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PPG 712-PETROLEUM GEOCHEMISTRY

M.Sc Petroleum Geoscience

PAN AFRICAN UNIVERSITY LIFE AND EARTH SCIENCES INSTITUTE

UNIVERSITY OF IBADAN, IBADAN NIGERIA
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WHAT IS ORGANIC GEOCHEMISTRY- This is the starting point and it denote the study of the origin and the fate
of sedimentary organic matter within the geosphere.

WHAT IS PETROLEUM GEOCHEMISTRY- It is the application of chemical principle to the study of the origin,
migration, alteration and accumulation of petroleum in the geosphere, and the use of this knowledge in the
exploration and recovery of oil and gas, as well as related bitumen. Through this knowledge, we get a clearer
picture (knowledge or understanding) of the processes especially when it proffers solution or answers to the
following:

 What are petroleum and its origin?

 How does it accumulate?
 How does it migrate?
 How does it change with depth, temperature and pressure variations?

Petroleum Geochemistry allows us to determine how and where the organic matter in sediments is
converted to gas and oil, by defining;

1. The concentration of organic matter in a rock i.e. TOC-Total Organic Matter content
2. The quality of the organic matter
3. The state of metamorphism/metagenesis of the organic matter
4. The amount of hydrocarbon which have been or could be generated from the rock

What is Petroleum- Petroleum is defined as a liquid substance composed principally of hydrocarbons which
occur in underground natural reservoir. More recently however, the definition has been broadened to
include Hydrocarbon (HC) gases occurring in similar reservoirs. For this lecture, HC occurring as liquid in
reservoir will be known as crude oil or oil, and those that are gaseous will be referred to as natural gas,
and those in vapor form in the reservoir will be referred to as condensate.

Generally, HC is broken into three families:

1. Natural gas : C1 – C5
2. Crude oil : C6 – C40
3. Bitumen : > C40
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Hydrocarbons are also chemical compounds whose molecules are composed of atoms of solely two
elements; Carbon & Hydrogen (C&H). It is this composition that makes them an important source of
energy, because in the presence of O2, they produce CO2 and H2O, and very large amount of energy.

CH4 + 2O2 → CO2 + 2H2O + Energy

ORIGIN OF CRUDE OIL OR BITUMEN

The origin looks controversial because of 2 basic reasons:

1. They are not found where they are formed.

2. As oil migrates, it changes its chemical composition i.e. there is a continuous chemical compositional
change during migration.

As a result of the above, there are 2 theories to the origin:

A. Abiogenic Origin/an inorganic origin

What are the evidences in support of this mode of origin?

1. H2O + metallic carbide will give HC [ 2H2O + C → CH4 + O2]

2. H2O + alkali earth metals will be give HC [Na + CO2 → CH4 + Na2O].
3. HC is believed to be one of the products of volcanism.
4. Atmosphere of other planets have been discovered to contain HC. If this is true, then there is the
possibility that the atmosphere of the Earth (primordial earth) contained HC during primordial time.
5. Meteorites have been discovered to contain HC.

However, these 5 points however fade off in the face of the following;

1. Carbide has not been documented to occur naturally; same goes for the alkali earth metals.
2. The amount of HC discovered cannot be explained by volcanism; same goes for the atmosphere of
other planets and the earth and also for meteorites.
B. Biogenic or Organic origin
The reasons/evidences in favour of this mode of origin are as follows:
1. In all the cases where petroleum products are analyzed, remains of organisms and plants have been
found in it.
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2. The C12/C13 ratio found in petroleum is the same as that found in living organisms.
3. The presence of substances peculiar to organic matter in HC has been established e.g. hermins (blood
pigments), porphyrins.
4. There’s an optical rotary property exhibited only by living organisms, and this is found in petroleum;
thus confirming that it is a product from it (The presence of vitrinite confirmed this).
5. The presence of sulphur and nitrogenous compounds in petroleum as well as inorganic compounds
also supported this hypothesis.
6. Analysis of recent sediments revealed the presence of HCs.

7. Geologically, the geologic interval attributed to the formation of HCs coincided with the evolution of
life.

PRODUCTION AND ACCUMULATION OF ORGANIC MATTER (OM)

Organic Matter means materials consisting of organic molecules in monomeric or polymeric forms
derived directly or indirectly from the organic part of the organism. The production and accumulation,
and preservation of undegraded organic matter are the prerequisite for the existence of petroleum
source rock. The production of organic matter involves two major processes i.e. synthesis
(biochemical) and deposition (geological).

Organic matter are synthesized by living organisms, deposited and preserved in sediments, and
depending on further geological events such as uplift and subsidence, part of the organic matter may
be transformed to petroleum-like substances.

Synthesis is the basis for mass production of organic matter through the process of photosynthesis. It
involves transfer of H2 from H2O to carbon dioxide (CO2) to produce OM in the form of carbohydrate
and O2.

6CO2 + 6H2O ↔ C6H12O6 + 6O2

Autotrophic organisms can synthesize glucose from tricose which will be successfully converted to
polysaccharides

3CO2 + 6H2O → C3H6O3 + 3O2 + 3H2O

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Thus, photosynthesis is the basis of the processes that accomplish the mass production of organic
matter on Earth and the source of organic matter is the biosphere. The primary producers of organic
matter fall within three categories:

SOURCES OF ORGANIC MATTER

Biosphere is the main source of organic matter. The primary producer of organic matter falls within 3
categories namely;

1. Plankton
I. Phytoplankton
II. Zooplankton [Both are unicellular organism found in aquatic environment( Phyto- plants and
Zoo- animals; Phyto produces food by photosynthesis and Zoo by feeding on phytons]
2. Bacteria.
3. Higher plants.

PLANKTON

In the Precambrian (2 billion years ago), the producers of organic carbon are the blue-green algae, the
photosynthetic bacteria. But by Cambrian, Ordovician and Silurian, varieties of bacteria, phyto-
organisms and blue-green algae dominated sources of organic carbon. By mid-Devonian, which
coincided with the appearance of land plants, the producers increased (land plants here refer to ferns,
because big woody plants came in Carboniferous). Presently, it is estimated that marine phyto-
planktons are responsible for 50–60% of the world’s organic carbon production. Group of
phytoplanktons include algae (found in fossil record as acritarchs, which can either be calcareous or
siliceous), dinoflagellates (which are calcareous), nannoplanktons e.g. coccolithophores (which are
siliceous), silicoflagellates (siliceous phytons e.g. diatoms). Of all these, the main producers are
dinoflagellates, diatoms and coccolithophores. The annual production of phytoplanktons in the world
ocean is about 5.5 × 109 tonnes.
For the Zooplanktons, planktonic foraminifera are the major contributors of organic matter, though
their quantities and qualities are dependent on phytoplanktons.

HIGHER PLANTS
These only became principal contributors of organic matter from Silurian. It became diversified in
Devonian. Higher plants refer to spores and pollens and because diversification of higher plants is very
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prominent in Carboniferous, is the reason why Carboniferous is associated with coal formation. In
summary, zooplanktons, phytoplanktons and higher plants are the main contributors of organic matter
in sediments. The natural association of the various groups, in various facies provinces determines the
composition and types of organic matter to be deposited and incorporated in the sediments.
Factors that affect the primary productivity of organic matters include light, chemical composition,
temperature, etc.
MAJOR COMPONENTS IN THE ORGANIC MATTER
All living organism consist essentially of small number of chemical substance which are mainly the
Proteins, Carbohydrates, the Lipids, Lignin and Tanins. Their proportion varies substantially on the
family of plant kingdom we are looking at.
PROTEINS- This generally formed a large share of Organic matter. They constitutes different types of
materials as Muscle fibres, silks sponges etc. They are highly organized polymer made from individual
amino acids. Though they are insoluble in water but in the presence of enzymes, they are broken down
to amino acid which is soluble in water. This process is known as Hydrolysis e.g Peptide bond

CHOCH (CH3) NHCOCH (CH3) NH2 + 2H2O +Enzymes COOHCH (CH3) ӤH2 COOHCH (CH3) ӤH2

CARBONHYDRATES- It derived the name from its empirical formula Cn (H2O)n. Carbonhydrates
includes glucose and their polymers implying industrial sugar and polymers i.e di, tri and poly
saccarides. They account for the major types of tissues especially such as Cellulose, chitin and
sporopollenin. They are amongst the most abundant constituents of plants and animals and are
sources of energy and form the supporting tissues of plants and certain animals. Cellulose is chiefly
produced by higher plants. Chitin is from animals while Sporopollenin are spores and pollen grain

LIPIDS- The term lipid apply to organically produced substance that are practically insoluble in H 2O,
but are extractable by organic solvents e.g Chloroform, ether, aliphatic and aromatic hydrocarbon as
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well as saturated and unsaturated fatty acid. Lipids include animal fats and vegetable oils. Fats are
utilize in energy budget f organism while waxes are use for protection. Lipids are abundance in algae
especially Botryoccus and Diatoms which forms up to 70% of the dry weight. They are also found in
pigment and pores which are rich in C-34 where they constitute high energy potential. Lipids also
contains fats which are esters of fatty acid and they include Terpenic compounds such as isoprenoids
which can be polymerise to long chain. Naturally occurring fats are actually mixtures of various
triglycerides which are classified as Triglycerides and can be hydrolised usually by aqueous NaOH
leading to the formation of Glycerols and components of fatty acids which end up as Sodium (Na) salt.

H3C- (CH2)n- C-O- CH2 HO- CH2

(+3OH)
H3C- (CH2)n- C-O- CH HO- CH2 + 3H3C- (CH2)n- C-O
(+3Na+) (+3Na+)
H3C- (CH2)n- C-O- CH2 HO-CH2
(Triglycerols) (Glycerol)

Fatty acids of natural fats have even number of carbon atoms because they synthesise from C 2 unit i.e
the acetate unit but most frequently occurring fatty acids are those with C16- C18 i.e Palmitic and Stearic
type acids. The unsaturated fatty acids are common e.g vegetable oil. There are also lipids like
components found in living organic matter such as oil soluble pigments e.g Terpenoids, Stereoids and
Phosphatides which are regarded as complex fats containing fossils. Natural gums which are produce
by some higher plants are poly-terpenes.

Lignin and Tanin- Both are characterized by phenolyic structure which is aromatic (unsaturated)
structure. The first is a polyphenol with high molecular weight of aromatic structure that forms the
skeleton of the tissue of the higher plants. The second one is less condescend phenol that impregnated
the cortex tissues. The aromatic ring are synthesise by plants and not by animals. Lignin occur as 3-
dimensional network located within soluble micelles of supporting tissue of plants. In plants, they are
synthesise by dehydration and decondensation of alcohols.
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CH2OH CH2OH CH2OH

CH CH CH
CH CH CH

Quantitatively, the Tannis are less important as Lignin but are wide spread and the name is derived
from tan- hides. Based on the reaction and composition, one can consider them as intermediate
between Lignin and Cellulose but they posssess both Carboxyl as well as phenolic groups on their
aromatic structure.

Their chemical formula varies considerably but they are all complex derivatives of Gallic and Ellagic
acids and they are found principally in higher plants and also in algae but concentrated at the back
(17%) and leaf (6.5%) in higher plants.

KEROGEN- The Parent Substance of Petroleum

Once the organic matter has been deposited, the process of chemical alteration and degradation
begins almost immediately. The various processes involved include the following:

1. Oxygenated water (Oxic Condition): Bacteria, fungi and scavengers quickly decompose and destroy
organic matter. Proteins and carbohydrates are the most unstable and soluble hence the most
destroyed. Lipids are more resistant to the activities of Bacteria, fungi and scanvengers but lignins are
the most resistant of all. Note that, if O2 is replenished by flowing H2O or by exposure of organic matter
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to air, even the more resistant materials will be oxidized to fusain or inertinite (species of mineral
charcoal).
2. Anoxic Condition: In an anoxic condition, the activities will be restricted to anaerobic bacteria. Under
this condition or environment, the destruction of lipids and lignin is held to a minimum. We may even
have residue of degraded proteins and carbohydrates. The above scenario can also occur in sediments
immediately below the water-sediment inter-phase, even though the overlying water is oxygenated. In
the fine grained sediments such as mud or silt, the pore space is a closed environment, separating the
interstitial water from the overlying sea or lake water. Aerobic bacteria activity quickly exhausts the
confined oxygen, and anaerobic conditions are set up.

Two processes result from anaerobic bacteria activities; namely Fermentation and Sapropelisation.

a. Fermentation: This is the process whereby micro-organisms obtain their oxygen from organic matter
particularly cellulose and carbohydrates to produce CO2, and various organic compounds. A closely
related anaerobic bacteria reaction, metanogenesis, produces large quantities of bacteria methane.
This is what is referred to as wet gas/ biogenic gas. It occurs early in the diagenetic history.
b. Sapropelisation: Process which destroys the physical structure of organic matter and reduces it to an
amorphous gel. It appears to be most effective on organic matter with high lipid content such as algal
material, but also occurs in the other components.
Thus from above, preservation of organic matter in sediments is dependent on the interplay of three
factors;
a. Rate of supply of organic material
b. Amount of preservation resulting from environment of deposition
c. Rate of burial
As the rate of burial of organic material increases, biochemical processes ceased, and subsequent
changes resulted from purely chemical processes. At this point, complex intermediate substances are
formed by a chemical process known as polycondensation, and the chief substance formed through
polycondensation are fulvic and humic acids. These acids are composed of huge complex molecules
often containing thousands of atoms which usually represent about 90% of the organic matter present.
The polycondensation is completed in the first few meters of sediments and is followed by a much
slower chemical process called insolubilisation. This process converts the intermediate substance into a
single stable substance known as kerogen, and the process takes place over appreciable geological
time and it is largely completed at depths of about 1000- 3500 feet (300-1000meters).
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Kerogen is a term applied to the organic constituent of sedimentary rocks which are insoluble in
organic or alkaline solvents. Kerogen is thus different from organic constituents which are soluble in
these solvents (bitumen). It is the most widespread form of organic matter on Earth. It is a thousand
times more than coal and liquid petroleum, and fifty times more than bitumen dispersed in non-
reservoir rocks.
From chemical standpoint, kerogen is a macromolecular complex compound of condensed benzene
ring connected by heteroatomic or aliphatic chain or links, it may also contain lipids. Structurally,
kerogen is in disordered state but assumes a degree of organization during catagenesis. Generally,
kerogen consists of heterogenous finely disseminated organic matter and like its precussor materials, it
is composed mainly of enormous complex molecules. Kerogen is relatively inert, it cannot be dissolved
in acids and is also insoluble in water or simple organic solvents such as chloroform or benzene. It is
resistant to bacterial attack but can be oxidized by certain chemical or by long exposure to air. In the
late stages of diagenesis, there is a decrease in the amount of Oxygen and a correlative increase of the
carbon content of the kerogen and this is shown by marked decrease of elemental oxygen/carbon ratio
(O/C) and a relatively slight decrease of Hydrogen/Carbon (H/C) ratio. It appears that the major
products of the chemical changes in the kerogen at this stage are CO2 and H2O.

TYPES OF KEROGEN

The types and amount of petroleum produced from a particular kerogen depends on the kerogen
characteristics, which in turn depends on the type of source material and the diagenetic history of the
kerogen concerned. When kerogen is examined under the microscope, it has been discovered that it
consist of similar or identical macerals as that of coal (as both coal and kerogen follow the same
diagenetic path, they also originate from the same organic sources), though the environment of
deposition are different, coal usually consists of much higher proportion of plant materials than
kerogen.
Microscopic maceral analysis has proved to be a simple and convenient way of classifying kerogens,
except in cases where the kerogen has large proportions of fine organic matter of sub microscopic size
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or has been sapropelised to the extent that the macerals are unrecognisable Kerogen researchers use
a modified coal maceral classification as the basis of kerogen type classification but when
unrecognized, back up chemical analyses are necessary to classify the kerogen. On the basis of Coal
maceral classification, we have;

I. Algnitic – Type I
II. Liptinitic- Exinitic – Type II
III. Vitrinitic – Huminitic – Type III
IV. Inertinitic – Type IV

ALGINITIC: It is a marceral derived from the algal remains and those considered as individual liptinite
marcerals are elevated to a separate class. Vitrinite and Inertinite are grouped together as one class,
but a three-fold division type of kerogen is now the standard. In the earlier literatures, a number of
synonyms were used for the kerogen types. Some are still being used till today. However, two are still
being used which are capable of causing confusion:

1. Sapropelic Kerogen: Sapropel is an amorphous secondary product of the bacterial degradation of

organic matter, and can be associated with any type of kerogen. Since lipids are the most easily
sapropelized, liptinite and especially alginate often have a high proportion of sapropelized organic
matter. Some authors thus use sapropelic kerogen to denote Type one and two, but others limit it to
Type one.
2. Amorphous Kerogen: The word ‘amorphous’ means ‘without form’, and has been variously used to
refer to sapropelized Type one or Type two kerogens, and also to unrecognizable component, often
very fine when kerogen is observed under the microscope. The use of the term amorphous in this way
has led to misleading interpretations in geochemical reports, where it was assumed that unidentifiable
amorphous material was Type one and/or Type two kerogen, and no backup analysis were made to
determine the nature.

Rarely is a detailed quantitative estimate made of the abundance of the various marceral components.
In a geochemical report, the result can be combined as Type I or II as oil-prone, and Type III and IV as
gas prone, for ease of interpretation. Alternatively, the three marceral types identified by numbers or
symbols may be listed in decreasing order of abundance in the kerogen being examined. Pure Type I
kerogens are relatively rare, they are most likely to occur in closed basins, lagoons and lakes, where
the major organic source is planktonic algae. Oxidation at the water-sediment interface is at a
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minimum due to stagnant bottom conditions and sedimentation is at minimum, so that the
concentration of organic matter in the sediments is very high.

A marine transgression over a broad shelf seems to be a very favorable environment for a widespread
deposition of type II kerogen or mixture of 2 or more types. Deltas, which are usually well supplied
with terrestrially derived organic matter, are favorable environments for Type III kerogens. Large oil
accumulations are associated with Type I or II kerogens, while gas prone areas are associated with
Type III kerogen or thermally metamorphosed Type I or II.

CATAGENESIS: The maturation of kerogen and production of petroleum

As rock containing kerogen is progressively buried more deeply in a subsiding basin, it is subject to
increasing temperature and pressure. Temperature may vary from 500C to higher than 1750C in the
major part of the sedimentary section; pressure can range from 1200psi to 10,000 psi in the same part
of the section. The increase of temperature represents an increase of energy available for chemical
reactions in the kerogen, thus, at subsequent temperatures of between 50-750C, the kerogen begins to
break up and produce hydrocarbons. This is caused by cracking and reforming of the large kerogen
molecules. The bridges which chain the kerogen molecules together are broken, resulting in generation
of smaller molecules, which is reflected in an increase in the bitumen content. The bitumen molecules
are intermediate which in turn are broken down into smaller molecules and these, along with the side
chains broken off from the kerogen molecules form the chain alkanes, napthenes and aromatic
hydocarbons, which are the components of petroleum. With further increasing temperature, the
reactions become more intense and the peak of main stage of petroleum generation is reached. In this
stage, most of the hydrocarbons generated have a low-medium molecular weight of C1-C40 with no
particular ordering. In this manner, the production of oil is accompanied with the production of a
considerable amount of natural gas, with increasing temperature, lighter hydrocarbons are produced
until methane becomes the predominant hydrocarbon. This stage is known as the wet gas stage of
catagenesis. At the end of the wet gas stage, the capacity of the kerogen to produce anything more
than a limited amount of CH4 is exhausted and the carbonization or metagenesis stage is reached. At
this point, the kerogen has been converted to a carbon residue, and the produced petroleum into
methane and pyrobitumen. Since catagenesis is a process which takes geologic time to accomplish,
kerogen buried for a long period will be at a latter stage of catagenesis than a kerogen exposed for a
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shorter geological period, given the same formation temperature. Studies of the history of geological
basins show that the generation of oil occurs over a period ranging from 5 to over hundred million
years, the timing and rate of oil generation is largely controlled by the timing and rate of basin
subsidence.

In the diagenetic stage, there is a major loss of oxygen, so that the oxygen-carbon ratio drops rapidly
the hydrogen-carbon ratio drops slowly. However, at the catagenetic stage, the elemental H-C ratio
drops rapidly and this is because of the hydrogen that the system consumed, the quantity of
petroleum produced is proportional to the differences between the H-C ratios at the beginning and at
the end of catagenesis. The mass balance equation developed by Dow (1977) suggest that Type I
kerogen can have a conversion rate of 68% by weight, Type II a conversion rate of 40% and Type III,
16%.

Finally, from the Van Krevlin diagram,it can be seen that in the stage of metagenesis, the elemental H-C
ratios of all three types of kerogen are almost identical and approached the H-C ratio of inertinite
(˂0.4). The same similarity is true in physical characteristics and in the zone of metagenesis, it is often
impossible to determine the type of kerogen by microscopic examination. However, since in most
cases, half or more of organic carbon content still remains, it is possible to obtain some indication of
the original carbon content by measuring the organic carbon concentration.

COMPOSITION AND CLASSIFICATION OF CRUDE OIL

Petroleum is complex organic compounds found in nature and composed mainly of hydrogen and
carbon, and in addition, the N-S-Os. There are three phases of occurrence of petroleum: solid (called
pitch or tar), liquid (crude oil) and in gaseous form (natural gas).

COMPOSITION OF CRUDE OIL

Three basic methods are used in determining the composition of crude oil. These are;

1. Isolation and individual determination of hydrocarbons and heteroatomic compounds which is the
main thing carried out by America Petroleum Institute (API Research Project 6).
2. Distillation of petroleum using wide or narrow fractions. We have 15 in this routine, and it is associated
with some chemical or physical measurements on the fraction e.g. density, viscosity, sulphur content.
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It is related to the procedure used in refining crude oil, since all the physical or chemical parameters
depend on the relative amount of the various types of the chemical compounds (alkanes, cycloalkanes,
aromatics, thiophene derivatives etc) in a given fraction.
3. This is the method based on quantitative separation of the various structural types and determination
of the molecular distribution within each type, and these are mostly useful for geochemical purposes.
The main advantage of this procedure is to avoid any distillation which could destroy or alter some
labile constituents of petroleum and it also allows a sound basis for oil-source rock correlation
(Biomarkers and stable isotopes) when a small amount of bitumen extracted from source rock is
removed. When we are not carrying out fractional distillation but chemical analysis right from the
shale, we extract the crude and then analyse it.

FLOW CHART OF CRUDE OIL ANALYSIS

Infra-red spectroscopy (IRS) is mainly used for identifying and analysis of hydrocarbons and resins.

C-C at 2100 → Saturated hydrocarbons

C-C at 1600→ Double Bond (Alkene-Unsaturated hydrocarbon)

C-C at 1200→ Triple bond (Alkyne- Unsaturated hydrocarbon)

C-C ˂1200 → Aromatics

The main groups of compounds in hydrocarbons are:

1. Saturated Hydrocarbons: These are the Normal-alkanes (n-alkanes), cycloalkanes (Napthenic) and iso
alkanes (Paraffinic).
2. Aromatic Hydrocarbons: They include pure aromatic, cycloalkanoaromatics (naphtenoaromatics)
molecules and cyclic sulphur compounds (benzothiophenes derivatives) which can be roughly
estimated or evaluated through sulphur content of the aromatic fraction.
3. Resins and asphaltenes: These are the high molecular weight polycyclic fraction of crude oil
comprising N-S-Os. Asphaltenes are insoluble in light alkanes, and thus precipitate with n-hexanes.
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Resins are more soluble but are likewise very polar and strongly retained on silica gel when performing
liquid chromatography, unless a polar solvent is used as the mobile phase.

TYPES OF HYDROCARBON COMPOUNDS IN CRUDE OIL

1. Saturated Hydrocarbon
a. N-alkanes→ They are straight chain (linear) C1-C40 are found in crude oil. They amount to 15-20% but
in degraded oil, it is very low; 10-15%. Greater than C20 have high cloud point, n-alkanes show a slight
predominance in even or odd number of molecules in certain immature crude oil basins e.g. Uita basin.
The ratio of even to odd, when >1 shows that the basin is matured, but when ˂1, it shows immaturity.
Even/Odd>1= mature while Even/Odd= immature. The amount of n-alkanes is dependent on genetic
conditions and the nature of the original materials. High wax crude oil is those derived from terrestrial
organic matter and contains a large proportion of n-alkanes whereas marine or mixed organic matter
yields more cyclic compounds.
b. Iso-alkanes→ These are branched alkanes, isoalkanes of less than or equal to C10 carbon atoms are
found in crude oil. Series C11-C25 (Isoprenoids) carbon atoms are also found. The highest concentration
of alkane is found between C6 and C8, and it may be up to 1% of the total crude oil. Martin et al., (1963)
provided the importance of isoalkane in crude oil. In their work, they discovered that the order of
decreasing abundance of 6 hexane isomers is nearly the same in all the crude oil, same is true for 9-
heptane isomers which was also supported by the work of Reucache. The source of long-chain (the
alkyl chain) is alkanes, acids, alcohols from waxes of higher plants and algae. The cracking of heavier
compounds results in iso- and n-alkanes and aromatics. In the medium range, C9-C25, with methyl
branch on every 4th carbon atom is isoprenoids.
CH3- CH2- CH2- CH2 (CH3)-CH2- CH2- CH2 – CH2 (CH3)- CH2- CH2 – CH2- CH2(CH3)- CH2 - CH2- CH2- CH2 (CH3)-
CH2- CH2- CH2- CH2(CH3)

CRACKING

This is thermal, not controlled and there can be an overlap. It can be thermal or catalytic, which is
controlled.

c. Cycloalkanes→ The cyclopentane, cyclohexane and their derivatives with carbon atoms ˂ C10 are
important compounds in crude oil of all types, methyl cyclohexane is the most important of them all, in
abundance and it is 2.4% of the total crude from Conroe basin. However, the methyl derivatives are
more abundant than the mother hexane. The mono and dicyclic cycloalkanes amount to 50-55% of the
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total cycloalkane of C- atoms greater than 10. Their abundance decreases as the number of carbon
atom decreases down. Dicycloalkanes amount to 20% of the total cycloalkanes.

2. Unsaturated
a. Alkenes→ Putsher (1952) identified the following alkenes in Pennsylvania crude oil; n-hexenes, n-
heptene and n-Octene. Apart from these, polycycloalkenes have also been reported in ancient
sediments (e.g Porphyrines). But light alkenes are never found in crude oil (e.g propene). The basic
reasons why light alkenes are never found are because they have strong affinity for hydrogen. They will
like to reach a stable compound, in the presence of hydrogen in crude oil, the double bond gives way
to form mother alkanes. C2H4 + H2 C2H6
3. Aromatics
The major aromatics in crude oil are the derivatives toluene; 1.3% of the total crude oil, while mother
aromatics is 1%. Xylene is up to 1% while the derivatives is also 1.3%.

4. Sulphur
This is the third most important constituent of crude oil, apart from the hydrogen and carbon, they are
present in medium and heavy fractions of crude oil. The sulphur content is not specifically related to
the heaviest crude oil as nitrogen will. In the low and medium molecular range i.e. C atom ≤ 25, sulphur
is associated with hydrogen and carbon only and above C25, it is associated with N-S-Os. The sulphur
compound found in C atom up to 25 belongs to 4 main classes:
1. Thiomercaptans (-SH)
2. Disulphide; CS2
3. Sulphides
4. Thiophenes

5. Nitrogen (N2)→ It is lower than sulphur in crude oil. 90% of crude oil worldwide contain 0.2% of N2,
the average value of N2 in crude oil is 0.95% by weight, but in degraded asphaltenes, they are
enriched as relative parts or resins and asphaltene is enriched. They occur in crude oil in forms of
Pyridine, Quinoline, Carbozole and Indoles.
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6. Oxygen→ Found in fatty acids and isoprenoids, the amount of carboxylic is about 2.5% in young
crude oil, when oxygen compounds have been identified in minute amounts and occurs as ketones
and phenols

7. Organometallics→ Vanadium, nickel, metals e.g. magnesium and pseudo-transitional metals.

CLASSIFICATION OF CRUDE OIL

There are various classification of crude oil, but geologists and geochemists are concerned with
analyzing and characterizing the crude oil to relate them to source rock and to measure their grade
evolution, therefore they rely on chemical and structural information on product constituents,
especially the molecules which are supposed to contain geometric information.

The classification of crude oil is based on content of normal and isoalkane, cycloalkanes and aromatic
compounds i.e. the peculiar distribution of crude oil and the geochemical consequences derived from
it are in essence the basis forour proposed classification.

1. Paraffinic
2. Paraffinic-Naphthenic
3. Naphthenic
4. Aromatic-Intermediate
5. Aromatic-Naphthenic
1. Paraffinic→ Light crude oil, some are fluid while some are wax. The specific gravity is below 0.85,
amount of asphalthene and resins is below10%. The aromatic content is composed of mono and
diatomics, benzothiophenes are scarce. The sulphur content is low.
2. Paraffinic-Naphthenic→ Moderate resins and asphaltenes content between 5-15%, low sulphur
content between 0 and 1%. Aromatics amount to between 21 to 40% of the hydrocarbons, benzo and
dithiophenes are moderately higher. Density and viscosity are higher than paraffinic but remain
moderate.
3. Naphthenic→ They are few; some immature oil can be mentioned. It has such oil from Jurassic and
Cretaceous from South America. It has mainly degraded oil containing 20% of normal and cycloalkanes.
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They are formed from biochemical alteration from paraffinic and paraffinic-naphthenic. It is low in
sulphur content.
4. Aromatic-Intermediate→ Composed of heavy crude oil, resins and asphaltenes amounting between 20
to 30% and sometimes more. The sulphur content is greater than 1%, while aromatics amount to 40-
70% of hydrocarbons. The content of mono-aromatic, especially those of steroid type is relatively low.
Talphene derivatives are abundant; there also exist 25-35% of aromatics. The specific gravity is greater
than 0.85, and they include the Jurassic and Cretaceous oils from Middle East.
5. Aromatic-Naphthenic→ Represented by altered crude oil, most of the oil from this group are heavy,
viscous resulting originally from degradation of paraffinic, paraffinic-naphthenic, naphthenic and
aromatic-intermediate asphaltenes and resins are above 25% and may reach 60%. The relative content
of resins and asphaltenes and the amount of sulphur may vary according to the type of the original
material or oil type. This classification based on the normal and isoalkanes. It can also be divided by
percentage metals or non-metals present in crude oil. To reduce the amount of sulphur in crude oil in
crude oil, we can add silica gel. It would have more organometallics and heavy fractions because they
are due to biodegradation of the others.

ALTERATION OF OILS IN THE RESERVOIR

The changes of petroleum composition throughout the various stages of catagenesis have been
described, and the principle is such that as catagenesis proceeds, lighter and lighter hydrocarbons are
produced, and finally we get to metagenesis stage where only CH4 and to a larger extent, pyrobitumen
are formed. However, oils which have already been generated and migrated into the reservoirs are
subject to other effects as well as the normal maturation process. These additional changes occur
when the continuity of the reservoir horizons permit either up-dip meteoric water or down-dip gas to
come in contact with the oil accumulation. On the basis of that, the following are the main alteration
types of oils in the reservoir and their courses:

1. Normal maturation
2. De-Asphalting
3. Biodegradation
4. Water Washing
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1. NORMAL MATURATION→ The process of cracking the more unstable and heavier compounds to
lighter ones, and the formation of normal alkanes, at the expense of the naphthenes and the
aromatics. (Cracking has to do with increasing temperature; as a basin matures, subsidence increases
and temperature increases also due to geothermal gradient, when temperature increases with the
subsiding basin, aromatics and naphthenes are cracked). Light oils and condensates found in the late
stages of catagenesis are usually highly paraffinic, the additional hydrogen needed to form the alkanes
is robbed mainly from the aromatics which become condensed, the final end of the maturation process
occur in the stage of metagenesis where only dry CH4 gas and pyrobitumen- carbonized aromatics and
asphaltenes are found in reservoir traps.
2. DE-ASPHALTING→ This occur when down-dip gas and condensates can migrate into the reservoir traps
or in some cases, when normal maturation produces an excess of gas and condensates. If gas and light
hydrocarbons pass through the oil in solution, they precipitate the asphaltenes as reservoir bitumen,
and often there’s sufficient bitumen precipitated to result in severe plugging of porosity, at the same
time, the oil becomes lighter in gravity and is upgraded by the removal of the asphaltenes, the effect of
de-asphalting are often difficult to distinguish from the effect of normal maturation; but de-asphalting
usually affects individual reservoirs rather than occurring on a regional scale (compartmentalization of
reservoirs allows gases to de-asphalt the hydrocarbon in that reservoir without affecting another
reservoir, but both de-asphalting and normal maturation ends up with the same thing; lighter oil).
3. BIODEGRADATION→ This occurs when oxygen-charged meteoric water carry aerobic bacteria from the
surface to the oil accumulation in the reservoir trap. These aerobic bacteria attack mainly the normal
alkanes, though on a small scale, they affect others. Note: The meteoric waters must have a dissolved
oxygen content of at least 0.8mgl-1, contain nutrient and be free of H2S which will poison the bacteria,
the subsurface temperature must be ˂65OC, bacteria biodegradation can be a rapid process. The
product of biodegradation is degraded oil, heavier oils are produced. It is more common in oils that are
not very deep.
4. WATER WASHING→ This occurs when reservoir trap is in contact with moving meteoric water, the
process is simply the flushing away of the light hydrocarbon compounds in amount proportional to
their solubility. The results are to decrease the gasoline range hydrocarbon content and particularly, a
decrease in light naphthenes and aromatics which in turn produces an enrichment in heavy
components such as asphalthenes and a decrease of API gravity so that a heavy oil devoid of light
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component is the end result. (Water is a universal solvent, a lot of flowing water in contact with the
reservoir, bacteria breaks down the bonds and then water can flush the lighter oils away).

AGENCIES

1. PRESSURE: With increasing pressure of the overburden, there may be a chemical combination of oil
and methane, and this pressure build-up is likely to affect oil quality indirectly by causing renewed
migration in incompletely compacted sediments (as pressure build-up from the top, it forces gas into
the oil, this will lead to deasphalting and then tertiary migration because of the lightness of the oil).
2. TEMPERATURE: Raising the temperature of crude oil by the intrusion of pneumatolytic fluid or igneous
dykes will tend to gasify and crack the oil so that liquid hydrocarbons are converted to gaseous
methane. In areas where metamorphism has taken place, occurrence of gas fields instead of oil fields
might therefore be expected. There’s also the possibility that less intense heating over a longer period,
possibly combined with the catalytic action of a contiguous clay mineral which could bring about
changes of oil composition without destroying temperature sensitive constituents e.g. in Appalachan
region of the US, many relative small gas and oil fields are intersparsed and there appear to be a
relationship between the occurences of heavy oil, light oil and gas accumulation and the distance and
shelter of a localty from the Appalachan localty.
3. IRRADIATION: Irradiation of crude oils leads to increase in the content of asphaltenes and gaseous
hydrocarbons. This may also explain at least in theory, the chemical addition to the oil, of the free
hydrogen resulting from the radioactive bombardment of the lower hydrocarbon. Therefore, the effect
of lengthy exposure to natural radiation may well bring about appreciable chemical changes to the oil.
4. TIME AND AGE: Age is very much less important than thermal history in influencing maturation, but
like any other kinetic reaction, maturation will occur in less time in younger reservoir, if the
temperature is increased.

TAR SANDS, HEAVY OIL AND OIL SHALE

Note that Tar sands and heavy oils are alteration products.

Heavy Oil→ The result from the degradation of a normal (conventional) oil, that occurs in the host
rock. It is based on the variation of the different components of crude oil, depending on the original
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normal oil from which they are formed. It contains ˂50% of hydrocarbon and greater than 50% of
aromatics and asphaltenes. They result from leaching by water, microbial or oxygen degradation of the
light component. Specific gravity is between 0.93 and 1, API is 10-120. The origin is divided into two;
primary and secondary. Primary heavy oils occur at shallow depth, have low maturity levels and are
from source rock or special lithology. They contain abundant heterocompounds i.e. resins and
asphaltenes, generally result from a breakdown of high sulphur kerogen. They are different degraded
heavy oil by the occurrence of n-alkanes which have not been bacterially destroyed. Secondary heavy
oils, on the other hand, originate from mineral oil which has been subsequently degraded from the
reservoir by one or several of the following alteration process; they are of high sulphur content and
absence of heavy conctituents, microbial degradation, leaching by fresh water, loss of volatile
constituents and inorganic oxidation.

Physical and Chemical properties→ This is very important, in order to determine their influence and
impact on production, transportation and refining processes. The specific gravity is high i.e. 0.93-1.06
gcm-3. The viscosity is also high, between 100 to 10,000 cp at reservoir conditions. This is dependent on
the temperature, because with increasing temperature, there is decreasing viscosity. Chemically, they
contain less hydrocarbons and more sulphur from aromatic compounds. Saturates amount to ˂25%,
with average of 16%, while resins and asphaltenes range from 25-70%. This causes hydrogen deficiency
of heavy oils. The sulphur content may be as high as 5.6%.

Production→ The mobile ones under reservoir conditions can be produced by conventional methods at
a low efficiency, but the immobile ones are produced by enhanced oil recovery techniques such as
steam injection and insitu combustion. The steam injection depends on the viscosity reduction of oil
while insitu combustion makes use of hot air which pyrolysis the heavy oil; thus cracking it to yield
lighter oil. The largest occurrence of heavy oils are found in Horinoko basin or Horinoko heavy oil belt
in Venezuela and the second largest is the Burgam complex in Kuwait.
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PETROLEUM SYSTEMS AND ANALYSIS

The petroleum system is a natural system that encompasses a pool of petroleum source rocks and all
related oil and gas. It includes all the geologic elements and process essentials, if hydrocarbon
accumulation is to exist. Because of this, there are some risks associated with petroleum systems,
namely

 The probability of spending exploration fund without economic success

 Determining how high the probability is that petroleum have migrated from a mature source rock
into a trap and has not escaped or been destroyed.

Successful exploration depends on

a. Existence of a trap. Traps involve structures, reservoir and seal.

b. Accumulation of petroleum trap: source, maturation, migration to the trap and timing.
c. Preservation of the entrapped petroleum, which includes thermal history and meteoric water.

The probability of success is the product of the probabilities of all three factors above. Modern isotope
and biomarker analysis on the molecular level readily allows the identification and separation of
multiple sources of oil in a petroleum system. This is because oil inherits the molecular and isotopic
character of the parent kerogen, whereas natural gases or gas do not inherit the molecular or isotopic
properties from their parent kerogen.

(a) bond breaking processes that produce C1-C4 hydrocarbon gases involve temperature dependent
isotope fractionation that varies with the number of carbon in the molecule, temperature, type of
precursor i.e. kerogen

(b) Identification of the source of gas requires a reconstruction and correction of the fractionations
that occur during gas formation.

SAMPLING REQUIREMENTS AND THE PROBLEMS IN ORGANIC GEOCHEMISTRY

Note that over 90% of all geochemical analysis carried out for petroleum exploration, use as materials,
drill cuttings, chips from exploratory wells. Geochemical analyses have been designed to analyze
possible source rock for the following:

1. Organic Richness; to ascertain if the rock has enough organic matter to form kerogen
2. Petroleum generation potential
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3. Organic quality; to ascertain the kerogen type to form either oil or gas
4. State of maturation

There are also correlation analysis designed to identify a particular source for petroleum accumulation,
we have rapid and inexpensive analysis that can be done to give a preliminary evaluation and act as a
screen so that the more sophisticated and expensive analysis can be concentrated on the most
favorable part of the section. Analysis can be classified as one on a whole rock, kerogen, sorbed gases
and bitumen. A preliminary lithologic examination under the microscope and a check of the electric log
is essential to choose samples from the true lithology penetrated at any point in the drilling.
Contamination of drilling chip samples present a problem, thus handpicking is done. Sorbed gas
analysis requires that the drilled cuttings be collected as soon as they reach the surface, and stored
wet as recovered in sealed containers to minimize loss of gas.

Total Organic Carbon: Organic content analysis is a whole rock analysis which is an ideal screen for
organic richness; results are expressed in % organic carbon in the rock. Rocks with organic carbon
concentration of 0.5% are lean, between 0.5-1% fair, 1-2% good and over 2% is organically rich. The
rock eval pyrolysis is a whole rock analysis which is an ideal screen for organic quality. During pyrolysis,
three quantitative measurements are made:

a. Volatilized hydrocarbon from bitumen – S1

b. Volatilized hydrocarbon from the pyrolysis of the kerogen
c. Carbon dioxide given off by the kerogen pyrolysis.

The temperature of the peak of ‘2’ is also measured. Kerogen analysis requires preparation of kerogen
by removal of the enclosing rock using acid digestion and floatation process. The kerogen is then
mounted on glass slides or polished for microscopic examination. Cuttings and core samples are usually
used for geochemical analysis. Empirical samples are not used because of weathering. Once samples
have been exposed for a long time, oxidation process will degrade the kerogen.

PETROLEUM GEOCHEMICAL LOG

A number of geochemical analysis have been designed to answer certain specific questions needed in
petroleum exploration. These are the following geochemical analysis and the specific questions they
answer:
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1. Organic richness→ sufficient concentration of organic matter to form an effective source for
petroleum. If the concentration is too lean, it is useless to proceed with other analysis. Total organic
carbon (TOC) concentration is used.
2. Hydrocarbon potential→ quantity of hydrocarbons that the rock has sourced to date, and its potential
at higher levels of maturation. The analysis used is to extract hydrocarbons measured in (mg/g TOC),
rock eval (ppm of rock). Pyrolysis yields in ppm of rocks.
3. Organic quality→ whether the organic matter of the kerogen is more likely to source oil or gas. The
analysis includes microscopic examination of kerogen, rock eval pyrolysis.
4. Maturity→ the level of maturity in relationship to the oil and gas generating stages of catagenesis. The
analysis includes spore correlation index/thermal alteration index (SCI/TAI), vitrinite reflectance.
5. Oil source correlation→ this is the probability of a given source bed originating a given petroleum
accumulation. The analysis includes geochemical fossils (including heavy naphthenes), carbon isotopes,
C15+ chromatography of alkanes, and C4-C7 gasoline component chromatography.

THE USE OF PETROLEUM GEOCHEMISTRY AS A PETROLEUM EXPLORATION TOOL

This is mainly used in three areas:

a. Evaluation during drilling of exploratory wells in unexplored or little known areas.

b. As a basin evaluator or reappraisal tool
c. To answer special exploration problems

A: The chief requirement here is to obtain the evaluation concurrently with the drilling program (wild cat
or exploratory well). A decision to abandon drilling or to select another prospect for further drilling may
have to be made quickly on the result obtained by the currently drilled well. But the presence of rich but
immature source bed will suggest that the next prospect to be drilled should be deeper in the basin, where
the sorce bed will be in the stage of catagenesis. The section to be drilled may be largely unknown,
therefore an adequate drilling program is necessary. Drilled cutting samples are usually taken at intervals
of 3-30m (10-100ft), depending on the speed of drilling and lithologies encountered. Regardless of the
interval, the geologist at the wellsite should ensure that samples are taken from any stratigraphic unit that
form lithologic examination and appears to have a good possibility of a source bed. A rapid and effective
screen analysis program is mandatory and for this, a combination of TOC measurements and rock eval
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pyrolysis analysis will give a good organic richness analysis. If canned sample analysis is available, C 1-C4
analysis is possible by sorbed gas analysis.

B: These are usually major projects with geochemical analysis being done on as many as 50 wells
distributed throughout the basin. The area concerned may be a new basin or part of a basin under active
exploration or an old area where exploration exists but fresh interests have developed, a new exploration
is proposed. Firstly, the available geological data must be integrated on a series of cross sections and maps
to show the regional geology of the basin and its depositional and tectonic history. From this data, a
suitable well on which samples are available are selected and a planned geochemical analysis program to
determine which strata possess source potential and where in the basin during the course of their history,
whether they’re matured enough to source petroleum. This data are then obtained and plotted on the
cross sections and maps and where necessary, new maps are constructed to show the extent of the source
area and beds. The relationship to carrier beds and maps is then studied to determine likely migration
routes and which traps are most likely to contain petroleum. Oil and/or gas to source rock correlation
analysis may be carried out to confirm the suggested migration route. However, basin analysis projects can
often supply very valuable information at an insignificant cost when compared to total exploration project
budget in remote or off-shore areas where the cost of one exploratory well can run into millions of pounds
or dollars.

C: Puzzling problems are common in petroleum exploration. Examples are; (a) why are structures,
stratigraphic reservoirs, pinch-out and apparently valid traps barren of petroleum in certain areas? (b) why
are certain parts of a basin or certain formations gas prone?

In many areas, geochemistry has given answer to the above. Barren traps are often caused by lack of
source beds within the distance petroleum can migrate. Gas prone provinces are related to Type two
kerogen or areas where Type one and 3 are absent, or whether some beds are within the zone of
metagenesis. In spite of this, meeting the challenge and solving special problems is probably more
mentally rewarding to the practical geologist or geochemist than any other task he may be called upon to
perform.