for further, more sophisticated geochemi- most workers obtain source-rock kinetic parameters using
cal analyses, such as gas chromatography-mass spectrometry programmed pyrolysis, partly because measured and pre-
(GCMS) of candidate petroleum source-rock extracts for bio- dicted petroleum generation rate curves from open-system
marker (molecular fossil) composition (Peters et al. 2005). pyrolysis are similar to those observed in natural maturation
Conventional and unconventional petroleum resources are series. These observations suggest that programmed pyrolysis
fundamentally different and require different vertical sample experiments can be used to reliably predict maturation over
spacing within wells for useful pyrolysis interpretations geologic time (e.g., Schenk and Horsfield 1998). Predictions
(Peters et al. 2015a, 2016a). As discussed below, conven- from BPSM that are based on laboratory kinetics agree with
tional and unconventional exploration commonly require field data from exploration wells (e.g., Figure 9 in Kuhn
10-m and 1-m or less sample spacing, respectively. Explora- et al. 2012).
tion for conventional resources aims to find petroleum that Some publications recommend open-system pyrolysis
migrated from organic-rich, thermally mature source rock to using a single temperature ramp and fixed frequency factor
reservoirs and traps. Unconventional rock or sediment units (e.g., Waples 2016 and references therein), but this is not
require stimulation, such as hydraulic fracturing, to produce recommended because one-ramp kinetics result in the poten-
the retained petroleum based on the balance between petro- tial for significant error (Peters et al. 2015b, 2016b). Several
leum viscosity and rock matrix permeability. According to publications describe how to optimize kinetic parameters
this definition, gas shales and gas hydrates are unconventional based on open-system programmed pyrolysis. Braun and
targets because very low permeability impedes the escape of Burnham (1987) showed that fitting to a single heating rate
hydrocarbon gases, such as methane, without stimulation. yields unreliable kinetic results for source rocks when both
Shale oil in “tight” mudstones is an unconventional resource the activation energy (Ea, kcal/mol) distribution and pre-
because the oil cannot readily pass through narrow pore exponential factor (A, s1) are optimized. Model fitting
throats in the rock. Oil sands are also unconventional based on single-ramp kinetics is deemed unacceptable by
resources because viscous biodegraded oil cannot readily Vyazovkin and Wight (1999), and it is not recommended by
escape from otherwise high-permeability sandstone without the Kinetics Committee of the International Confederation for
stimulation. Thermal Analysis and Calorimetry (Vyazovkin et al. 2014).
Sundararaman et al. (1992) and Dieckmann (2005) also
showed that a single pyrolysis heating rate experiment gives
Petroleum Generation Kinetics for Rock Samples unreliable discrete Ea distributions. Both authors concluded
that reliable kinetic results require multiple pyrolysis experi-
Kinetic parameters for the transformation of organic matter to ments on aliquots of the source-rock sample at widely differ-
petroleum are required to compute petroleum yields and ing heating rates.
generation rates in basin and petroleum system modeling. Other methods that differ from open-system programmed
Artificial maturation based on programmed pyrolysis of pyrolysis have been proposed to obtain kinetic parameters for
organic matter in source-rock samples can be used to generate the thermal decomposition of organic matter. These include
independent first-order reactions that are constrained by a closed-system isothermal pyrolysis, such as hydrous pyroly-
distribution of activation energies and a corresponding pre- sis (e.g., Lewan et al. 1979; Lewan and Ruble 2002), micro-
exponential factor (Tissot and Espitalié 1975). These kinetic scale sealed vessel pyrolysis (MSSV, e.g., Horsfield et al.
parameters were used in many early BPSM simulations (e.g., 1989), or gold tube reactors (e.g., Behar et al. 1992). Some
Sweeney et al. 1987; Espitalié et al. 1988; Ungerer 1990; papers discuss the reliability of kinetics determined using
Programmed Temperature Pyrolysis 3

open- versus closed-system pyrolysis (e.g., Schenk and considered for positioning of horizontal wells within source-
Horsfield 1993; Ritter et al. 1995; Barth et al. 1996; Lewan rock intervals (Peters et al. 2016a).
and Ruble 2002). In this paper, we focus on open-system
programmed pyrolysis because it is the most commonly Kinetic Measurements
used and likely the most reliable method to obtain source- For kinetic measurements, the ideal sample consists
rock kinetic parameters. ~3–10 mg of organic-rich, unweathered source rock that has
undergone diagenesis but has not yet generated appreciable
petroleum (vitrinite reflectance equivalent 0.5%). Whole
Methods rock samples typically yield kinetic parameters similar to
isolated kerogen (Tegelaar and Noble 1994; Reynolds and
Rock-Eval Pyrolysis Burnham 1995). The organofacies in the sample must be
For Rock-Eval pyrolysis, samples of drill cuttings, sidewall representative of that within the effective source rock in the
core, or conventional core are first screened by binocular study area because the rate of thermal decomposition of
microscope and then crushed to fine sand particle size organic matter to petroleum can differ for different source
(0.125–0.25 mm), and ~100 mg of each dried (<50
C) sample rocks (Tegelaar and Noble 1994) and even vertically or later-
is loaded into pyrolysis crucibles. The samples are pyrolyzed ally within the same source rock (Peters et al. 2006).
under flowing helium at 300
C for 3–4 min, followed by Continuous temperatures are measured during each pro-
heating at 25
C/min to 550
C or 600
C, depending on the grammed pyrolysis experiment using a calibrated thermocou-
pyroanalyzer model. Pyrolysis products from each sample, ple in close contact with the sample. Performance and
such as hydrocarbons (compounds that contain carbon and accuracy of temperature measurements for each pyrolysis
hydrogen) and carbon dioxide generated by the pyrolysis, are system need to be evaluated independently. Products volatil-
measured in ~20 min. Programmed temperature pyrolysis also ized during decomposition of the kerogen are transferred to a
produces large quantities of nonhydrocarbons (compounds that flame ionization detector, typically by helium flow at
contain nitrogen, sulfur, and oxygen, in addition to carbon and 50 ml/min. Pyrolyzate peaks for kerogen decomposition can
hydrogen). Both hydrocarbons and nonhydrocarbons are mea- be processed by using various types of software, such as
sured by a flame ionization detector (FID). Kinetics05 or Kinetics2015, using methods originally
Programmed temperature pyrolysis and TOC data from described by Burnham and Braun (1999). Kinetic parameters
wells are best interpreted using large numbers of samples are determined by iterative linear–nonlinear regression,
taken at closely spaced intervals from each well. For conven- where energy weighting factors are determined by
tional exploration, 10-m spacing is recommended, regardless constrained linear regression for a given frequency factor
of lithology (Peters and Cassa 1994). For unconventional and the logarithm of the frequency factor is varied under
exploration, increased resolution of 1-m spacing or less may Levenberg–Marquardt nonlinear regression (Levenberg
be needed to optimize the best zone to position horizontal 1944) until the root mean square deviation between measured
wells within source-rock units prior to hydraulic fracturing. and calculated generation rates of pyrolyzate yields a
Wireline tools offer the advantage of continuous rather than minimum.
discrete measurements of TOC but cannot be used to interpret Samples of thermally immature source rock that are age
kerogen quality or thermal maturity (e.g., compare Figures 3.3 equivalent with the effective source rock in a basin are com-
and 3.7 in Peters et al. 2016a). monly unavailable. In such cases, a common but flawed
A “sweet spot” is that portion of unconventional source rock practice in BPSM is to use default kinetic parameters avail-
having more favorable porosity, permeability, water saturation, able in the software for other source rocks that are assumed to
fluid properties, and/or rock stress that is likely to produce more contain organic matter similar to that in the study area based
petroleum than adjacent rock (Peters et al. 2016a). Identifica- on kerogen type (e.g., Waples et al. 1992) or depositional
tion of sweet spots requires properly scaled geochemical mea- environment and stratigraphic age (e.g., Pepper and Corvi
surements. Multiple geochemical logs (see below) can be used 1995). We do not recommend this assumption because kero-
to create maps to identify the lateral and vertical distributions of gen type as defined by Rock-Eval pyrolysis hydrogen index
sweet spots. For critical samples that define source rock, reser- (HI, mg hydrocarbon/g TOC) is not systematically linked to
voir rock, or potential productive zones for horizontal wells, kinetic response and it is risky to infer kerogen type or
interpretations from the pyrolysis results should be verified by kinetics based on source-rock depositional environment
other analyses, such as organic petrography, vitrinite reflec- (Peters et al. 2006). Thus, default kinetics for source rock
tance, gas chromatography of extracts, and petrophysical mea- from one basin may not apply to that in other basins, even
surements. This paper does not describe geomechanical when the HI for immature equivalents of each source rock are
properties of the rock, such as Young’s modulus, Poisson’s identical.
ratio, or preexisting fracture orientation, which must also be
4 Programmed Temperature Pyrolysis

Interpreting Rock-Eval Pyrograms (e.g., sulfur-, nitrogen-, or oxygen-containing compounds)

provided that the latter contain carbon atoms.
An example of a programmed temperature pyrogram shows Rock-Eval Tmax is a measure of thermal maturity based on
products generated from low-maturity source rock that has programmed pyrolysis oven temperature that should not be
not yet reached the oil-generative window (Fig. 1, upper left). confused with geologic temperature. In the absence of fluid or
The thick red line shows oven temperature through time. The particulate contamination (discussed below), Tmax commonly
shaded peaks represent S1 (volatile hydrocarbon yield at correlates with other thermal maturity parameters, such as
300
C), S2 (hydrocarbons cracked from kerogen in the vitrinite reflectance (Ro). For example, Jarvie et al. (2001)
range 300–550
C), and S3 (carbon dioxide generated up to recommend the following formula to convert Rock-Eval
390
C). S1 generally increases at the expense of S2 during pyrolysis Tmax to Ro:
thermal maturation of source rocks (Fig. 1, right column),
Ro ðcalculatedÞ ¼ ð0:0180ÞðTmax Þ  7:16 (1)
although loss of some S1 due to expulsion can occur. S1 is
high in active source rocks and reservoir rocks that contain
The formula was derived from a collection of shale sam-
petroleum. S2 is a measure of the remaining petroleum-
ples containing low-sulfur Type II and Type III kerogen
generative potential. S2 is a better indicator of generative
(Jarvie et al. 2001) but can be inaccurate for Type
potential (quality) than TOC (quantity), which does not dif-
I kerogens. Kerogen type is defined by Rock-Eval HI in
ferentiate between oil-prone, gas-prone, or inert carbon. S2 is
Table 1. Use of the formula is not recommended for very
high in potential and active source rocks but low in post-
low- or high-maturity samples (where Tmax is <420
C or
mature (spent) source rocks, non-source rocks, and many
>500
C) or when S2 is less than 0.5 mg HC/g rock. How-
reservoir rocks. Ideally, S3 indicates carbon dioxide cracked
ever, these correlations are best determined on a case-by-case
from the kerogen. However, some carbonate-rich rocks that
basis (Wüst et al. 2013). Tmax determined on very small S2
contain clays generate carbon dioxide below the 390
C trap
peaks (<0.2 mg HC/g rock) can be inaccurate. HI can be low,
temperature (Peters 1986). Oxidation of organic matter in
while Tmax is high compared to isolated kerogen from
weathered outcrop samples and over-grinding during sample
organic-lean (<1 wt.% TOC) clay-rich rocks due to adsorp-
preparation can also elevate S3. S1 and S2 are measured by
tion of pyrolyzate on clays (Peters 1986).
FID, while S3 is measured by thermal conductivity detection
(TCD). FID measures hydrocarbons and nonhydrocarbons

Programmed Temperature Pyrolysis, Fig. 1 Schematic pro- (S1 + S2)]. Crude oil or contamination by oil-based drilling mud can
grammed temperature pyrogram (upper left) shows S1 (volatile petro- yield anomalously high S1, high PI, and low Tmax (asterisk at lower left;
leum) and S2 (kerogen pyrolyzate; mg hydrocarbons (HC)/g rock), S3 S3 not shown). Column at right shows typical evolution of S1, S2, Tmax,
(organic carbon dioxide, mg CO2/g rock), and Tmax (oven temperature in and PI due to increasing thermal maturation of source rock. Pyrograms


C at the maximum of the S2 peak). Calculated parameters include that show high S1 and PI with a very low or no S2 peak could represent
hydrogen index (HI = 100  S2/TOC; mg HC/g TOC), oxygen index postmature source rock or petroleum reservoir rock
(OI = 100  S3/TOC; mg CO2/g TOC), and production index [PI = S1/
Programmed Temperature Pyrolysis 5

Programmed Temperature Pyrolysis, Table 1 Programmed pyrol- table must be interpreted separately. Thickness of the rock unit is also
ysis, and vitrinite reflectance (Ro) parameters used to determine quantity, important for volumetric considerations
quality, and thermal maturity of rock samples. The three segments of the
Quantitya Qualityb Thermal maturityc
TOCm, PI,
Amount TOCo, wt.% wt.% Type HIo, mg HC/g TOC Product Stage Ro, wt.% Tmax (
C) [S1/(S1 + S2)]
Poor <1 <1 I >600 Oil Immature 0.20–0.60 <435 <0.10
Fair 1–2 1.0–1.5 II 300–600 Oil Early mature 0.60–0.65 435–445 0.10–0.15
Good 2–3 1.5–2.0 II–III 200–300 Oil/ gas Peak mature 0.65–0.90 445–450 0.25–0.40
Very good 3–4 2.0–2.5 III 50–200 Gas Late mature 0.90–1.35 450–470 >0.40
Excellent >4 >2.5 IV <50 None Postmature >1.35 >470 –
a
TOCo = original total organic carbon content for thermally immature source rock; TOCm = measured total organic carbon for thermally mature or
postmature source rock (unconventional target). Approximate values determined using data for nine top shale gas plays (data from Jarvie 2012a)
b
Type = kerogen type based on pyrolysis hydrogen index, HIo (= 100  S2/TOC for thermally immature source rock)
c
Ro = oil-immersion vitrinite reflectance; Tmax = pyrolysis oven temperature at maximum of S2 peak; for onset of oil generation: Type I ~ 445
C,
Type II ~435
C, Type III ~440
C; PI = production index, where S1 = petroleum volatilized at 300
C and S2 = petroleum cracked from the kerogen
in the range 300–550
C during pyrolysis at 25
C/min

The production index [PI = S1/(S1 + S2)] increases with III pathway on the Van Krevelen diagram, which could be
depth in fine-grained rocks because thermally reactive com- incorrectly interpreted to indicate kerogen dominated by
ponents in the kerogen (S2) are gradually converted to vola- vitrinite macerals with the potential to generate only hydro-
tile hydrocarbons (S1). Coarse-grained conventional carbon gases. Pyrolysis–gas chromatography of such a sam-
reservoir rocks stained with oil show anomalously high S1 ple could be used to reveal significant oil-generative potential
and PI values that deviate from the depth trend in the adjacent (e.g., Peters et al. 1983).
fine-grained rocks. In some cases, Tmax may be suppressed Jarvie (2012a) derived original hydrogen indices (HIo) for
due to carry-over of heavy ends in the oil from S1 into S2 thermally immature samples of the ten top North American
(Fig. 1, lower left). Oil-based drilling mud additives can also shale gas plays: Barnett, Bossier, Eagle Ford, Fayetteville,
interfere with pyrolysis measurements, especially S1 and Haynesville, Marcellus, Montney, Muskwa, Utica, and
PI. Oil-based contamination of cuttings samples commonly Woodford formations. He determined the average present-
yields a large S1 peak, a low-temperature shoulder that inter- day TOC (TOCm) on collections of samples from those
feres with the S2 peak and represents heavy ends of the oil plays showing mostly gas window thermal maturity. The
rather than kerogen, and a corresponding anomalously low equation below excludes data from the Hayneville Shale,
Tmax value (Fig. 1, lower left). S1 values >1 mg HC/g rock which began with an unusually high HIo, (722 mg HC/g
and anomalously high PI may indicate contamination of cut- TOC), resulting in a point far off the correlation line. The
ting samples by migrated oil or oil-based contamination. Such remaining nine data points show a linear correlation between
samples are routinely extracted with organic solvent (e.g., TOCo and TOCm with a high correlation coefficient (>0.98):
n-heptane) and reanalyzed in order to derive more accurate
TOCm ¼ 0:5468ðTOCo Þ þ 0:3261 (2)
measures of HI and Tmax (Peters 1986; Peters and Cassa
1994). Provided that their presence is recognized, particulate
This relationship was used to calculate the approximate
additives, such as walnut hulls or polyethylene, can be
cutoff values for poor, fair, good, very good, and excellent
removed under a binocular microscope.
TOCm for unconventional targets in Table 1. These TOC
Hydrogen index [HI = 100(S2)/TOC] and oxygen index
values represent quantity (not quality), and they are based
[OI = 100(S3)/TOC) are based on combined pyrolysis and
on an average HIo of ~438  62 mg HC/g TOC. Peters et al.
TOC parameters. Modified Van Krevelen plots of OI versus
(2005, pp. 97–100) provide mass balance calculations to
HI or plots of Tmax versus HI must be used with caution to
determine TOCo from TOCm.
infer kerogen type and approximate level of thermal maturity
(Espitalié et al. 1977; Peters 1986). Because kerogen consists
of mixtures of macerals, plot locations on the modified Van
Historical Development of Rock-Eval
Krevelen diagram can be deceptive (Dembicki 2009).
Pyroanalyzers
Macerals are microscopically recognizable particles of kero-
gen that show distinct physicochemical properties. The three
Since the 1970s, various Rock-Eval pyroanalyzers were
main maceral groups include liptinite, vitrinite, and inertinite.
developed to characterize rock samples from wellbores and
For example, a mixture of oil-prone type II (liptinite macerals)
outcrops, and these have become the most popular
and inert type IV (inertinite macerals) might plot near the type
6 Programmed Temperature Pyrolysis

programmed pyrolysis instruments used by the petroleum during hydraulic fracturing in order to increase exposed sur-
industry. Many commercial laboratories still use Rock-Eval face area in the rock and enhance gas and oil production.
2 instruments (Espitalié et al. 1977), which include automatic Zones that readily fracture and have OSI values >100 mg
sampling and microprocessor control not available in Rock- oil/g TOC are favorable for unconventional oil recovery
Eval 1. In Rock-Eval 2, the S1 peak includes all hydrocarbons (Jarvie 2012b).
volatilized at 300
C over a 3-min isothermal heating. TOC is Interpretation of geochemical logs can be facilitated using
determined separately on splits of the same sample by com- automated software. For example, AGEL (automated geo-
bustion. Rock-Eval 3 (oil show analyzer) effectively separates chemical log interpretation) is proprietary Schlumberger soft-
the volatile components into two peaks, S0 and S1. ware that interprets large amounts of pyrolysis, TOC, and
S0 includes light gas or condensate hydrocarbons in the vitrinite reflectance data using a set of interactive and heuris-
range C1–C8 that are volatilized during a 90
C isothermal tic rules. Figure 2 shows an AGEL geochemical log with
heating for 1–5 min, while S1 includes hydrocarbons volatil- accepted and rejected data for the Caribou N-25 well from
ized at 300
C during a 3-min isothermal heating. Contami- the Mackenzie Corridor, Canada. Interpretation of raw data
nation of samples during drilling or evaporative loss during and the log would have been difficult without the use of
sample handling can seriously affect S0 values. Rock-Eval heuristic rules to screen anomalous results. Note that the
3 combusts the residue from the pyrolysis, which allows correlation between Ro and Tmax differs from that in Eq. 1
determination of TOC without the need to split rock samples as follows (R2 = 0.96):
for separate pyrolysis and TOC analyses. Since the combus-
Ro ðmeasuredÞ ¼ ð0:0132ÞðTmax Þ  5:25 (3)
tion in Rock-Eval 3 occurs at the same maximum temperature
as the original pyrolysis (550–600
C), TOC values for highly
Although programmed pyrolysis and TOC data represent a
mature rock samples are commonly lower than conventional
valuable screening tool to evaluate hundreds or thousands of
combustion results (>1000 C) because they may contain
measurements, some pitfalls must be acknowledged (for more
organic matter that is not readily oxidized.
details, see Peters 1986; Peters and Cassa 1994; Dembicki
The Rock-Eval 6 pyroanalyzer improves on earlier ver-
2009):
sions by providing S1, S2, S3, as well as carbonate carbon and
TOC. Similar results can be obtained using the SR Analyzer
1. Pyrolysis sample size should be uniformly near 100 mg.
TPH/TOC™. Combustion in the Rock-Eval 6 oven occurs at
2. There is no simple relation between TOC and S1 or S2
850
C, resulting in more efficient oxidation for TOC
(quantity versus quality).
determination.
3. Bitumen, migrated oil, and oil-based drilling additives can
interfere with parameters, particularly S1, S2, PI, HI, and
Tmax. Extraction to remove these fluids results in loss of S1
Data Interpretation Using Geochemical Logs
during evaporation of the solvent and may not improve
measurements of S2, HI, and Tmax.
Geochemical logs simplify data interpretation by showing
4. Lithology and mineral/organic matter ratio can influence
large amounts of pyrolysis, TOC, and other data, such as
response.
vitrinite reflectance, versus depth in wells (Fig. 2). Multiple
5. Tmax is inaccurate for small peaks (<0.2 mg HC/g rock).
geochemical logs can be used to create maps to identify the
6. Some carbonate-rich rocks can contribute to S3 and OI.
lateral and vertical distributions of sweet spots. Trends and
7. Some coals (>50 wt.% TOC) show anomalously high HI
anomalous data are readily apparent on geochemical logs and
values.
can be validated by examination of pyrograms, inquiries
8. Pyrograms should be examined, especially when contam-
about well conditions or sampling methods, and, if necessary,
ination or migrated oil is suspected.
repeat or additional analyses.
9. Geochemical logs simplify interpretation and should be
Geochemical logs that include carbonate content and the
constructed using data that have been evaluated using
oil saturation index (OSI = 100  S1/TOC) provide informa-
heuristic rules to control data quality.
tion on both geomechanics and geochemistry that is useful to
evaluate unconventional resources. OSI can be used to indi-
cate zones within unconventional strata that are likely to be
Extrapolation of Kinetic Measurements to
productive, provided that significant amounts of brittle car-
Geologic Time
bonate or silicate minerals are present to effectively receive
proppant upon hydraulic fracturing. The injected proppant
Discrete activation energy (DAE) modeling requires optimi-
keeps fractures open, thereby increasing surface area in the
zation of both Ea and A to determine the rate of kerogen
target rock and increasing fluid flow into the well. Proppant
decomposition at any laboratory temperature. The
consists of sand or man-made ceramic particles injected
Programmed Temperature Pyrolysis 7

Programmed Temperature Pyrolysis, Fig. 2 Typical geochemical Tmax data are indicated using solid and open symbols, respectively. Raw
log of programmed pyrolysis, TOC, and vitrinite reflectance data for the data are from Allen et al. (2008)
Caribou N-25 well, Mackenzie Corridor, Canada. Accepted and rejected

“compensation law” shows that a wide range of Ea and Summary

A combinations can satisfy the Arrhenius equation for the
laboratory rate constant, but extrapolation of incorrect Ea Programmed temperature pyrolysis, TOC, and vitrinite reflec-
and A to geologic time can result in incorrect temperature tance are rapid and inexpensive tools that are commonly
predictions (Peters et al. 2016b). DAE uses a single frequency combined in geochemical logs to evaluate the quantity, qual-
factor for all possible activation energies associated with the ity, and thermal maturity of source-rock organic matter and
discrete distribution. The value of A can be optimized by the the presence of petroleum in conventional or unconventional
software (e.g., Kinetics05, Kinetics2015; http://geoisochem. rock units. Pyrolysis and TOC measurements are most effec-
com/software/kinetics2015/index.html) or it can be an tive when based on large numbers of closely spaced samples
assumed, universal value (not recommended). Use of a uni- in wellbores: typically 10-m or <1-m spacing in conventional
versal value for A (e.g., 1  1014 s1; Waples 2016 and or unconventional resources, respectively.
references therein) can lead to erroneous results (Peters et al. Good, very good, and excellent quantities of organic car-
2016b). For robust solutions, the pyrolysis experiments must bon are in the ranges 2–3, 3–4, and >4 wt.% TOC for
include three or more widely differing heating rates using an thermally immature equivalents of conventional source
energy spacing of 1 kcal/mol or less (Fig. 3). rocks and 1.5–2.0, 2.0–2.5, and >2.5% for thermally mature
unconventional source rocks. Four measured and three
8 Programmed Temperature Pyrolysis

Programmed Temperature Pyrolysis, Fig. 3 Left: pyrograms for six fraction (i.e., transformation ratio) and A value. Right: Extrapolation to
programmed pyrolysis experiments on aliquots of the same thermally geologic conditions assuming a constant heating rate of 3
C/my.
immature source-rock sample (dotted curves) fit using Kinetics05 soft- Fraction = transformation ratio or extent of conversion of kerogen to
ware (solid curves). Extremely slow (<1
C/min) or fast (>30
C/min) petroleum. This plot is useful to compare the response of different
heating rates are not recommended due to volatilization or thermal lag source-rock kerogens. In BPSM, the burial history and paleo-heat flow
effects (Peters et al. 2016b). Center: calculated Ea distribution versus would be used to calculate extent of conversion

calculated parameters from Rock-Eval programmed temper- (1) location on the modified Van Krevelen diagram of OI
ature pyrolysis are as follows: versus HI and (2) approximate Tmax, where immature
<435
C, mature = 435–470
C, and postmature >470
C.
1. S1 represents free hydrocarbons (gas and oil) in the sample
(mg HC/g rock). S1 > 1 mg/g rock may indicate an oil Open-system programmed pyrolysis of source-rock sam-
show. Crude oil and oil-based drilling mud can interfere ples can be used to generate kinetic parameters for petroleum
with S1 and other pyrolysis parameters. generation assuming independent first-order reactions that are
2. S2 represents hydrocarbons cracked from the kerogen constrained by a distribution of activation energies and a
(mg HC/g rock), which indicates the remaining potential corresponding pre-exponential factor. The method assumes
of the rock to generate oil and gas if buried further. Partic- that thermal alteration of organic matter can be described by
ulate additives, such as walnut hulls or polyethylene, can first-order reactions that conform to the Arrhenius law. Most
interfere with HI, Tmax, and other pyrolysis parameters. workers obtain source-rock kinetic parameters using pro-
3. S3 is the amount of carbon dioxide generated from the grammed pyrolysis rather than other methods, such as
kerogen (mg CO2/g rock). Some carbonate minerals hydrous pyrolysis, because measured and predicted petro-
decompose below 390
C and can interfere with S3. Oxi- leum generation rate curves from open-system pyrolysis are
dation due to weathering of outcrop samples or over- similar to those of natural maturation series. Predictions from
grinding during sample preparation can also contribute to BPSM that are based on laboratory kinetics agree with field
S3. data from exploration wells.
4. Tmax is the oven temperature at the maximum yield of S2,
which gives an indication of the level of thermal maturity
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thermally immature rock identifies oil-prone type ▶ Petroleum Source Rock
I (>600 mg HC/g TOC) and type II (300–600 mg HC/g ▶ Total Organic Carbon
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Programmed Temperature Pyrolysis 9

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167031-MS
B

Biomarkers in Sediments and Petroleum establish this critical link between precursors in the biosphere
and biomarkers in the geosphere. The geosphere includes the
Kenneth E. Peters deep earth and the oceanic and continental crust but excludes
Schlumberger, Mill Valley, CA, USA the biosphere (life), atmosphere, and oceans. Since 1979 the
Department of Geological Sciences, Stanford University, prestigious Alfred E. Treibs Medal has been presented on
Stanford, CA, USA behalf of the Organic Geochemistry Division of the Geo-
chemical Society to scientists who have had a major impact
on the field of organic geochemistry through long-standing
Synonyms contributions.
After a hiatus of nearly 30 years since the pioneering work
Biological markers; Molecular fossils of Treibs, Eglinton et al. (1964), and Eglinton and Calvin
(1967) provided additional evidence that biomarkers in petro-
leum and ancient rocks originate from biological remains and
Definition yield information about past life and depositional conditions.
Later work expanded the use of biomarkers in crude oils to
Biomarkers (Eglinton et al. 1964) are complex, recalcitrant describe the depositional environments of their source rocks
organic compounds that show little or no change in chemical (Seifert and Moldowan 1978) and showed how chemometrics
structure from their parent lipids in once-living organisms (multivariate statistics) of biomarker data can be used to
(Whitehead 1973). They are common in petroleum and recent extract even more information (Peters et al. 1986). Renewed
to ancient sediments and are composed mainly of carbon and interest in the transformation of organic matter into petroleum
hydrogen but can include other elements, such as sulfur, (Hunt 1979, 1996; Tissot and Welte 1984) led to increasingly
nitrogen, vanadium, or nickel. Biomarkers are useful in petro- detailed studies of biomarkers as environmental indicators
leum exploration and production (Peters et al. 2005) as well as (e.g., Brassell et al. 1986) and sensitive records of microbial
environmental forensics (Wang et al. 2006). Readers should processes (e.g., Hinrichs et al. 1999; Kuypers et al. 2003).
be aware that since 1980 (Aronson 2005), the term “bio- Although an abiogenic origin for petroleum from the earth’s
marker” has been adopted by the medical profession for mantle was resurrected by Gold (1999), virtually all credible
compounds that indicate normal biological processes, the evidence obtained since the early work of Treibs supports the
presence or severity of disease, or pharmacologic response biological origin of both biomarkers and petroleum (Peters
to therapy (NIH Definitions Working Group 2000). 1999; Peters et al. 2005).

Historical Development Structure and Stereochemistry

Alfred Treibs (1936) identified tetrapyrrole rings in chloro- Unlike other biological macromolecules, such as carbohy-
phyll and heme from living plants and animals, respectively, drates or proteins, lipids are particularly resistant to microbial
as precursors for free-base and metal-complex porphyrins in degradation during sedimentation and early burial. Lipids are
sediments and crude oil. Treibs is widely regarded as the soluble in oil but insoluble in water and include fatty acids,
father of organic geochemistry because he was the first to waxes, pigments, and terpenes (steroids, hopanoids and

# Springer International Publishing AG 2017

R. Sorkhabi (ed.), Encyclopedia of Petroleum Geoscience,
DOI 10.1007/978-3-319-02330-4_8-1
2 Biomarkers in Sediments and Petroleum

related compounds). Preservation of lipids is enhanced under Like the hopanoids, steroids can be modified by side chain
anoxic conditions when oxygen is low or absent in the water rearrangements, addition of polar functional groups, and
column and sediments (Demaison and Moore 1980). changes in the number or position of double bonds. The
One line of evidence for a biogenic origin is that bio- biomarker product of cholesterol is cholestane, which has
markers and many lower molecular weight compounds in 27 rather than 30 carbon atoms. Terpenoids that do not strictly
crude oil obey the isoprene rule. The isoprene rule states obey the isoprene rule due to reactions that cause the gain or
that terpenes originate from isoprene units and thus have loss of substituents can still be categorized in their parent
molecular formulae that are multiples of C5H8. Figure 1 terpenoid family. For example, cholestane (C27), ergostane
shows the proposed origin of two monoterpenes, each from (C28), and stigmastane (C29) are three homologs in the sterane
two isoprene units during biosynthesis. 2,6-Dimethyloctane series that are common biomarkers in petroleum. These suc-
and 2-methyl-3-ethylheptane (0.50 and 0.64 volume%, cessive homologs differ by one methylene group (-CH2-) in
respectively) are more abundant than the sum of all other the side chain but are genetically linked to the parent C30
49 possible structural isomers of these compounds (0.44 steroid precursor, squalene.
volume%) in Ponca City crude oil because of their biosyn-
thetic origin (Mair et al. 1966). Isomers are compounds hav-
ing the same molecular formula, but different arrangements of Analysis of Biomarkers
their structural groups.
Hemiterpanes (C5), monoterpanes (C10), sesquiterpanes Because concentrations of individual biomarkers can be as
(C15), diterpanes (C20), and sesterterpanes (C25) are saturated low as a few ppm, most laboratories pretreat samples of crude
biomarkers that contain one, two, three, four, and five iso- oil or source rock extracts by separating saturate, aromatic,
prene subunits, respectively. For example, phytane is a head- and polar fractions using high-performance liquid chroma-
to-tail linked acyclic diterpane that originates mainly from the tography. Quantitative addition of internal standards to these
side chain in chlorophyll from plants. Triterpanes and steranes fractions is recommended in order to calculate concentrations
(C30) are composed of six isoprene subunits, tetraterpanes of individual biomarkers from mass chromatograms. Internal
(C40) contain eight, and polyterpanes contain nine or more standards ideally should have structures and mass spectro-
isoprene units (C45+). Polycyclic terpanes include the metric fragments similar to the biomarkers to be measured,
steranes and hopanes. but with side chains or isotope substitutions that do not occur
Squalene is a unsaturated C30 acyclic triterpene that is a in petroleum. This paper focuses on biomarkers in the saturate
critical precursor for biomarkers in all domains of life. fraction, but additional biomarkers occur in the aromatic and
Eukaryotes comprise a domain that includes all higher organ- polar fractions (Peters et al. 2005).
isms having well-defined chromosomes and membrane- Several types of biomarker analyses are available, each
bound nuclei and organelles. Prokaryotes include Eubacteria with advantages and disadvantages. Gas chromatography
and Archaebacteria. Under anoxic conditions, prokaryotes mass spectrometry (GCMS) is used by most service compa-
cyclize squalene to diploptene, a pentacyclic triterpenoid nies, because the instrumentation is comparatively inexpen-
that serves as the biosynthetic precursor for the hopanoids. sive, and the data can be used to solve the vast majority of
This complex cyclization is a single-step enzymatic reaction problems in exploration, production, or forensic geochemis-
that requires alteration of 13 covalent bonds to yield five rings try. However, GCMS for many compound classes can show
and nine stereoisomeric carbon atoms (Kannenberg and considerable interference. For example, various sterane
Poralla 1999). During deposition and burial, hopanoid pre- homologs (i.e., C26-C30 steranes) can interfere on m/z
cursors can be degraded, or they may lose functional groups, 217 mass chromatograms. The m/z 217 mass-to-charge frag-
such as double bonds or hydroxyl groups, while retaining the ment ion is the most abundant ion (base peak) formed during
carbon skeleton of the precursor. For example, C35 bacterio- mass spectrometry of steranes, while m/z 191 is the base peak
hopanetetrol is a key component in bacterial cell membranes for hopanes (dashed arrows in Fig. 1).
that consists of diploptene linked to D-pentose during bio- Gas chromatography-mass spectrometry-mass spectrome-
synthesis (Rohmer 1993). One of the principal try (GCMSMS) in parent-daughter mode removes interfer-
defunctionalized products of bacteriohopanetetrol is the C35 ence from sterane homologs, because it yields separate mass
17a,21b(H)-hopane (pentakishomohopane; Fig. 1) in sedi- chromatograms for C26, C27, C28, C29, and C30 steranes that
ments and crude oil. The alpha and beta symbols refer to would otherwise be combined on one GCMS mass chromato-
stereochemistry at C-17 and C-21 as discussed below. gram (Fig. 2). For example, parent-daughter GCMSMS
Under oxic conditions, eukaryotes can convert squalene to experiments for m/z 400 ! m/z 217 and m/z 414 ! m/z
steroids, such as cholesterol. The aerobic eukaryotic biosyn- 217 yield separate mass chromatograms for C29 and C30
thetic pathway to steroids evolved from the anaerobic path- steranes, respectively. Although generally more expensive
way to hopanoids in the prokaryotes (Rohmer et al. 1979). than GCMS, GCMSMS improves sterane fingerprints for
Biomarkers in Sediments and Petroleum 3

Biomarkers in Sediments and Petroleum, Fig. 1 Most petroleum that contains six isoprene units. Prokaryotes can cyclize squalene to
biomarkers are steranes or hopanes biosynthesized in organisms from diploptene, a pentacyclic triterpenoid that is the precursor for bacterio-
isoprene (C5H8) units. Light hydrocarbons show evidence for an origin hopanetetrol in bacteria and bacteriohopane in petroleum. Eukaryotes
from biomarkers. For example, 2,6-dimethyloctane and 2-methyl-3- convert squalene to sterols, such as cholesterol, the precursor for
ethylheptane are more abundant than all other 49 possible structural cholestane in petroleum. The base peaks (most abundant mass spectral
isomers in crude oil. Phytane is a regular isoprenoid that originates fragment ions) for hopanes and steranes have mass/charge (m/z) 191 and
mainly from the phytol side chain of chlorophyll and consists of four 217, respectively
isoprene units linked head to tail. Squalene is a C30 acyclic isoprenoid

correlation and is critical to identify low concentrations of mixed to a highly stratified photic zone in the Pacific Ocean
certain biomarkers, such as C26 24-nordiacholestanes during Miocene time. The carbon isotopic compositions of
(age-sensitive biomarkers from diatoms; Holba et al. 1998), the steranes largely represent algae in the photic zone, while
C30 24-n-propylcholestanes (diagnostic of chysophyte algae the hopane isotopes reflect biomass living below the photic
and marine source rock; Moldowan et al. 1990), and C30 zone. Guthrie (1996) used CSIA to characterize extracts from
24-isopropylcholestanes (indicators of Porifera that suggest core samples in the Upper Ordovician Maquoketa Group of
Upper Proterozoic to Lower Cambrian source rock; the Illinois Basin. Isotopic data for pristane, phytane, steranes,
McCaffrey et al. 1994; Peters et al. 1995). aryl isoprenoids, and other compounds in the samples were
As separation technologies improve, compound-specific used to improve the understanding of the sources of organic
isotope analysis (CSIA) of biomarkers has become a viable matter and paleoenvironmental conditions during the deposi-
tool to reconstruct carbon cycling and correlate oil and source tion of the source rock.
rock samples. For example, Hayes et al. (1987, 1990) and The identification of biomarkers by GCMS or GCMSMS
Freeman et al. (1990) showed that stable carbon isotope can be difficult for highly mature condensates where bio-
compositions of biomarkers in Eocene Messel Shale help to marker concentrations are very low. Correlations based on
identify the sources for various compounds and can be used to biomarkers in such samples are notoriously unreliable
reconstruct carbon cycling within the ancient lake. Schoell because the few remaining biomarkers may be highly altered
et al. (1992, 1994) monitored carbon isotope compositions of and/or they may represent contaminants picked up during
hopanes and steranes in crude oil and rock extracts from the migration through less mature organic-rich rocks. In such
Miocene Monterey Formation. The isotopic variations in cases, the distributions and isotopic compositions of
these biomarkers parallel the inorganic record of oxygen diamondoids are recommended because of their extreme ther-
isotope ratios, indicating gradual evolution from a well- mal stability (Dahl et al. 1999).
4 Biomarkers in Sediments and Petroleum

Biomarkers in Sediments and Petroleum, Fig. 2 Gas mass of m/z 414. GCMS (m/z 217) of this sample would combine all five
chromatography-mass spectrometry-mass spectrometry (GCMSMS) GCMSMS mass chromatograms into one sterane mass chromatogram,
allows parent-daughter experiments that separate stereoisomers among resulting in significant interference. Most compound peaks in the figure
the C26–C30 homologs of the steranes. For example, GCMSMS focuses are identified in Peters et al. (2005). The box shows four C29 sterane
exclusively on C30 steranes (top) by monitoring only those characteristic stereoisomer peaks identified in Fig. 6
sterane fragment ions (m/z 217) that originate from parent ions having a

Biomarkers to Identify Source one can predict migration pathways and the composition of oil
in any intervening traps that are evident from seismic data.
Biomarkers carry isotopic and structural signatures inherited Figure 3 shows examples of oil-oil and oil-source rock corre-
during biosynthesis of their precursors in living organisms, lation based on C27, C28, and C29 homologs of the steranes and
which distinguish them from abiogenic compounds that are diasteranes isolated from the saturate fractions of four crude
common in interstellar space. Furthermore, saturated bio- oils and a prospective source rock from the Czech
markers, such as linear isoprenoids, steranes, and terpanes, resist Republic. The sterane and diasterane “fingerprints” in the
degradation and have been found in very old rocks (Brocks et al. figure support two genetic oil families. Direct oil-source rock
1999). Not long after the inception of the term biomarker, correlation is indicated by the similar fingerprints of the
Burlingame et al. (1965) indicated that isoprenoid alkanes Zdanice-7 and Damborice-16 samples and an Upper Jurassic
could serve as “biological markers” in the search for evidence source-rock extract from the Sedlec-1 well. Another geochem-
of life in carbonaceous meteorites. For the above reasons, bio- ical study also supports an origin for many oils in this area from
markers, such as isoprenoids, steranes, and terpanes, represent Upper Jurassic source rock (e.g., Franců et al. 1996).
promising tools in the search for extraterrestrial life. Biomarkers can be used for indirect oil-source rock correla-
Biomarkers can be used to assist in oil field development tion when samples of thermally mature prospective source rock
by differentiating reservoir compartments and the timing of are unavailable (e.g., Dahl et al. 1994; Peters et al. 2005). For
various oil charges to those compartments (Zumberge et al. example, oleanane and 24-nordiacholestanes are markers of
2005; Peters et al. 2013). Finally, biomarkers can be used to angiosperms (flowering plants; Moldowan et al. 1994a) and
identify sources of petroleum contamination in the environ- diatoms (Holba et al. 1998), respectively. Elevated oleanane
ment and the progress of remediation (Eganhouse 1997). and 24-nordiacholestane ratios in crude oil samples can be used
Successful correlation of a crude oil, seep, or piston core to indicate an approximate age of the source rock because these
sample with the source rock provides a competitive exploration compounds reflect the evolution of the organisms from which
advantage. For example, if a genetic link can be established they originated (Fig. 4). Oleanane is generally absent in Jurassic
between seep oil and mature source rock from a deep well, then or older oil and source rock because angiosperms did not evolve
Biomarkers in Sediments and Petroleum 5

Biomarkers in Sediments and Petroleum, Fig. 3 Ternary diagrams show evidence of mild biodegradation. If more severe biodegradation
show the relative abundance of C27, C28, and C29 steranes (top) and had affected the steranes, the correlation could still be achieved using
diasteranes (bottom) determined by GCMSMS of saturate fractions for only the more resistant diasteranes or other biomarkers above rank 7 in
four crude oils and bitumen extracted from thermally mature Upper Fig. 8. The Zdanice-7 and Damborice-16 oils correlate with the Upper
Jurassic source rock from the Czech Republic (Picha and Peters 1998). Jurassic source rock extract. Repeatability approaches the diameter of
The data distinguish two oil families. The Lubna-18 and Zdanice-7 oils each symbol

Biomarkers in Sediments and Petroleum, Fig. 4 Oil from the source rock from the Sedlec-1 well. Upper Jurassic organic-rich Mikulov
Zdanice-7 well in the Czech Republic is produced from Precambrian marls are up to 1000-m thick in the area and contain up to 10 weight%
crystalline basement rocks (Picha and Peters 1998), which might be TOC of oil-prone organic matter (Reprinted with permission by
interpreted to indicate an abiogenic origin. However, sterane and ChevronTexaco Exploration and Production Technology Company, a
diasterane fingerprints in Fig. 3 support correlation of both Zdanice-7 division of Chevron USA)
and Damborice-16 oil (Carboniferous reservoir) with Upper Jurassic

until Cretaceous time. 24-Nordiacholestane ratios (NDR) in geology suggested only Paleogene and Upper Jurassic source
crude oil >50% indicate Tertiary source rock. rocks for the Czech oil samples in Fig. 3 (Picha and Peters
Geochemical logs, including total organic carbon content 1998). The data in Fig. 4 support the interpretations from
and Rock-Eval pyrolysis hydrogen index, as well as regional Fig. 3 that two oil families occur within the study area.
6 Biomarkers in Sediments and Petroleum

Although suitable samples of Paleogene source rock were two tasks that set it apart from other correlation methods:
unavailable for correlation, abundant oleanane and (1) classification is based on a training set of oil samples,
24-nordiacholestanes in the Lubna-18 and Dolni Lomna-1 and (2) it provides a quantitative assessment of the degree of
oil samples support Paleogene source rock. Low uncertainty for each class assignment. Peters et al. (2007)
24-nordiacholestanes and lack of oleanane confirm the used 20 source- and age-related biomarker and stable carbon
sterane and diasterane data indicating Upper Jurassic source isotope ratios and a training set of 622 oil samples to create a
rock for the Zdanice-7 and Damborice-16 oil samples. chemometric decision tree for classification of circum-Arctic
A few other examples of source-related biomarkers samples. The decision tree was used to identify 31 genetically
include botryococcane, b-carotane, C26/C25 tricyclic terpanes distinct oil families from a dataset consisting of more than
(lacustrine), bicadinanes (Dipterocarpaceae, higher plants), 1000 crude oil and source rock-extract samples.
gammacerane (salinity stratified water), pristane/phytane,
C35/C34 hopanes (redox), isorenieratane (photic zone anoxia),
C29/C30 hopanes, C22/C21 tricyclic terpanes (carbonate), Biomarkers to Assess Thermal Maturity
diasteranes/steranes, and C24/C23 tricyclic terpanes (shale)
(Peters et al. 2005 and references therein). The complex structures of biomarkers result in multiple
Commingled black oils are common and can result from asymmetric carbons atoms characterized by covalent bonds
natural mixing during accumulation in the reservoir or mixing (at 109.5o angles) to four different substituents. Asymmetric
from different zones during production. Alternating least carbons have two mirror image structures that cannot be
squares of biomarker concentrations (not ratios) can be used superimposed, i.e., they consist of left- and right-handed
to reliably deconvolute mixtures of two or more oil types forms (Fig. 5). Diasteromers are compounds that have multi-
because the concentrations of compounds in mixtures ple asymmetric centers. For example, cholestane (C27 sterane)
vary as linear functions of the amount of each oil type has eight asymmetric carbon atoms at C-5, C-8, C-9, C10,
(Peters et al. 2008). Mixing of black oil with condensate is a C-13, C-14, C-17, and C-20, resulting in 256 (28) potential
more difficult problem that requires the use of diamondoids stereoisomers of cholestane. However, the biological configu-
(Dahl et al. 1999). ration of cholestane inherited from cholesterol in living organ-
Petroleum systems (Magoon and Dow 1994) are best isms has only one configuration. Geological configurations of
defined using multiple source-related biomarker and isotope cholestane result from the thermal process of stereo-
ratios to correlate oil and source rock samples. Simple oil-oil isomerization during burial. Although many geological config-
or oil-source rock correlations based on only a few parameters urations are possible, only a few are generally useful to describe
(e.g., Fig. 3) can be enhanced by applying chemometrics the extent thermal maturation (Fig. 5) using the simple ratio
(multivariate statistics) to many source-related parameters. B/(A+B), where A and B are biological and geological config-
Decision-tree chemometrics (Peters et al. 2007) accomplishes urations of cholestane in the reaction A ! B. Immature source

Biomarkers in Sediments and

Petroleum, Fig. 5 Asymmetric
carbon atoms (top) can show left-
or right-handed stereoisomers that
are mirror images (dashed vertical
line). The labeling nomenclature
for steranes and hopanes includes
rings (letters) and carbon positions
(numbers). Hydrogen atoms are
not shown. Stereochemistry of the
biological configuration of
cholestane (X = H) is 5a(H),8b
(H),9a(H),10b(CH3),13b
(CH3),14a(H),17a(H)20R
Biomarkers in Sediments and Petroleum 7

rocks have B/(A+B) that begins at zero and increases to some maturity assessment than stereoisomer ratios. For
endpoint value, depending on the relative stability of the par- example, Ts/(Ts+Tm) increases with maturity because Tm
ticular cholestane stereoisomer. (C27 17a-22,29,30-trisnorhopane) is less stable than Ts
Biomarker stereochemistry for any asymmetric carbon in a (18a-22,29,30-trisnorneohopane). However, Ts/(Ts+Tm)
ring system is given using Greek alpha (down) and beta can have nonzero values prior to thermal maturation, and it
(up) symbols. The labels R (right-handed) or S (left-handed) varies depending on the source rock. Therefore, Ts/(Ts+Tm)
are used to describe asymmetric carbon atoms in side chains. is most reliable as a maturity parameter when evaluating oil
Specific details on how to describe stereochemistry are in Peters samples from a common source rock. Ts/(Ts+Tm) could be
et al. (2005). Two key stereoisomer ratios of the form B/(A+B) useful to rank the maturity of sample I compared to the other
for the C29 steranes involve positions C-14, C-17, and C-20: bb/ Monterey oil samples discussed above.
(bb+aa) and 20S/(20S+20R) (Fig. 6). All peaks needed to
calculate these ratios can be obtained from the GCMSMS C29
sterane mass chromatogram (Figs. 2 and 6 inset). These and Biomarkers to Assess Biodegradation
other biomarker maturity ratios are discussed in Moldowan et al.
(1994b) and Peters et al. (2005). Because of their complex structures, biomarkers resist bio-
Samples G and H in Fig. 6 provide an example of the degradation compared to normal alkanes and light hydrocar-
method to bracket thermal maturity using biomarker ratios. bons. This makes biomarkers particularly useful for
Sample G has achieved the endpoint for the 20S/(20S+20R) correlation of oil samples that have experienced secondary
ratio (~52–55% in Fig. 7). Once the endpoint is reached, alteration due to biodegradation. However, different bio-
stereoisomer ratios do not respond to higher maturity. How- marker classes show differing resistance to biodegradation,
ever, sample G has not achieved the endpoint for the slower which facilitates their use to assess the relative extent of
reaction indicated by the bb/(bb+aa) ratio (~67–71%). biodegradation (Fig. 8). Biodegradation rank should always
Therefore, sample G has achieved maturity near the peak of be determined prior to correlation studies because heavy
the oil window or about 0.8–0.9% vitrinite reflectance equiv- biodegradation can alter source-related biomarker ratios. For
alent (Fig. 7). Sample I has achieved endpoint for both example, if steranes in a sample are biodegraded, then they
20S/(20S+20R) and bb/(bb+aa). Therefore, sample I has should not be used to attempt a correlation with other
undefined maturity greater than the peak of the oil window. samples.
Another, slower biomarker reaction would be needed to Mixtures of biodegraded oil with a second charge of non-
assess the maturity more accurately. biodegraded oil can be recognized using various biomarkers.
Some of the ratios in Fig. 7 are not based on stereo- For example, the complete homologous series of
isomerization, and they are generally less useful for thermal 25-norhopanes is diagnostic of heavy biodegradation (Peters

Biomarkers in Sediments and Petroleum, Fig. 6 Two C29 stereo- bb/(bb+aa): 14a,17a(H)20S/[14a,17a(H)20S + 14a,17a(H)20R] and
isomer ratios can be used to assess the relative thermal maturity of oil [14b,17b(H)20R + 14b,17b(H)20S]/[ 14b,17b(H)20R + 14b,17b(H)
samples generated from the Miocene Monterey Formation in the off- 20S + 14a,17a(H)20S + 14a,17a(H)20R] (Reprinted with permission
shore Santa Maria Basin, California (Peters et al. 2005). Endpoints for by ChevronTexaco Exploration and Production Technology Company, a
each reaction are indicated by shaded area. Inset identifies the four division of Chevron USA)
GCMSMS stereoisomer peaks used in the ratios 20S/(20S+20R) and
8 Biomarkers in Sediments and Petroleum

Biomarkers in Sediments and

Petroleum, Fig. 7 Biomarker
maturity parameters respond to
thermal maturation at different
rates and can be used to bracket
the maturity of crude oil or source
rock extracts relative to the oil
window. Approximate ranges of
each maturity parameter are
shown versus vitrinite reflectance
and a generalized oil generation
curve (modified from Peters and
Moldowan 1993). Variations of
0.1% reflectance or more for
biomarker ratios can occur
(Reprinted with permission by
ChevronTexaco Exploration and
Production Technology Company,
a division of Chevron USA)

Biomarkers in Sediments and Petroleum, Fig. 8 The extent of simultaneously, but the rates of degradation decrease with increasing
crude oil biodegradation can be ranked using a nonlinear 1–10 scale rank for each compound class. A more detailed biodegradation ranking is
based on differing resistance of compound classes to microbial attack in Peters et al. (2005) (Reprinted with permission by ChevronTexaco
(Peters and Moldowan 1993). Steranes are far more resistant to biodeg- Exploration and Production Technology Company, a division of Chev-
radation than normal alkanes and isoprenoids. Biodegradation is quasi- ron USA)
sequential because all compounds in petroleum are attacked by microbes

et al. 1996). The occurrence of 25-norhopanes with intact commonly include drill stem test (DST) formation pressures,
normal alkanes and acyclic isoprenoids in crude oil, seep, or Horner-corrected bottom-hole temperatures (BHT), and/or
piston core samples is a strong evidence for mixing of non- vitrinite reflectance (e.g., Hantschel and Kauerauf 2009;
biodegraded and heavily biodegraded oil. Peters and Nelson 2012). Many BPSM simulators also offer
the option to use measured biomarker ratios for calibration,
assuming published first-order kinetic parameters for the
Biomarkers to Calibrate Basin and Petroleum reactions (A ! B as described above). Mackenzie and
System Models McKenzie (1983) were the first to suggest the use of bio-
marker ratios to calibrate BPSM, in particular sterane and
Computerized basin and petroleum system models (BPSM) hopane isomerizations. However, laboratory and field studies
require calibration using field measurements, which conducted after the work of Mackenzie and McKenzie show
Biomarkers in Sediments and Petroleum 9

that sterane and hopane isomerization are not simply redox, and age, even when samples of suitable source rock are
described by single-step equilibrium reactions at asymmetric unavailable.
carbon atoms (Walters et al. 2012 and references therein).
BPSM calibrations based on biomarker ratios are not
recommended because the kinetic parameters are based on Cross-References
simplistic reaction pathways, lack of sufficient precision, or
insufficient documentation to evaluate their usefulness. ▶ Biomarkers: Assessment of Petroleum Source Rock Age
and Depositional Environment
▶ Biomarkers: Assessment of Thermal Maturity
Summary ▶ Gas-Chromatography and Gas-Chromatography Mass
Spectrometry (GC and GC-MS)
Biomarkers are indispensible tools for petroleum exploration
and production and environmental forensics. Advanced ana-
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W.H. Freeman and Company, New York (2008) De-convoluting mixed crude oil in Prudhoe Bay field, North
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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-
tions of source- and age-related geochemical data for many
K.E. Peters1,2, C.C. Walters3 and J.M. Moldowan4 samples can be facilitated using chemometrics (multivariate
1
Schlumberger, Mill Valley, CA, USA statistics).
2
Department of Geological Sciences, Stanford University,
Stanford, CA, USA
3
ExxonMobil Corporate Strategic Research, Annandale, NJ, Introduction
USA
4
Biomarker Technologies, Inc., Rohnert Park, CA, USA 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
Definition preserved in marine or lacustrine sediment. If the organic-
rich sediment undergoes burial diagenesis and catagenesis, it
Biological markers (biomarkers) are molecular fossils from may become a petroleum source rock that expels oil rich in
once-living organisms found in crude oils and solvent extracts biomarkers inherited from biochemical precursors in the con-
of petroleum source rocks. Source-related biomarkers are tributing organisms. Diagenesis consists of chemical, physi-
hydrocarbons that are diagnostic for specific taxa of organ- cal, and biological changes during sedimentation and
isms and/or specific depositional settings. Taxon specificity lithification, but prior to significant alteration of organic mat-
may be as narrow as individual species or as broad as a ter by burial heating. Catagenesis consists of thermal alter-
kingdom. Depositional conditions can be inferred from the ation of organic matter in the range of ~50–150  C.
type of biotic input or environmental conditions that influence Table 1 shows selected, commonly used source- and age-
the preservation and/or diagenetic alteration of specific bio- related biomarker ratios that can be measured in crude oil to
markers. Age-specific biomarkers are taxon-specific and describe the source rock, even when the oil may have
indicative of the age of evolutionary emergence of that migrated to a reservoir far from the source rock. Interpreta-
taxon based on the geologic fossil record. tions for all of the parameters in the table are subject to
Source- and age-related biomarkers can be used for direct revision pending further research. In addition to information
correlation of crude oil samples to other oils or to solvent on the source rock, some biomarkers also include information
extracts from thermally mature source rock. When samples of on the geologic age of the organisms that contributed to the
prospective source rock are unavailable, source- and age- original sediment. These compounds are thus both source-
related biomarkers in oil can be used for indirect correlation and age-related biomarkers. Table 2 and Fig. 1 show more
to the source rock because they provide useful genetic infor- detail for several common age-related biomarkers and their
mation, including the type of organic matter input, redox inferred distributions through geologic time. Peters et al.
conditions in the depositional environment, and constraints (2005) provide an extensive survey of source- and age-related
on geologic age. Geochemical correlations of oils and source biomarker parameters.
rocks (oil-oil and oil-source rock correlation) are based Chemometrics is a powerful tool for genetic oil-oil and oil-
mainly on biomarker and isotopic measurements, which source rock correlation. In chemometrics, measured proper-
yield valuable insight that can be used to establish petroleum ties (e.g., biomarker and isotope ratios) are mathematically

# Springer International Publishing AG 2017

R. Sorkhabi (ed.), Encyclopedia of Petroleum Geoscience,
DOI 10.1007/978-3-319-02330-4_9-1
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 References
Marine C42–46 alkyl cylopentanes, odd/even predominance Carlson et al. (1993), Hsieh and Philp (2001)
C30 24-n-propylcholestanes, 24-n-propyldiacholestanes; Moldowan et al. (1985, 1990), Peters et al. (1986, 1999a)
chrysophyte algae
Mid-chain monomethylalkanes and dimethylalkanes; Shiea et al. (1990), Thiel et al. (1999a)
stromatoporids, demosponges, also hot springs
C19–C30 tricyclic terpanes; Tasmanites Aquino Neto et al. (1983), Volkman et al. (1989), De Grande
et al. (1993)
Lacustrine Botryococcane, cyclobotryococcanes, polymethylsqualanes; Moldowan and Seifert (1980), Brassell et al. (1985), McKirdy
chlorophyte algae, Botryococcus braunii, brackish/fresh water et al. (1986), Metzger and Largeau (1999), Summons et al.
(2002)
C15–C34 macrocyclic alkanes, C17–C26 methylated derivatives; Audino et al. (2002)
Botryococcus braunii; brackish/fresh water
Low steranes/hopanes; relative input of eukaryotes Moldowan et al. (1985)
vs. prokaryotes
C26/C25 tricyclic terpanes >1 Zumberge et al. (2000), Peters et al. (2005)
High tetracyclic polyprenoids; brackish/fresh Holba et al. (2000, 2003)
Low C3122R homohopane/C30 hopane (C31R/hopane) Zumberge et al. (2000), Peters et al. (2005)
C42–46 cyclopentylalkanes, even/odd predominance = saline Carlson et al. (1993), Hsieh and Philp (2001)
lacustrine, even ~ odd = freshwater
Fluvio- Pristane/phytane >3; also coal Hughes et al. (1995)
deltaic
Algal input Elevated nC15, nC17, nC19 alkanes; lacustrine or marine Gelpi et al. (1970), Tissot and Welte (1984), Reed et al. (1986)
High steranes/hopanes; relative input of eukaryotes Moldowan et al. (1985)
vs. prokaryotes
Higher- Elevated nC27, nC29, nC31 alkanes; post-Silurian Eglinton and Hamilton (1967), Tissot and Welte (1984)
plant input Oleananes, lupanes, taraxeranes; angiosperms (flowering plants) Zumberge (1987), Ekweozor and Udo (1988), Riva et al.
(1988), Moldowan et al. (1994)
Bicadinanes; angiosperms, Dipterocarpaceae dammar resin Cox et al. (1986), van Aarssen et al. (1990, 1992)
Lupane, norlupanes, bisnorlupanes; angiosperms Rullkötter et al. (1982), Curiale (2006)
Retene, cadalene, tetracyclic diterpanes; gymnosperms Noble et al. (1985a)
Beyerane, kaurane, phyllocladane, isopimarane (diterpanes); Noble et al. (1985b), Murray et al. (1998), Zinniker (2005)
gymnosperms
C29/(C27–C29) steranes (some exceptions, e.g., Precambrian) Huang and Meinshein (1979), Moldowan et al. (1985),
Czochanska et al. (1988)
Hypersaline Pristane/phytane <0.5 ten Haven et al. (1987)
b-Carotane; carotenoid pigments in halophilic bacteria or algae, Hall and Douglas (1983), Jiang and Fowler (1986), Koopmans
e.g., green alga Dunaliella salina in sea salt fields or evaporative et al. (1997); Peters et al. (1999a)
lakes
High gammacerane; stratified anoxic water, halophilic bacteria, Moldowan et al. (1985), Brassell et al. (1988), Sinninghe
bacterivorous eukaryotes by gene transfer Damsté et al. (1995), Grice et al. (1998a), Takishita et al.
(2012)
2-Methyldocosane; bacteria? Connan et al. (1986)
2,6,10,15,19-pentamethyleicosane (PMIa); methanotrophic and Elvert et al. (1999), Schouten et al. (1997), Thiel et al. (1999b),
methanogenic Archaea, anoxic, hypersaline (not yet confirmed Greenwood and Summons (2003), Maslen et al. (2009)
in crude oil)
Trimethyl chromans; hypersaline photic zone 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 rocks (Moldowan 2000). For example, dinosteroids occur in
complex data sets. Various techniques are available, but the pre-Triassic rocks, although they are presumed to originate
most common are hierarchical cluster analysis and principal from dinoflagellates whose cysts are found only in Triassic or
component analysis. For example, Peters et al. (2007) ana- younger rocks (Moldowan et al. 1996; Barbanti et al. 2011).
lyzed source- and age-related biomarker and isotopic data for 24-Norcholestanes occur in some lower Phanerozoic rocks,
more than 1000 oil samples collected from the circum-Arctic whereas fossil evidence for their presumed precursor organ-
(>55oN). A multitiered chemometric decision tree allowed isms (diatoms) first appears in Jurassic rocks (Holba et al.
automated classification of 31 genetically distinct oil families 1998). Small amounts of oleanane can be found in some
based on a 622-sample training set. Decision-tree Paleozoic rocks (Taylor et al. 2006), although the precursor
chemometrics uses principal component analysis and tiers of compounds occur only in angiosperms and first appear in
K-nearest neighbor and SIMCA (soft independent modeling small amounts in Lower Cretaceous rocks. Biomarkers in
of class analogy) models to classify and assign confidence rocks that predate the first macrofossil evidence for their
limits for newly acquired samples of oil or source-rock precursor organisms might be explained as (1) contamination
extracts. 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
Taxon-Specific Biomarkers in other organisms prior to evolution of the recognized fossil
morphology of the precursor organism.
Taxon-specific biomarkers are a class of source-related bio- The evolution of life is characterized by new biochemical
markers that can be directly related to precursor organisms. synthetic pathways and many compounds that might become
Taxon-specific biomarkers commonly occur in rocks depos- age-diagnostic biomarkers. However, only a few biomarkers
ited during or after the biotic radiation of the precursor organ- are known to be reliable age indicators (Table 2) because they
isms, but they may also occur in low concentrations in older must (1) originate from a biochemical uniquely synthesized
Biomarkers: Assessment of Petroleum Source-Rock Age and Depositional Environment 5

Biomarkers: Assessment of Petroleum Source-Rock Age and Absence of such compounds cannot strictly be used to interpret age, but
Depositional Environment, Fig. 1 Several common age-related bio- may still be useful to support an age assessment when combined with
markers and their approximate temporal range in millions of years before other data. See Peters et al. (2005) for further details on each parame-
present (Ma). When present in samples, age-related biomarkers can be ter.? = uncertain occurrence (Figure modified from Walters et al. (2017))
used to infer the age and identify of the source rocks for crude oils.

by organisms having a known geologic age range, (2) be and tends to exceed this value thereafter. However, similar
preserved over geologic time, and (3) contribute sufficient high values characterize older strata in the Neoproterozoic,
biomass to the source rock to be detectable in related crude suggesting that either non-cyst-forming dinoflagellates
oil. Most common biomarkers originated from membrane evolved much earlier than their cyst-forming counterparts or
lipids produced by biosynthetic pathways that evolved in that these compounds were produced by extinct acritarchs,
the Proterozoic. Their occurrence in Precambrian strata may organic-walled microfossils of unknown affinity. It is unclear
help resolve when certain organisms first evolved, such as whether the acritarchs represent an early form of dinoflagel-
Eukarya or cyanobacteria, but these compounds are ubiqui- lates or whether the biosynthetic pathways for dinosterols
tous in younger rocks and crude oils. Grantham and Wake- evolved independently in these two lineages.
field (1988) observed that the C28/C29 sterane ratio in crude Source rocks and related crude oils dominated by input
oils generally increases through Phanerozoic time, which they from Gloeocapsomorpha prisca are characterized by a strong
ascribed to increasing biodiversity of phytoplankton. Some odd carbon-number preference of n-alkanes from C11 to C19
biomarkers have complex temporal relationships. and unusually low amounts of higher hydrocarbons. This
Dinosteranes and triaromatic dinosteroids are derived from organism probably evolved in the Late Cambrian and
dinosterols that today are nearly exclusively produced by flourished in the Ordovician where it contributed nearly all
dinoflagellates. Many dinoflagellates produce a resting stage of the organic matter in some organic-rich shales (Fowler
or cyst that can be fossilized. These organisms became impor- 1992). Although G. prisca dominance is mostly restricted to
tant contributors to the Mesozoic fossil record based on the the Ordovician, it is rarely reported in the Silurian, and the
abundance of dinosterol-derived biomarkers (Moldowan organism became extinct in the Late Devonian (Fowler
et al. 1996, 2001). For example, the dinosterane/[dinosterane et al. 2004).
+ (20R)-3b-methylstigmastane] ratio in extracts of source Several age-related biomarkers signal the evolution of land
rocks is less than 0.35 from the Silurian through the Permian 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 gouge from the nearby Helmsdale fault that was eroded and
trace the emergence of gymnosperms (e.g., conifers), charac- transported along a stream bed to the beach. Based on bio-
terized by certain tricyclic diterpanes (Zinniker 2005; Auras marker source and biodegradation parameters, the oil cement
et al. 2006), or angiosperms (flowering plants), characterized is a mixture of marine and lacustrine input (Peters et al.
by certain pentacyclic triterpenoids. For example, abundant 1999a). For example, like oil from the nearby offshore
oleanane marks the radiation of angiosperms in the Late Beatrice field, the oil cement contains 24-n-propylcholestanes
Cretaceous and Early Tertiary, and the oleanane index is one and ß-carotane, which suggest marine and arid, possibly
of the most widely used age-related parameters (Moldowan lacustrine source rocks, respectively (Table 1). The oil cement
et al. 1994). However, small amounts of oleanane occur in also contains pristane, phytane, residual n-alkanes (mild bio-
older rocks. The angiosperm fossil record extends into the degradation), and a complete series of 25-norhopanes (heavy
Early Mesozoic, and limited oleanane in Paleozoic strata biodegradation), which also indicate a mixture. The first
supports an even earlier evolution as indicated by DNA charge to the Helmsdale fault consisted of oil from a nearby
phylogenetic analyses of living plants (Peterson et al. 2007). Devonian source rock that was heavily biodegraded after it
Similarly, bicadinanes occur throughout Mesozoic strata and migrated to shallow depth. The origin of the second charge is
also indicate angiosperms, but Dipterocarpaceae synthesize unclear. Unlike Beatrice oil, the oil cement contains oleanane
resins that yield bicadinanes and their abundance in oil or and shows a higher 24-nordiacholestane ratio, suggesting
source-rock extracts suggest Oligocene or younger age. input from a Cretaceous or younger, paralic marine shale
The record for C26 24-norcholestanes and source rock (Table 2, Fig. 1). Although Cretaceous and Paleo-
24-nordiacholestanes extends to the Neoproterozoic (Zhang cene source rocks are inferred to exist in various depocenters
et al. 2002), although concentrations in source rocks remain in the northeast Atlantic margin, subcrops of these rocks
low until the Jurassic and can be high in the Tertiary (Holba offshore Brora are thermally immature. Alternatively, the
et al. 1998). This temporal relationship arises from multiple second charge could have originated from an effective Middle
taxonomic origins for precursor sterols. Dinoflagellates and Jurassic source rock that contained oleanane. Mass spectrom-
related species contributed these compounds since the Mid- etry of extract from the nearby Middle Jurassic Brora coal
Precambrian, but the evolution and rise of diatoms in the confirms small amounts of oleanane. This is one of only a few
Mesozoic provided a second source (Rampen et al. 2007). pre-Cretaceous source-rock extracts that contain low levels of
Hence, abundance of 24-norcholestanes and oleanane.
24-nordiacholestanes indicates post-Triassic sediments, par-
ticularly those of Tertiary age deposited at high latitude. Carbonate Versus Shale
Similarly, C25 highly branched isoprenoids characterize Peters et al. (2008) used biomarker and stable carbon isotope
rhizosolenid diatoms that emerged in the upper Turonian ratios to determine the age, organic matter input, lithology,
(Sinninghe Damsté et al. 2004). and depositional environment of source rocks for 388 samples
The fossil record for Botryococcus extends into the Pre- of crude oil, seep oil, and stranded tarballs in coastal Califor-
cambrian, but biosynthetic pathways for production of nia. Chemometric analysis of the data identified three families
C30–C37 botryococcenes only developed recently by modifi- of 13C-rich oil that originated from thermally mature equiva-
cation of the squalene synthase gene. Hence, the presence of lents of three members of the Miocene Monterey Formation
botryococcane and a monoaromatic hydrocarbon produced like that exposed at Naples Beach near Santa Barbara. Oil
from lycopadiene-related lipids are specific for modern races families 1, 2, and 3 correspond to the clayey-siliceous, carbo-
of Botryococcus braunii and provide the youngest age-related naceous marl, and lower calcareous-siliceous members that
biomarkers known (Volkman 2014). 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-
Examples of the Application of Source- and Age- tions. For example, Ts/Tm and Ol/H, which are sensitive to
Related Biomarkers clay content and angiosperm (flowering plant) input respec-
tively, show high, intermediate, and low values for families 1,
The following discussion gives examples of how diverse 2, and 3, respectively, consistent with the progression from
biomarkers in crude oil can be used to describe the source- nearshore to deep water organofacies of the same source rock.
rock age and depositional environment. Stable carbon isotope ratios for saturate and aromatic hydro-
carbons from the oil samples and the calculated canonical
Marine Versus Lacustrine variable (Sofer 1984) are consistent with 13C-rich Monterey
An unusual rounded cobble containing brecciated angular Formation source rock dominated by marine organic matter.
sandstone clasts cemented by heavy oil was collected from a
beach near Brora, Scotland. The cobble originated as fault
Biomarkers: Assessment of Petroleum Source-Rock Age and Depositional Environment 7

Photic Zone Anoxia isotope ratios of saturate and aromatic hydrocarbons

Enhanced bioproductivity and restricted water circulation in (d13Csaturates, d13Caromatics), distributions of C27–C29 steranes
marine or lacustrine settings commonly result in anoxia and diasteranes, oleanane/(oleanane + hopane), and several
(<0.5 ml oxygen/L water) or euxinia (anoxic with abundant tricyclic and tetracyclic terpane ratios, which effectively dif-
hydrogen sulfide from microbial sulfate reduction), which ferentiate the two principal oil groups. Oils inferred to origi-
contributes to preservation of organic matter due to elimina- nate from Tertiary and Triassic–Jurassic source rocks in the
tion of benthic metazoan life (Demaison and Moore 1980). study area occur north and south of 2 S latitude, respectively.
Purple and green sulfur bacteria (Chromatiaceae and This approximately corresponds with the famous Wallace
Chlorobiaceae, respectively) may thrive when water column Line, which separates Oriental and Australian faunal regions.
euxinia occurs within the photic zone. Photosynthetic pig- The data indicate that 20 low-sulfur oils mainly from Sula-
ments in these organisms include aromatic carotenoids, such wesi and Irian Jaya originated from Tertiary marine marlstone
as isorenieratene, renieratene, renierapurpurine, okenone, and source rock deposited under suboxic conditions, probably the
chlorobactene (Schaeffer et al. 1997; Sinninghe Damsté et al. upper Miocene Klasafet Formation. These oils show 13C-rich
2001; Brocks and Schaeffer 2008). Diagenesis of these pre- carbon isotope ratios and high oleanane, 24-nordiacholestane,
cursors in hydrogen sulfide-rich sediments facilitates their and pristane/phytane ratios (Tables 1 and 2), which together
incorporation into the kerogen via sulfur-carbon bonds. are diagnostic of Tertiary oils and source rocks. Five high-
These bonds are readily broken during catagenesis of the sulfur oils from Seram were interpreted to originate from
source rock, yielding various products, including saturated Triassic–Jurassic marine carbonate source rock deposited
biomarkers that can be used to interpret marine photic zone under anoxic conditions. These oils lack oleanane and show
anoxia (Table 1). For example, crude oil generated from low 24-nordiacholestane and pristane/phytane ratios. Low-
Aptian source rocks in the Sergipe-Alagoas Basin, Brazil sulfur Aliambata seep oil from Timor originated from a
(Sousa Júnior et al. 2013), shows low pristane/phytane more oxic, terrigenous-influenced marine clastic equivalent
(reducing), abundant gammacerane, and ß-carotane (saline of this carbonate source rock.
to hypersaline), as well as various carotenoid derivatives,
including isorenieratane and aryl and diaryl isoprenoids Infracambrian Versus Phanerozoic
(photic zone anoxia). Based on biomarker and isotope data, nonbiodegraded, heavy
oil from the Baghewala-1 well in northwestern India origi-
Tertiary Versus Mesozoic nated from anoxic marine carbonate-rich source rock that
Source-related biomarkers, such as distributions of C27–C29 contained algal and bacterial organic matter with no higher-
steranes and diasteranes, C31–C35 homohopanes, and the plant input (Peters et al. 1995). Age-related biomarkers in the
occurrence of C30 n-propylcholestanes, identify two marine oil indicate that the source rock was Infracambrian in age.
petroleum systems in the Czech Republic, one from Jurassic Geochemical characteristics of the Baghewala-1 oil are sim-
and the other from Paleogene source rocks (Picha and Peters ilar to those of Huqf-sourced oils from southern Oman,
1998). Two oils from the sub-Carpathian foreland plate including strong predominance of C29 steranes, pristane/phy-
(Lubna-18 and Dolni Lomna-1) have similar geochemical tane ratios generally <1.0, low diasteranes, and very negative
compositions, including elevated oleanane and stable carbon isotope ratios in the range 32 to 36‰. The
24-nordiacholestane age-related biomarker ratios (Table 2, oil lacks oleanane, dinosteranes, and aromatic dinosteroids,
Fig. 1), consistent with an origin from Paleogene source indicating Triassic or older source rock (Table 1, Fig. 1). It
rock. These rocks were inferred to be either the Menilitic shows high C29/(C27–C28) regular sterane and monoaromatic
shales of the Carpathian thrust belt or autochthonous Paleo- steroid ratios, typical of many Devonian or older oils and
gene deposits buried below the thrust belt. Two other oils source rocks (Moldowan et al. 1985). High C29 steranes in
from the sub-thrust plate (Zdanice-7 and Damborice-16) cor- Tertiary crude oils commonly indicate a land-plant source
relate geochemically with extracts of thermally mature Juras- (e.g., Huang and Meinschein 1979; Czochanska et al. 1988),
sic source rocks in the study area. Like the rock extracts, these but the Baghewala-1 oil shows no evidence of land-plant
two oils lack oleanane and show low 24-nordiacholestane input. The oil originated from Infracambrian source rock
ratios, supporting an origin from Jurassic marl source rock. because it contains abundant 24-isopropylcholestanes and
One oil sample from the Vienna Basin (Tynec-34) appears to shows an elevated 24-isopropyl/n-propylcholestane ratio
be a mixture with contributions from both source rocks. (Table 1), typical of oils from Vendian (upper Precambrian)
Biomarker geochemistry reveals genetic relationships to lower Cambrian carbonate source rock (e.g., McCaffrey
among crude oil samples from eastern Indonesia and their et al. 1994). Many oils and rock extracts of Vendian to Early
source-rock ages and depositional environments (Peters et al. Cambrian age from Siberia, the Urals, Oman, Australia, and
1999b). Chemometric analysis was based on 13 source- the Baghewala-1 oil have high 24-isopropyl/
related geochemical parameters, including stable carbon 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) Barbanti SM, Moldowan JM, Watt DS, Kolaczkowska E (2011) New
suggest that abundant 24-isopropylcholestanes in these sam- triaromatic steroids distinguish Paleozoic from Mesozoic oil. Org
Geochem 42:409–424
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B

Biomarkers: Assessment of Source Rock thermal maturity parameters are measured using irreversible
Thermal Maturity reactions, uplifted petroleum source rocks may show higher
maturity than expected based on their present-day burial
Kenneth E. Peters1,2 and J. Michael Moldowan3 depth.
1
Schlumberger, Mill Valley, CA, USA Vitrinite reflectance is a common maturity parameter, but
2
Department of Geological Sciences, Stanford University, because Ro is based on organic petrography, it cannot be
Stanford, CA, USA determined on oil samples. Furthermore, vitrinite phytoclasts
3
Biomarker Technologies, Inc., Rohnert Park, CA, USA are rare or absent in some rock samples, they cannot be
identified by age and thus can represent contamination due
to caving of material from shallower zones in each well, and
Definition Ro measurements based on organic-rich source rock samples
can be unreliable due to suppressed reflectance (Peters and
Thermal maturity consists of temperature/time-driven dispro- Cassa 1994; Barker et al. 2007). Because vitrinite originates
portionation reactions that convert sedimentary organic mat- from higher plants, the kinetics that control increasing Ro with
ter into light and heavy fractions of petroleum and finally into maturity may differ substantially from those that control
hydrocarbon gas and pyrobitumen or graphite. Different geo- petroleum generation from oil-prone macerals in source
chemical scales commonly used to describe the extent of rock. Macerals are recognizable particulate organic compo-
thermal maturation include vitrinite reflectance (Ro), pro- nents of kerogen that can be classified within the liptinite
grammed pyrolysis (e.g., Rock-Eval) Tmax and production (hydrogen-rich, oil-prone), vitrinite (gas-prone from land-
index, and biomarker maturity ratios (e.g., Peters et al. 2005). plant tissues), or inertinite (hydrogen-poor) groups (Peters
and Cassa 1994).
Certain biomarker stereoisomer ratios are among the most
Introduction common measures of thermal maturity because, unlike Ro and
other parameters, biomarkers are nearly ubiquitous in crude
Geochemists divide thermal maturation into three stages: oil and sedimentary rock. Stereoisomers have the same
diagenesis, catagenesis, and metagenesis. Diagenesis consists molecular formula and the same bonds between atoms but
of chemical, physical, and biological changes in the organic different spatial arrangements of the atoms around each asym-
matter during and after sediment deposition and lithification metric carbon atom. Asymmetric carbon atoms are
at temperatures below ~50
C (Ro < 0.6%). Diagenesis surrounded by four different substituents, thus allowing mir-
occurs prior to thermogenic oil and hydrocarbon gas genera- ror image molecules having the same molecular formula, such
tion but can include formation of microbial methane. as L or D amino acids (Fig. 1). Stereoisomers include enan-
Catagenesis includes thermal alteration of organic matter tiomers (mirror image structures having one or more asym-
during burial at ~50–150
C (Ro ~ 0.6–2.0%), which may metric carbon atoms) and diastereomers (epimers), which
require millions of years. The depth interval corresponding to differ at certain asymmetric centers but may be identical at
catagenesis is called the oil window or principal zone of oil others.
formation. Metagenesis cracks organic molecules to gas and
pyrobitumen at ~150–200
C (Ro ~ 2.0–4.0%), prior to
greenschist metamorphism (>200
C). Because common

# Springer International Publishing AG 2017

R. Sorkhabi (ed.), Encyclopedia of Petroleum Geoscience,
DOI 10.1007/978-3-319-02330-4_10-1
2 Biomarkers: Assessment of Source Rock Thermal Maturity

Biomarkers: Assessment of Source Rock Thermal Maturity, inversion of all asymmetric centers leads to the enantiomer (mirror
Fig. 1 Inversion of one asymmetric carbon atom (epimerization) in an image). Inversion of one or more, but not all asymmetric centers, yields
amino acid results in a type of stereoisomer called an enantiomer, which a diastereomer. Biomarkers in petroleum and source rock extracts have
is a molecule having a non-superimposable mirror image (indicated by many asymmetric centers, and therefore many diastereomers and enan-
dashed line). Nearly all living organisms have amino acids in the tiomers are possible for each
L configuration. In molecules having more than one asymmetric center,

Method Parameters

Gas chromatography-mass spectrometry (GC-MS) can be Various saturated and aromatic biomarker ratios can be used
used to generate mass chromatograms, which measure to assess thermal maturity of crude oils or source rock extracts
steranes and other biomarkers by focusing on the principal (Peters et al. 2005). Most ratios are expressed as the product
mass fragment ion that is diagnostic for that class of bio- (B) divided by the reactant (A) plus the product, i.e.,
markers (e.g., Fig. 2; m/z 217 for steranes). Three asymmetric B/(B + A). These ratios are based on two reaction types:
centers in sterols (C-14, C-17, and C-20) are always in the (1) stereoisomerization at asymmetric carbon atoms in satu-
“biological” configuration: 14a,17a(H),20R, i.e., aa20R. rated biomarkers and (2) cracking and/or aromatization,
During thermal maturation, the biological configuration can including so-called side-chain scission reactions in aromatic
undergo stereoisomerization to more stable “geological” con- biomarkers. It is more likely that relative stability of the short
figurations by formation of a carbocation and migration of a versus long side-chain compounds is the basis for these
hydrogen ion. The biological and three key geological stereo- cracking parameters. Relative stability is the basis for several
isomers are readily quantified by gas chromatography-mass other saturated biomarker maturity parameters, such as C23
spectrometry (m/z 217; Fig. 2, far right). Two common tricyclic terpane/C30-hopane; diasteranes/steranes; Ts/Tm
sterane maturity ratios are (1) 100  aa20S/(aa20S + aa20R), [18a-trisnorneohopane/17a-trisnorhopane, usually presented
also called %20S, and (2) 100  (bb20S + bb20R)/ as Ts/(Ts + Tm)]; and 18a,30-norneohopane/17-
(bb20S + bb20R + aa20S + aa20R), also called %bb. a-30-norhopane [abbreviated as C29Ts/C29Hop or C29Ts/
X = H, CH3, C2H5, and other groups. These ratios are nor- (C29Ts + C29Hop)]. The latter two and many other maturity
mally measured for the C29 sterane homolog, which is called parameters are not stereoisomerizations but are based on the
stigmastane (X = C2H5). relative kinetic and/or thermodynamic stability of the compo-
However, sterane homologs at C27, C28, C29, and C30 in oil nents toward C-C bond cracking. Thus, Ts/(Ts + Tm) pro-
or extract samples can interfere with each other on mass gresses from low values in immature samples to one
chromatograms, resulting in inaccurate assessment of stereo- (or 100%) at late oil-window maturity due to greater relative
isomer ratios. Gas chromatography-mass spectrometry-mass stability of Ts compared to Tm. Such parameters, termed
spectrometry (GC-MS-MS) eliminates interference among irreversible, become important for maturity estimation from
homologs by means of parent-daughter ion monitoring. For before the peak to the end of the oil window, a maturity range
example, C29 steranes can be monitored using triple- in which sterane and hopane stereoisomer ratios have maxi-
quadrupole mass spectrometry (Fig. 3) by allowing only mized at some value between zero and one.
ions having a parent mass (M+) of m/z 400 to enter the second Stereoisomerization ratios are preferred because the reac-
or collision quadrupole for further fragmentation. The third tant in thermally immature sediments is 100% in the biolog-
quadrupole focuses only on the appropriate daughter mass for ical configuration, whereas the product geological
steranes (m/z 217), thus resulting in a mass chromatogram configurations are absent. In reality, even stereoisomer ratios
that is unique for C29 steranes (Fig. 4, Table 1). cannot be described strictly by simple conversion of A to
B. For this reason, kinetics derived for these presumed reac-
tions cannot be reliably used to calibrate basin and petroleum
Biomarkers: Assessment of Source Rock Thermal Maturity 3

Biomarkers: Assessment of Source Rock Thermal Maturity, other positions, resulting in some proportion of thermally more stable
Fig. 2 Steranes in petroleum originate from sterols in once-living geological stereoisomers (mass chromatogram at right; Seifert and
organisms (top left). During early diagenesis, steranes retain the original Moldowan 1979). The extent of each reaction varies depending on the
biological stereochemistry at positions C-14, C-17, and C-20 (aa20R). specific atomic geometry at each asymmetric center but can also be
During catagenesis, steranes undergo stereoisomerization at these and influenced by temperature and catalysis by minerals

Biomarkers: Assessment of Source Rock Thermal Maturity, rods (not to scale). Three quadrupoles allow highly selective parent-
Fig. 3 Schematic view of a gas chromatograph equipped with a triple- daughter ion detection (e.g., only daughter ion B from parent compound
quadrupole mass spectrometer consisting of three sets of quadrupole A)
4 Biomarkers: Assessment of Source Rock Thermal Maturity

x104 m/z 217 44

2
C30 42 43
1 m/z 414 217 X 39 40 41

0
x104 33
5 C29 34 36 37
38
3 35
m/z 400 217
1

x104 23 24
Response

4
3 C28 25 26
27
30 31
m/z 386 217 28 32
2 29
1
0
x104 15
7
5
C27 16 19-21
m/z 372 217 17 18 22
3
1

x104 14 m/z 217

m/z 358 217
1.4
1.0
C26 2 3
5 6-8
9-13 5β-Cholane
(C24)
4
0.6
0.2

87 88 89 90 91 92 93 94 95 96 97 98 99 100 101 102 103 104 105 106 107 108 109 110

Time
Biomarkers: Assessment of Source Rock Thermal Maturity, inset identify the m/z 217 daughter ion. X = H, CH3, C2H5, and C3H8 for
Fig. 4 Gas chromatography-mass spectrometry-mass spectrometry the C27–C30 homologs (parent ion, M+ = m/z 372, 386, 400, and
(GC-MS-MS) of a crude oil mixture (Stanford-1) in parent-daughter 414, respectively). 5b-Cholane (lower right) is a C24 sterane not abun-
mode (M+ ! m/z 217) differentiates sterane epimers by carbon number, dant in crude oil that is used as an internal standard to quantify peaks.
thus reducing interference seen in GC-MS. Stanford-1 is a blend of Peaks 35–38 (Table 1) can be used to generate two C29 sterane stereo-
several oil samples and some pure synthetic compounds blended to isomer ratios used to assess the thermal maturity of crude oil and source
include most biomarkers in crude oils derived from source rocks depos- rock extracts (Fig. 5): %20S/(20S + 20R) and % bb/(bb + aa). Peaks
ited in various depositional environments. Dashed arrows in the upper 23–26 were recently identified in Peters et al. (2014)

system models (Walters et al. 2012). Four of the most com- scission parameters are similar to Ts/Tm in that they extend
monly used ratios are based on isomerization of hydrogen the application of biomarker maturity estimates from the
atoms around asymmetric carbon atoms at C-20 [%20S/ middle to well into the late oil window, where stereo-
(20S + 20R)] and C-14 and C-17 [%bb/(bb + aa)] in the isomerization ratios are ineffective.
steranes, C-22 in the hopanes [%22S/(22S + 22R)], and both
C-17 and C-21 in the hopanes [%bb /(bb + ba + ab)], as
indicated in Fig. 5. Other saturated biomarker maturity Data Interpretation
parameters supplement these isomerization ratios, such as
moretane/17a-hopane [17ß,21a/17a,21ß]. Biomarker ratios can be used to assess the relative thermal
Another biomarker cracking ratio is based on the conver- maturity of crude oils and source rock extracts, particularly
sion of monoaromatic (MA) to triaromatic (TA) steroids when the samples are genetically related based on oil-oil or
(Fig. 5). The TA/(MA + TA) ratio is less commonly applied oil-source rock correlation using source-related biomarker
for maturity assessment than isomerization ratios, because and stable carbon isotope ratios (Peters et al. 2005). Figure 6
(1) quantification of aromatic steroids can be difficult, and shows the relative thermal maturity of nine genetically related
(2) thermally immature samples may not start with 100% of crude oils based on two C29 sterane stereoisomer ratios from
the presumed reactant. Some additional aromatic maturity GC-MS-MS.
parameters are based on ratios of aromatic steroids with Assessment of thermal maturity relative to the oil window
short versus long side chains (commonly described as side- or vitrinite reflectance using biomarker ratios (Fig. 5) is not as
chain cleavage reactions). These aromatic steroid side-chain straightforward as relative maturity assessment (Fig. 6). All
Biomarkers: Assessment of Source Rock Thermal Maturity 5

Biomarkers: Assessment of Source Rock Thermal Maturity, internal standard (peak 1 not shown in Fig. 4), which is measured from
Table 1 Identification of biomarker peaks from Fig. 4, including the m/z 330 to 217 parent-daughter transition with calibration using the
peaks 35–38 that are used to generate two C29 sterane stereoisomer ratios Stanford-1 external standard (Peters et al. 2005)
in Figs. 5 and 6. Peaks are quantified using the C24 sterane 5b-cholane
Peak Identification Carbon number
1 5b-Cholane 24
2 13b,17a(H)-24-Nordiacholestane 20S 26
3 13b,17a(H)-24-Nordiacholestane 20R 26
4 13b,17a(H)-27-Nordiacholestane 20S 26
5 13b,17a(H)-27-Nordiacholestane 20R 26
6 5a,14a,17a(H)-24-Norcholestane 20S 26
7 5a,14b,17b(H)-24-Norcholestane 20R 26
8 5a,14b,17b(H)-24-Norcholestane 20S 26
9 5a,14a,17a(H)-24-Norcholestane 20R 26
10 5a,14a,17a(H) + abb(H)-21-Norcholestane 26
11 5a,14a,17a(H)-27-Norcholestane 20S 26
12 5a,14b,17b(H)-27-Norcholestane 20R 26
13 5a,14b,17b(H)-27-Norcholestane 20S 26
14 5a,14a,17a(H)-27-Norcholestane 20R 26
15 13b,17a(H)-Diacholestane 20S 27
16 13b,17a(H)-Diacholestane 20R 27
17 13a,17b(H)-Diacholestane 20S 27
18 13a,17b(H)-Diacholestane 20R 27
19 5a,14a,17a(H)-Cholestane 20S 27
20 5a,14b,17b(H)-Cholestane 20R 27
21 5a,14b,17b(H)-Cholestane 20S 27
22 5a,14a,17a(H)-Cholestane 20R 27
23 13b,17a(H)-Diaergostane 20S,24R 28
24 13b,17a(H)-Diaergostane 20S,24S 28
25 13b,17a(H)-Diaergostane 20R,24S 28
26 13b,17a(H)-Diaergostane 20R,24R 28
27 13a,17b(H)-Diaergostane 20S,24R + 20S,24S 28
28 13a,17b(H)-Diaergostane 20R,24S + 20R,24R 28
29 5a,14a,17a(H)-Ergostane 20S,24R + 20S,24S 28
30 5a,14a,17a(H)-Ergostane 20R,24R + 20R,24S 28
31 5a,14b,17b(H)-Ergostane 20S,24R + 20S,24S 28
32 5a,14a,17a(H)-Ergostane 20R,24R + 20R,24S 28
33 13b,17a(H)-Diastigmastane 20S,24R + 20S,24S 29
34 13b,17a(H)-Diastigmastane 20R,24R + 20R,24S 29
35 5a,14a,17a(H)-Stigmastane 20S,24R + 20S,24S 29
36 5a,14b,17b(H)-Stigmastane 20R,24R + 20R,24S 29
37 5a,14b,17b(H)-Stigmastane 20S,24R + 20S,24S 29
38 5a,14a,17a(H)-Stigmastane 20R,24R + 20R,24S 29
39 13b,17a(H)-24-Dia-n-propylcholestane 20S,24R + 20S,24S 30
40 13b,17a(H)-24-Dia-n-propylcholestane 20R,24R + 20R,24S 30
41 5a,14a,17a(H)-24-n-Propylcholestane 20S,24R + 20S,24S 30
42 5a,14b,17b(H)-24-n-Propylcholestane 20R,24R + 20R,24S 30
43 5a,14b,17b(H)-24-n-Propylcholestane 20S,24R + 20S,24S 30
44 5a,14a,17a(H)-24-n-Propylcholestane 20R,24R + 20R,24S 30

relationships between reaction extent and the stage of oil The most reliable approach to assess thermal maturity
generation or vitrinite reflectance (Ro) are approximate. from Fig. 5 is to start by using stereoisomer ratios based on
Readers are cautioned against inferring equivalent Ro from a fast reactions (e.g., C32 hopane %22S/(22S + 22R)). For
single biomarker ratio. Reflectance inferred from multiple example, if a sample achieved the endpoint for %22S/
biomarker ratios may show variations of 0.1% Ro. (22S + 22R) (~60%), this nominally represents maturity
6 Biomarkers: Assessment of Source Rock Thermal Maturity

100 Etio/(Etio +DPEP) Vanadyl

Porphyrins 100 Etio/(Etio +DPEP) Nickel
25 100 PMP
(30) (83) 100 TA[C20/(C20+C28, 20R)
10 60 100 TA( I )/TA(I + II)
Aromatic 10 60 100 MA( I )/MA (I + II)
Steroids 100 TA28/(TA28+MA29)

100 Dia/(Dia+Reg) Steranes

Steranes 25 70 ββ/(ββ+αα) C29 Steranes
55 20S/(20S+20R) C29 Steranes

10
18β/(β+α) Oleanane
100 Tric/(Tric+17αHopanes)
100 Ts/(Ts + Tm)
Terpanes 5 βα/(βα+αβ) C30 Hopanes
60 22S/(22S + 22R) C32 Hopanes
0 ββ/(ββ+αβ+βα) Hopanes

Ro% 0.4 0.5 0.6 0.7 0.9 1.3 2.0

Condensate
Immature

Late

Wet Gas
Early

Peak

Amount
Stages of Oil Generation
Biomarkers: Assessment of Source Rock Thermal Maturity, parameters, except 18ß/(18a + 18ß)-oleanane, ßa/(aß + ßa)-hopanes
Fig. 5 Approximate ranges of some biomarker maturity parameters (C30), and ßß/(ßß + aß + ßa)-hopanes, where 10, 5, and 0 are minimum
relative to the oil generation window (modified from Peters and values, respectively. Intermediate values are shown for a few ratios
Moldowan 1993). Solid bars show the range for each ratio relative to within the bars to indicate earlier stages of maturity (Reprinted with
the stages of oil generation. Each ratio reaches a constant percentage permission by ChevronTexaco Exploration and Production Technology
indicated at the end of the bar, which normally does not change with Company, a division of Chevron U.S.A. Inc.)
further maturity. This ratio is the maximum value for most of the

equivalent to at least the beginning of the oil window respond at low maturity, thus resulting in no systematic trend.
(Ro ~ 0.6%). All samples in Fig. 6 have achieved endpoint Nevertheless, ratios for these slow reactions can show sys-
for this ratio. Next, proceed to the ratio for a slower reaction, tematic variations with maturity in some cases, and it is
such as C29 sterane %20S/(20S + 20R). If the endpoint for % preferable to consider as many biomarker maturity parameters
20S/(20S + 20R) has been achieved, then proceed to an even as possible to corroborate interpretations.
slower reaction, such as C29 sterane %bb/(bb + aa). If this
ratio did not achieve endpoint (~70%) for a sample (e.g.,
sample H in Fig. 6), then the thermal maturity is bracketed Supporting Analyses
by the endpoints for %20S/(20S + 20R) and %bb/(bb + aa)],
which approximately corresponds to the peak of the oil win- Perhaps the most straightforward biomarker maturity param-
dow or Ro ~ 0.9% (Fig. 5). If the sample achieved endpoint eters rely simply on biomarker concentrations in oil and rock
for %bb/(bb + aa), e.g., sample I in Fig. 6, then further extract samples. Biomarker concentrations can be measured
assessment requires use of ratios from even slower reactions by GC-MS or GC-MS-MS by introducing calibration factors
such as mono- or triaromatic side-chain cleavage parameters: determined through analysis of an external standard, where
MA(I)/MA(I + II) or TA(I)/TA(I + II), which are not based on the abundance of the ion being measured for each biomarker
stereoisomerization. We do not recommend that maturity (e.g., m/z 217 for steranes by GC-MS or the m/z 400 ! 217
assessment begin with ratios based on such slow reactions, transition for C29-steranes by GC-MS-MS) is calculated
because (1) reactions controlling these ratios are complex and based on its known concentration in the standard. Biomarker
the initial amounts of reactant and product may not be 100% concentrations steadily decrease from a maximum before the
and 0%, respectively, and (2) these robust ratios may not even beginning of the oil window to zero at or before the end of the
Biomarkers: Assessment of Source Rock Thermal Maturity 7

Biomarkers: Assessment of Source Rock Thermal Maturity, two and four peaks, respectively. Sample A is the least mature. Sample
Fig. 6 Relative thermal maturity for nine genetically related crude oil G is less mature than samples H and I. Sample I is more mature than
samples based on two C29 sterane stereoisomer ratios. Inset shows peaks H because it has achieved endpoint for both ratios. Complete maturity
used for the C29 sterane ratios from GC-MS-MS analysis (m/z assessment of sample I requires additional biomarker ratios that respond
400 ! 217; peaks 35–38 in Fig. 4). The %20S and %bb ratios require at higher levels of thermal maturity

oil window, depending on which biomarker is being mea- methylphenanthrene index (Radke and Welte 1983), can be
sured. One such biomarker concentration that is commonly used to corroborate biomarker assessment of oil maturity.
used in this way is that of the aaa20R-C29-sterane
(sometimes named stigmastane) when plotted versus the
sum of the concentrations of two diamondoids: 3- and Summary
4-methyldiamantanes (Dahl et al. 1999). Diamondoid con-
centrations are measured by adding deuterated diamondoids In general, the relative thermal maturity of genetically related
to the oil or extract sample before analysis (diamondoid oil or source rock extract samples can be readily assessed
methods and applications are reviewed by Moldowan et al. using various biomarker maturity ratios. Maturity ranking
2015). This method accounts for maturity from the beginning may not be possible for samples that are contaminated,
of the oil window extending into the gas window, i.e., from heavily biodegraded, or so highly mature that specific bio-
Ro ~ 0.6 to 4.0% or more. The aaa20R-C29-sterane reaches markers are low (<3–5 ppm) or absent. However, highly
negligible concentrations at approximately the maturity mature samples can still be evaluated using the quantitative
where oil begins to crack to gas and pyrobitumen is being biomarker-diamondoid method. Estimates of maturity rela-
formed. On the other hand, the diamondoids are thermally tive to the oil window or vitrinite reflectance using biomarker
very stable and actually become more concentrated after ratios may not be as straightforward as relative maturity
significant oil cracking begins. Thus, Fig. 7 can be used to assessment. Biomarker maturity ratios are limited in the effec-
determine relative maturities of oil samples both within and tive maturity ranges that they cover. Therefore, the most
far beyond oil-window maturity. reliable maturity assessments are based on multiple bio-
Biomarker maturity assessment is best supported by addi- marker ratios from progressively slower reactions, which
tional maturity measurements. For example, vitrinite reflec- bracket the maturity of each oil or rock extract sample. Ste-
tance or programmed pyrolysis Tmax and production index for reoisomer ratios are preferred because the initial amount of
rock samples can be used to help verify biomarker interpre- reactant in the biological configuration is 100%, while that of
tations based on the corresponding rock extracts. Non- the product is 0%.
biomarker maturity parameters, such as the
8 Biomarkers: Assessment of Source Rock Thermal Maturity

Biomarkers: Assessment of Source Rock Thermal Maturity, baseline concentrations after significant oil cracking begins. Oil samples
Fig. 7 The biomarker-diamondoid method can be used to assess ther- showing mixed maturity signals, i.e., elevated stigmastane and elevated
mal maturity of crude oil or source rock extract samples. Oil samples 3- and 4-methyldiamantane concentrations (triangles), represent mix-
having maturities within the oil window show significant C29 sterane tures of both oil-window (e.g., black oil) and postmature components
(stigmastane) concentrations and low concentrations of diamondoids (e.g., light oil or condensate) that result from multiple charge events in
(3- and 4-methyldiamantanes). Diamondoids increase rapidly from the petroleum reservoir (Figure adapted from Dahl et al. (1999))

Cross-References Peters KE, Cassa MR (1994) Applied source rock geochemistry. In:
Magoon LB, Dow WG (eds) The petroleum system – from source
to trap. Am Assoc Petrol Geol Mem 60:93–117.
▶ Basin and Petroleum System Modeling Peters KE, Moldowan JM (1993) The biomarker guide. Prentice-Hall,
▶ Biomarkers in Sediments and Petroleum Inc., Englewood Cliffs, 363p
▶ Biomarkers: Assessment of Petroleum Source Rock Age Peters KE, Walters CC, Moldowan JM (2005) The biomarker guide.
and Depositional Environment Cambridge University Press, Cambridge, 1155 p
Peters KE, Moldowan JM, LaCroce MV, Kubicki JD (2014) Stereochem-
▶ Petroleum Source Rocks istry, elution order, and molecular modeling of four diaergostanes in
▶ Programmed Temperature Pyrolysis petroleum. Org Geochem 76:1–8
▶ Thermal Maturity Radke M, Welte DH (1983) The methylphenanthrene index (MPI).
▶ Vitrinite Reflectance A maturity parameter based on aromatic hydrocarbons. In:
Bjorøy M, Albrecht C, Cornford C, de Groot K, Eglinton E,
Galimov E, Leythaeuser D, Pelet R, Rullkötter J, Speer G (eds)
Advances in organic geochemistry 1981. John Wiley and Sons,
Bibliography New York, pp 504–512
Seifert WK, Moldowan JM (1979) The effect of biodegradation on
Barker CE, Lewan MD, Pawlewicz MJ (2007) The influence of extract- steranes and terpanes in crude oils. Geochim Cosmochim Acta
able organic matter on vitrinite reflectance suppression: a survey of 43:111–126
kerogen and coal types. Intl J Coal Geol 70:67–78 Walters CC, Lillis PG, Peters KE (2012) Molecular indicators of geo-
Dahl J, Moldowan JM, Peters KE, Claypool GE, Rooney MA, Michael thermal history. In: Harris NB, Peters KE (eds) Analyzing the thermal
GE, Mello MR, Kohnen ML (1999) Diamondoid hydrocarbons as history of sedimentary basins: methods and case studies, SEPM
indicators of natural oil cracking. Nature 399:54–57 Special Publication 103, pp 17–28
Moldowan JM, Dahl JE, Zinniker D, Barbanti SM (2015) Underutilized
advanced geochemical technologies for oil and gas exploration and
production-1.The diamondoids. J Pet Sci Eng 126:87–96
P

Petroleum Geoscience p. 1). Petroleum geoscience is also an active field of education

and investigation in many universities around the world with
Rasoul Sorkhabi research projects and consortia often sponsored by oil
University of Utah, Energy & Geoscience Institute, Salt Lake companies. Petroleum geoscience, whether in academia or
City, UT, USA industry, is such a vast field that no single person can claim
to be a petroleum geoscientist; the experts are usually catego-
rized as exploration geologists, petroleum geochemists,
Definition petrophysicists, seismic geophysicists, and so forth.
The term “petroleum geoscience” has been used in the title
The term “geoscience” or “geosciences” has been used in two of the journals Petroleum Geoscience (published quarterly by
different ways. Sometimes, it is a short term for “geological the Geological Society of London and the European Associ-
sciences” and is thus synonymous with “geology.” It may also ation of Geoscientists and Engineers) and Petroleum Geosci-
mean “Earth science” or “Earth sciences” which would ence (an open-access, peer-reviewed journal published by
include not only geology but also geophysics, geochemistry, China University of Petroleum under the brand
meteorology (and other atmospheric sciences), oceanography SpringerOpen) as well as in the titles of several textbooks
(and other hydrological sciences), as well as soil science such as those by Gluyas and Swarbrick (2004) and
(pedology) (Jackson 1997). “Petroleum geoscience” Bjørlykke (2015).
embraces all geological, geophysical, and geochemical disci-
plines which are used for exploration and production of
petroleum in its various physical forms (oil, natural gas, Cross-References
condensate, and bitumen). Four main branches, depending
on their methodology, are usually recognized in the academia ▶ Petroleum Exploration
and industry: Petroleum geology, petroleum geochemistry ▶ Petroleum Geochemistry
(closely associated with organic chemistry), petroleum geo- ▶ Petroleum Geology
physics (an important aspect of exploration geophysics), and ▶ Petroleum Geophysics
petrophysics (including formation evaluation and well log-
ging and closely related to both geophysics and petroleum
engineering). All of these branches are interrelated and should References
be used in an integrated manner for petroleum exploration.
Although rooted in geosciences, “petroleum geoscience is Bjørlykke K (2015) Petroleum geoscience: From sedimentary environ-
ments to rock physics, 2nd edn. Springer, Heidelberg. 662 p
intimately linked with making money, indeed profit. The role
Gluyas J, Swarbrick R (2004) Petroleum geoscience. Blackwell Publish-
of the petroleum geoscientist, whether in a state company, a ing, Oxford. 376 p
massive multinational company, or a small independent com- Jackson J (1997) Glossary of geology, 4th edn. American Geological
pany, is to find petroleum (oil and hydrocarbon gas) and help Institute, Alexander. 769 p
produce it so that it can sold” (Gluyas and Swarbrick 2004,

# Springer International Publishing AG 2017

R. Sorkhabi (ed.), Encyclopedia of Petroleum Geoscience,
DOI 10.1007/978-3-319-02330-4_11-1
P

Petroleum Industry petrochemical plants. (3) Downstream refers to the refining

of crude oil, processing of natural gas and petroleum prod-
Rasoul Sorkhabi ucts, as well as marketing and distribution of liquid hydrocar-
University of Utah, Energy & Geoscience Institute, Salt Lake bons (gasoline/petrol, diesel oil, kerosene, jet fuel, etc.),
City, Utah, USA natural gas, liquefied petroleum gas (LPG), solid hydrocar-
bons (lubricants, waxes, asphalt, etc.), and petrochemicals to
customers and consumers. Sometimes, midstream operations
Definition are included in the downstream sector.
The terms upstream and downstream may be used in a
The petroleum industry includes all activities related to the relative sense; they may refer to facilities and operations,
exploration, extraction, refining, transportation and marketing respectively, before and after a point of reference. Thus, oil
of oil, natural gas, and petroleum products. Because oil, production is upstream from transportation, and transporta-
natural gas, and petrochemicals are vital to modern societies tion is upstream from refining. In other words, transportation
and standards of life, the petroleum industry has become a key is downstream from oil production, and refining is down-
component of international economy, national security, and stream from transportation (Langenkamp 1994). However,
advanced technology. Many oil and gas companies with their upstream, midstream, and downstream in the oil industry are
valuable products have a significant presence in stock usually defined in the three-fold classification made above. In
exchange markets. The petroleum industry is one of the this scenario, oil flow or the oil industry’s workflow is likened
largest employers of geologists, engineers, business man- to that of a river or stream with its source up in the mountain
agers, and other professionals relevant to their activities. and flowing downward to the sea. This three-part categoriza-
The petroleum industry has also contributed greatly to sci- tion of the petroleum industry is based on the concept of
ences (especially geology and chemistry) and technologies “value chain” management, that is, the full range of activities
(for example, drilling and subsurface imaging). that a business entity has to conduct in order to bring a product
Although asphalt, oil, and natural gas were known to and or a service to its customers. A vertically “integrated petro-
used by various peoples even in the ancient times, the modern leum company” is engaged in upstream, midstream as well as
petroleum industry equipped with mechanical drilling downstream activities. This can be afforded only by large
emerged in the mid-nineteenth century. The 1859 Drake dis- companies (state-owned national or public-owned interna-
covery well in Titusville, Pennsylvania, is often regarded as a tional) which possess enormous financial, technical, and
milestone that ushered in the modern age of petroleum; nev- human resources. Many petroleum companies deal with a
ertheless, oil production and utilization were underway in the single sector such as E&P, drilling, transportation, or refining.
mid-nineteenth century in several other regions around the The modern petroleum E&P began onshore in the mid-
world as well, most notably Azerbaijan (Baku fields, then part nineteenth century, and as technology and economical prop-
of Russia), Romania, Burma (Myanmar), and Canada. ositions permitted, the industry expanded its activities to
The petroleum industry is usually divided into three sec- offshore areas, initially shallow continental shelves and then
tors. (1) Upstream includes exploration and production (E&P) deep marine basins.
of crude oil and natural gas. (2) Midstream involves storage Day (1922), Dunstan et al. (1938), Hager (1939), and
and transportation of petroleum by pipelines, tankers, barges, DeGolyer (1940) give reviews of the petroleum industry
trucks, or rail from producing fields to refineries and in the early decades of the twentieth century, while Royal

# Springer International Publishing AG 2017

R. Sorkhabi (ed.), Encyclopedia of Petroleum Geoscience,
DOI 10.1007/978-3-319-02330-4_19-1
2 Petroleum Industry

Dutch/Shell Group (1983), Anderson (1984), Conway Day DT (ed) (1922) A handbook of the petroleum industry, 2 vols.
(1991), Berger and Anderson (1992), Grace (2007), Jahn Wiley/Chapman & Hall, New York/London, Volume I x + 960 p,
Volume II vi + 1006 p
et al. (2008), Legault (2008), Bret-Rouzaut (2011), Denehy DeGolyer EL (ed) (1940) Elements of the petroleum industry. American
(2011), Hyne (2012), and Hilyard (2012) provide more recent Institute of Mining, Metallurgical, and Petroleum Engineers
reviews. (AIMME), New York. 519 p
Denehy, D. (ed.), 2011. Fundamentals of petroleum, 5th edn. University
of Texas at Austin, Petroleum Extension Service PETEX, Austin,
TX. 720 p
Cross-References Dunstan AE, Nash AW, Brooks BT, Tizard H (eds) (1938) The science of
petroleum, 4 vols. Oxford University Press, Oxford. 3192 p
▶ Petroleum Exploration Grace R (2007) Oil: an overview of the petroleum industry, 6th edn. Gulf
Publishing Co., Houston. 161 p
▶ Petroleum Production Hager D (1939) Fundamentals of the petroleum industry. McGraw-Hill,
▶ Refining New York. 445 p
Hilyard JF (2012) The oil and gas industry: a nontechnical guide.
PennWell, Tulsa. 332 p
Hyne NJ (2012) Nontechnical guide to petroleum geology, exploration,
References drilling and production, 3rd edition. PennWell, Tulsa, xxv + 698 p
Jahn F, Cook M, Graham M (2008) Hydrocarbon exploration and pro-
Anderson KE (1984) Fundamentals of the petroleum industry. The duction, second edn. Elsevier, Amsterdam. 396 p
University of Oklahoma Press, Norman, xii + 390 p Langenkamp RD (ed) (1994) The illustrated petroleum reference dictio-
Berger BD, Anderson KE (1992) Modern petroleum: a basic primer of nary, 4th edn. PennWell, Tulsa. 904 p
the industry, 3rd edn. PennWell, Tulsa. 517 p Legault A (2008) Oil, gas and other energies: a primer, translated from
Bret-Rouzaut N (2011) Oil and gas exploration and production: reserves, the French by Barbara Chunn and Betsy McFarlane. Paris: Editions
costs, contracts. Editions Technip, Paris. 309 p Technip, xx + 286 p
Conway CF (1991) The petroleum industry: a nontechnical guide. Royal Dutch/Shell Group (1983) The petroleum handbook, 6th edn.
PennWell, Tulsa. 289 p Elsevier, Amsterdam. 710 p