ORGANIC GEOCHEMISTRY

IN OIL EXPLORATION

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 OUTLINES:

1. Introduction to Organic Geochemistry.

2. Source Rock Evaluation:-

A. Quantity of organic matter.

B. Quality of organic matter.
C. Thermal Maturation.
D. Extraction of bitumen.

3. References.
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 1. Introduction to Organic
Geochemistry.
 Petroleum originates from a small fraction of the organic matter
deposited in sedimentary environments.
 This organic matter is usually a combination of marine and
terrestrially-derived organic (plant) and zooplankton (animal), which
constitutes more than 95% of the life in the oceans.
 Terrestrial organisms are mainly wind-blown spores and pollen, along
with some woody debris from rivers and swamps.
 All living matter is composed of four main constituents, lipids,
proteins, carbohydrates and lignin.

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 1. Introduction to Organic
Geochemistry.
 The optimum requirements for accumulation and preservation of
organic matter include:
a. A large supply of organic matter.
b. An intermediate rate of sedimentation of fine-grained material.
c. An oxygen-poor environment to reduce oxidation and aerobic
microbial degradation of dead organic matter.
 Lagoons, estuaries, deep basins within the continental margins have
both organic contributions, sedimentation and a reasonable
anaerobic environment required for organic matter accumulation.
 Kerogen is a general term describing any insoluble organic matter in
sedimentary rocks and best described as a heterogeneous, highly
polymerized organic material.
 Bitumen is the soluble fraction of the organic matter. 4

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 1. Introduction to Organic
Geochemistry.
 Formation of oil and gas:-
 The process of petroleum generation is divided into three stages;
diagenesis, catagenesis and metagenesis.
A. Diagenesis (Ro 0.5% and Tmax 410⁰C to 420⁰C) .
 The first stage in the transformation of freshly deposited organic
matter into petroleum is called diagenesis.
 This process begins at the sedimentary interface and extends to
varying depths, but usually no deeper than a few hundred meters.
 During early diagenesis, one of the main agents of transformation is
microbial activity.
 During diagenesis, biological polymers (lipids-proteins,--) become
geopolymers then humin then finally kerogen with increasing T, P,
Overburden.
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 Diagenesis causes a decreasing O/C, with only a slight decrease
in H/C.
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1. Introduction to Organic
Geochemistry.
B. Catagenesis
 Catagenesis is the stage of thermal degradation of kerogen that forms oil
and gas.
 As a result of the temperature, kerogen is cracked to form liquid
petroleum and gas.
 Later stages of catagenesis results in the formation of methane from
kerogen.
 The end of catagenesis is generally accepted to be when all the major
sidechains of kerogen have been cracked.
C. Metagenesis
 Occur in areas of high geothermal gradients at shallower depths of about
4000 m.
 Towards the end of metagenesis, no hydrocarbons are being generated
from the kerogen. 6
 The H/C ratio and hydrogen index decrease only slightly during
metagenesis.
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  Oil Window is the depth range
over which oil generation occurs.

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 2. Source Rock Evaluation.
 Source rock evaluation can done through:-
A. Quantity of organic matter (TOC%).

 TOC% is the main factor in determining the quantity of organic

matter in source rock.
 TOC indicates the richness of the organic matter in the rock which
includes both the insoluble organic matter (kerogen) and the soluble
organic matter (bitumen). 8

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 2. Source Rock Evaluation.
 TOC analyses are usually run on a LECO carbon analyzer, which simply
combusts a sample of powdered, carbonate-free rock at very high
temperature in the presence of a large excess of oxygen.
 Mechanism of analysis:
1. ground the sample and remove carbonates by acid treatment.
2. combust the sample in the presence of excess oxygen in high temperature.
3. All organic carbon will convert to CO2
4. The CO2 is trapped till full
combustion and then is released
to a detector.

 When the TOC in shale greater than 5% ,It is Excellent.

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 When the TOC in Carbonate greater than 2% ,It is Excellent.
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 2. Source Rock Evaluation.
B. Quality of organic matter.

 Quality of organic matter can obtained by:

1. Rock Eval Pyrolysis (direct method).

 Pyrolysis is the decomposition of organic matter by heating in the

absence of oxygen
 The Rock Eval instrument provides a fast determination of the type
and evolution stage of kerogen, together with a direct evaluation of
hydrocarbon source potential.
 The type and quality of kerogen are usually interpreted on a graph
derived from the traditional Van Krevelen Diagram, by replacing the
H/C and O/C ratios with the hydrogen index (HI) and the Oxygen
index (OI).
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 2. Source Rock Evaluation.
 The maturation stage is usually obtained from T(max).

Rock Eval Pyrolyser

Out put of Rock Eval Pyrolyser 11

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 2. Source Rock Evaluation.
 S1: is the amount of free hydrocarbons that can be easily flushed
out of the rock during the early part of Pyrolysis.
 S2: is thermal decomposition of kerogen.
 S3: is the quantity of O2 in kerogen.
 S2/S3: is an indicator of hydrogen richness in the kerogen.
 S2/TOC: is related directly to the potential of the rock to generate
 oil rather than gas. The higher the hydrogen richness of the
kerogen, the higher the potential to generate oil.
 T(max): This is the Pyrolysis temperature of the S2 peak which can
obtain the maturation state. It is a useful back-up to vitrinite
reflectance, particularly in the late immature to strongly mature
stage.
 Hydrogen Index: of sample used as indicator of oil vs. gas
proneness. HI = S2 (mg/g)/%TOC × 100
 Oxygen Index: Oxygen richness of sample used as indicator of the
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kerogen type/degree of weathering.
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 2. Source Rock Evaluation.
 Type I

 This type of kerogen is characterized by having

a high initial hydrogen to carbon atomic ratio and
a low oxygen to carbon atomic ratio.
 Its primary source is from algal sediments.
 Called alginite kerogen (algal sediments, such as
 lacustrine deposits).
 Best source for oil-prone maturation.
 very rare.
 Type II

 This type of kerogen has a relatively high H/C ratio

and a low O/C ratio .
 Called exinite (marine sediments, where autochtho
-nous organic matter (bacteria, phytoplankton and
Van Krevelen Diagram
zooplankton) have been deposited.
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 It is a good oil or gas prone kerogen.
 It is more common than alginite.
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 2. Source Rock Evaluation.
 Type III

 This type of kerogen has a relatively low H/C ratio

and low O/C ratio.
 The main source of this type of kerogen are
continental plants found in thick detrital
sedimentation along continental margins.
 Called vitrinite kerogen.
 It is less favorable for oil generation, but will
provide a source rock for gas.

 Type IV

 Known as inertinite.
 This type of kerogen is usually associated with
coal or organic matter that has been greatly Van Krevelen Diagram
oxidized. 14

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 2. Source Rock Evaluation.

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 2. Source Rock Evaluation.
2. Vitrinite Reflectance (Ro%)

o A coal maceral group that is the dominant organic constituent of

humic coals.
o Used long time ago for measuring the rank of coals and used now to
measure the maturity of organic matters in rocks.
o How to measure the vitrinite reflectance:
 Isolate kerogen from the rest of the rock matrix with HCL and HF.
 Embed kerogen particles in epoxy and polish them.
 Measure the fraction of the incident beam that is reflected from an
individual vitrinite particle using photomultiplier.
 At least 30 individual grains of vitrinite from a rock sample is
measured.

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 2. Source Rock Evaluation.
C. Thermal Maturation.

1. Tmax.
o It is the temperature at which the maximum rate of hydrocarbon
generation occurs (peak of S2).
o As maturity increases,
temperature at which the
maximum rate of Pyrolysis
occurs increases.

o Problems associated with Tmax:

1. dependant upon kerogen type.
2. b/c kerogen type may vary from
3. sample to sample along well
profile.
4. Tmax does not show regular 17
progression with depth
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 2. Source Rock Evaluation.
C. Thermal Maturation.
1. Production Index (P.I).

o Called also transformation

ratio which is S1/(S1+S2).

o With increasing maturity,

kerogen is converted to
bitumen (i.e. S2 decreases
while S1 increases).

o Migration of hydrocarbons
into and out of rocks
complicate the pictures.

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THERMAL ALTERATION INDEX
The table below shows a very generalized correlation of kerogen
maturity parameters with SCI and TAI

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Vitrinite refle Spore Thermal Generalized
Pyrolysis
ctance coloration alteration hydrocarbon
Tmax (°C)
(%Ro) index (SCI) index (TAI) zone
0.40 4.0 2.0 420 Immature
0.50 5.0 2.3 430 Immature
0.60 6.0 2.6 440 Oil
0.80 7.4 2.8 450 Oil
1.00 8.1 3.0 460 Oil

1.20 8.3 3.2 465 Oil & wet gas

1.35 8.5 3.4 470 Wet gas

1.50 8.7 3.5 480 Wet gas
2.00 9.2 3.8 500 Methane
3.00 10 4.0 500+ Methane 19
4.00 10+ 4.0 500+ Overmature
SPORE COLORATION INDEX (SCI) SCALE
PROPOSED BY FISCHER ET AL. (1981).

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 Rate of Maturation

Source: North, F.K. (1985) Petroleum Geology, Allen & Unwin

Temperature is the single most important factor in thermal maturation.

 Rate of Maturation ctd.

Source: North, F.K. (1985) Petroleum Geology, Allen & Unwin

Time is the second most important factor in thermal maturation

Purposes of Maturation Indicators
• To recognize and evaluate potential source rocks for oil and
gas by measuring their contents in organic carbon and their
thermal maturities
• To correlate oil types with probable source beds through their
geochemical characteristics and the optical properties of
kerogen in the source beds
• To determine the time of hydrocarbon generation, migration
and accumulation
• To estimate the volumes of hydrocarbons generated and thus
to assess possible reserves and losses of hydrocarbons in the
system.
Lopatin’s TTI Index

V. Lopatin (1971) recognized the

dependence of thermal maturation
from temperature and time. He
developed a method where in the
temperatures are weighted with the
residence time the rock spent at this
temperature. Periods of erosion and
uplift are also taken into account. This
so-called time-temperature index TTI
is still in use, although in variations.

The plot on the right shows a simple

depiction of it. Rock of age A enters the
oil-generating window at time y, while
the older rock B has been at that time
already in the gas-generating window
and will stay there until the present.

Source: North, F.K. (1985) Petroleum Geology, Allen & Unwin

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 2. Source Rock Evaluation.
D. Extraction of Bitumen.

TLC

GCMS LC
Extraction
of
Bitumen

GC MPLC
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 2. Source Rock Evaluation.
D. Extraction of Bitumen.
o Soluble organic matter (Bitumen fraction) Isolated from the finely
powdered rocks by organic solvents (e.g. dichloromethane).
o The separated Bitumen fraction consists of mixtures of different
classes of organic compounds.
o We will go through many techniques for further extraction of
bitumen and biomarkers as follow:

1. Thin Layer Chromatography (TLC).

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 2. Source Rock Evaluation.
o Thin layer of absorbent (stationary phase) on a flat solid support.
o Sample dissolved in a solvent (mobile phase), applied to the
lower edge and therefore, migrate upwards by capillary action.
o Separation theory, Solutes partitioned differentially between the
stationary and mobile phases

2. Liquid Chromatography (LC).

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 2. Source Rock Evaluation.
3.Medium Pressure Liquid Chromatograph (MPLC).

o (MPLC) is a quantitative method of

analysis used to separate sample into
saturated hydrocarbons, aromatic
hydrocarbons and polar materials.

o It utilizes a pre-column containing

thermally-deactivated silica and
a main column of activated silica as
the stationary phase (SP) with
n-hexane serving as the mobile phase
(MP).

o Used for separation of saturates, aromatics, NSO and asphaltine.

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 2. Source Rock Evaluation.
4. Gas Chromatography (GC).

o After obtaining the less

complex fractions, we use GC.
o Separation using GC depends
on the partitioning of analyte
between the gaseous mobile
phase and the liquid stationary
phase.
o Steps:

1. Solution of the sample introduces by syringe into injector.

2. Mobile phase (Carrier gas) sweeps the sample into capillary column
in an oven where analytes are separated.
3. On elution from the column analyte passes into a detector where
signals is generated, amplified and converted onto digital signal 30
stored by computer.
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 2. Source Rock Evaluation.

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 Biomarkers

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 2. Source Rock Evaluation.
Biomarkers obtained from GC.
o Biomarkers are organic compounds that act as chemical tracer of
certain ancient organisms.
o Found in just one group of organisms.
o Known as molecular fossils, geochemical fossil and biological marker.

I. Alkanes.

Carbon Preference Index{CPI}:-

o It is odd/even ratio

o CPI used to determine the depositional environment as follow:-

o If CPI > 1 → (i.e., Marine Source Rock)
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o If CPI< 1 → (i.e,Terrestrial to Lacustrine sourse rock)

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 2. Source Rock Evaluation.
II. Isoprenoids.

Pristane/Phytane ratio.

o Isoprenoids are lipids constructed from isoprene or isoprane(5-

carbon) subunits.
o When phytol undergoes diagenesis and catagenesis, pristane and
phytane pristane and phytane are two of the major biomarkers
that are produced.

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 2. Source Rock Evaluation.
o Pristane/phytane Ratio used to determine depositional
environment.

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 2. Source Rock Evaluation.
5. Gas Chromatography Mass Spectrometry (GCMS).

o Analytes in the sample are separated

in capillary column of GC
unit and introduced MS.
o In the mass spectrometer, electrons
from a heated filament ionize the analyte
molecule.
o The ionized molecules are focused into
quadrupole mass analyzer which causes
ions of successive mass-to-charge
ratios (m/z) values to be transmitted. GCMS
o The ions from the mass analyzer then
impinge on electron multiplier that induce
a current that can be measured and send
to the computer for manipulation and storage. 36

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 2. Source Rock Evaluation.

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 2. Source Rock Evaluation.
Biomarkers obtained from GCMS
(Saturated Hydrocarbon Biomarkers).

I. Triterpanes.

Oleanane Index(O.I).
o Oleanane is the name given to chemicals produced by many
flowering plants, which have a suppressing effect on some insect
pest organisms.
o Technically they are oleanane triterpanes.
o They are considered a key marker differentiating flowering plants
from other life, and have been used in the effort to study their
evolution which is as of yet poorly documented in the fossil record.
o When Oleanane present with Oil →( i.e,Typically non marine origin)
o O.I is held to be a marker of angiosperm of Upper Cretaceous or
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Younger Tertiary age.
o O.I = (Oleanane ÷ C30 Hopane)* 100.
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 2. Source Rock Evaluation.
Gamma Cerane Index (G.I):-
o Gamma Cerane is high relative to C31hopanes in oils derived from
sources deposited under hyper saline depositional conditions.
o High values of G.I indicates stratified water column during sourse
deposition.
o If G.I > 30% in oil or sourse rock i.e, the environment is marine of
high salinity.
o G.I = (Gamma Cerane ÷ C30 Hopane)* 100.

Ts/Tm ratio:-
o Ts → 18α-22,29-30 trisnorhopane.
o Tm→ 17α-22,29,30 trisnorhopane.
o Ts/(Ts+Tm) appears to be sensitive to clay catalyzed reactions so,
oil from carbonate sourse rocks appears to have low
Ts/(Ts+Tm) ratios compared with those from shales.
o Bitumen from many hyper saline sourse rocks show high
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Ts/(Ts+Tm)ratio.

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 2. Source Rock Evaluation.
C35/C34 Homohopane ratio (H.I).
o Increasing this ratio indicates strongly reducing environment
“Marine evaporates and carbonates”
o Abundance of C35 Homohopane in oils is correlated with source
rock hydrogen index.

II. Sterane.

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 2. Source Rock Evaluation.
o Higher plants contain
abundant C29.
o Abundant C27
in zooplanktons.
o Abundant C28
in phytoplankton.
o Triangle plot of C27, C28
, C29 sterols can aid in
differentiating,
• marine
• estuarine
• lacustrine
• terrestrial
o based on the Sterane Ternary Diagram
characteristic associations of contributing organisms.
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 3. References.

o Geochemistry in petroleum exploration, Douglas W.Waples.

o http://www.oiltracers.com/services/explorationgeochemistry/oil-
biomarker-summary.aspx.

o Petroleum geology, Baker Hughes Inteq, 1999.

o Petroleum geochemistry and geology, John M. Hunt, 1995.

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 THANK YOU

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