CHAPTER 7

• ORIGIN OF PETROLEUM
 Origin of Petroleum

• Inorganic theories
– Cosmic sources: hc’s found in meteorites
• The discovery (Mueller, 1963) of a type of meteorite
called carbonaceous chondrites.
• Chondritic meteorites contain greater than 6%
organic matter and traces of various hydrocarbons
including amino acids.
• The chief support is that the hydrocarbons methane,
ethane, acetylene, and benzene have repeatedly
been made from inorganic sources.
 Origin of Petroleum

– Reaction of metal carbides in the earth

• Mendele’ve (1902) reasoned that metallic carbides
deep within Earth reacted with water at high
temperatures to form acetylene.
CaC2 + 2H2O = C2H2 + Ca(OH)2
• Then Porfir’ev (1974) – iron carbide react with
percolating water to form methane and other oil
hydrocarbons.
FeC2 + 2H2O = CH4 + FeO2
• There is little evidence for the existence of iron
carbide in the mantle.
 Origin of Petroleum

- Hydrocarbon from the mantle (Outgassing theory)

• Detailed analysis of the gases escaping onto the
surface of the earth during earthquakes reveal the
presence of methane, CO2, H2S.
• Peyve (1956) and Gold and Held (1987) have argued
that subcrustal abiogenic hydrocarbon and other
gases migrate up the major faults to be trapped in
sedimentary basins.
• Limitation: This theory implies that to find limitless
quantities of oil and gas all that needs to be done is to
drill adjacent to faults.
 Origin of Petroleum

• Organic theory
• From transformation of biomatter.
• The biogenic origin of petroleum is widely
accepted on the basis of geochemical studies.
• The deposition of an organic-rich sediment is
favored by a high rate of production of organic
matter and a high preservation potential.
• The preservation of organic matter is favored by
anaerobic bottom conditions and a rapid
sedimentation rate.
Origin of Petroleum
 Basic Components of Organic Matter

• The principal biological components of living organisms

are:
• PROTEINS
– More abundant in animals: O, C, N, H
• CARBOHYDRATES
– Occur in both. Cn(H2O)n
– sugars, cellulose, starch
• LIPIDS (Fats)
– Occur in both: C, H, O
– Fats, oils, waxes (e.g. leaf cuticles)
• LIGNIN
– Occurs in plants: complex aromatic ring structures, large
molecules
 Average Composition of Biomolecules

Average Composition of
C
C H O S N

Lipids 76 12 12 - -

Proteins 53 7 22 1 17

Carbohydra 44 6 50 - -
tes

Lignin 63 5 31.6 0.1 0.3

Petroleum 83-87 10-14 0.1-1.5 0.5-6 0.1-1.5

 Basic Components of Organic Matter (OM)

• How do living organisms become Organic Matter?

Organism dies: decay begins
Complex molecules break down rapidly.

• How then does OM accumulate in the vast

quantities needed for identified oil volumes?
Accumulation of large quantities of living organisms
requires Oxygen.
To facilitate oil generation, the OM produced by the
death of these organisms must be preserved.
Preservation of large quantities of dead organisms
requires Anoxia (anoxic environment).
 Productivity and Preservation of
Organic Matter

• Geochemical evidence that oil source beds were

deposited in four main anoxic environments in
the geological record.
– Large anoxic lakes
– Anoxic silled basins
– Anoxic layers caused by upwelling
– Open-ocean anoxic layers
 Productivity and Preservation of
Organic Matter

– Large anoxic lakes

Permanent stratification promotes development of
anoxic bottom waters, particularly in large lakes not
subject to seasonal overturn.
E.g. Lake Tanganyika: warm equitable conditions all
year.
Lake Tanganyika

NW SE

PERMANENT THERMOCLINE
1.5km
CH4 , H2S

Longitudinal section
525km
 Productivity and Preservation of
Organic Matter
– Anoxic silled basins
• Landlocked silled basins with positive water balance:
good chance of developing anoxia.
E.g. Black Sea, Baltic Sea.
In arid-condition silled basins (Red Sea,
Mediterranean).
 Productivity and Preservation of
Organic Matter

– Anoxic layers caused by upwelling

• Only develop when surface biological processes
exceed deep water oxygen supply
E.g. Benguela current, Peru coastal upwelling.
 Total Organic Carbon (TOC)
-Source rock evaluation
• If a rock contains significant amounts of organic carbon,
it is a possible source rock for petroleum or gas.
• The TOC content is a measure of the source rock
potential and is measured with total pyrolysis.
• The table below shows how TOC (in weight percent)
relates to the source rock quality.
TOC Quality
0.0-0.5 poor
0.5-1.0 fair
1.0-2.0 good
2.0-4.0 very good
>4.0 excellent
 How does OM become Oil?

• 2 stages:
• Conversion of OM to kerogen
• Conversion of Kerogen to oil
and gas
 Transformation of OM into Kerogen

• As the organic matter is buried, it transforms from basic

biological components into new polymeric organic
compounds that eventually become kerogen.
• What is kerogen?
• Insoluble in organic solvents
• Complex mixture of high molecular weight organic
materials
• Kerogen is composed of varying proportions of C, H,
and O. General composition may be described as:
• (C12H12ON0.16)x
 Type of Kerogen
- Source rock evaluation

• It is important to identify the type of kerogen in a source

rock.
• Type I : algal kerogen
• “best” oil source
• Lipid-rich
• Type II: herbaceous (liptinic) kerogen/ lipid-rich kerogen
• Good oil source
• Includes zooplankton (sapropelic)
• Type III: woody (coaly/humic) kerogen
• Good gas source
• Rich in humic components
• Type IV: amorphous kerogen
 Type I Kerogen
• Rare
• High-grade algal sediment
• Generally lacustrine
• Contains sapropelic OM
• Oil shales, coorongite & tasmanite,
Boghead coals
• H:O = 1.2- 1.7; H:C = 1.6 – 1.8
• Lipids are the dominant compounds
 Type II Kerogen
• Intermediate derivation
• Commonly marginal marine
• Mixture of continental and aquatic
(planktonic) OM
• Algal tissue, pollen, spores
• Principal source for oil
• H:C = about 1.4
 Type III Kerogen
• Sediment containing primarily humic OM
• Terrestrial (woody) origin
• Equivalent of coal vitrinite
• Deposited at the oxic water/ sediment
interface
• Gas-prone
• H:C < 1.0 (more C than H)
 Type IV Kerogen
• From any source
• Oxidized, recycled or altered during an
earlier thermal event
• Inert carbonaceous material
• H:C < 0.4
• No evolutionary path left: no hydrocarbons
generated.
 What happens to kerogen as it is
buried and heated?
• Large molecules crack to smaller low mol. wt.
Geomonomers: 1000-6000m depth; 50-175°C
– Initial products are H2O and CO2
• Increased temp and burial:
– Volatile products lost (hydrogen, CH4) and liquids
(C13 – C30)
– O2 lost rapidly by dehydration and decarboxylation
(loss of CO2 from fatty acids)
– C and N lost least readily
• Thus with increasing temperature:
– C-content of kerogen rises
– H:C ratio decreases

• Two fractions are produced by thermal

transformation of kerogen:
– Fluid high in H (petroleum and natural gas
precursor)
– Residue high in C (e.g. bituminous coal, bitumen)
 What happens when we subject kerogen to
subsurface conditions?
KEROGEN
Shallow subsurface
Normal pressure and temperature
Diagenesis Released: CH4, CO2, H2O
• Overall decrease in O
• Overall increase in H and C

Deeper subsurface
Increased pressure and temperature
Catagenesis Released: oil & gas
• Overall decrease in H and C

Metamorphism
High temperature and pressure
Metagenesis Only C remains: becomes graphite
When is oil expelled?
 The result of this?
• The amount of oil generated increases
linearly with time
• The amount generated increases
EXPONENTIALLY with temperature.
• Thus, TIME IS AN IMPORTANT FACTOR
 Time and oil generation
• The younger the source, the higher the
temperature required to generate oil
• RESIDENCE TIME
 This Introduced the Concept of the
OIL WINDOW

• A range of temperatures through which oil

generation can occur
• Below 60°C: sediments are immature
• Above the critical temperature (Approx
120°C): sediments are post-mature
• Assumes that no migration of the oil has
occurred (I.e. into lower temperature regimes)
The principal zone of oil formation
during the thermal generation of
petroleum hydrocarbons
Temperature is the single most important factor in thermal maturation
Time is the second most important factor in thermal maturation
 Maturation of Kerogen
- Source rock evaluation

• Establishing the level of maturation of kerogen in the

source rocks is vital in petroleum exploration.
• The maturity of a source rock is a measure of the degree
to which reactions have proceeded in the generation of
petroleum products from organic matter.
• With increasing maturity, first oil and then gas are
expelled.
• The rate of maturation may be dependent on
temperature, time, and, possibly, pressure.
 Maturation of Kerogen
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.
 Maturation of Kerogen
• Several techniques have been developed.
• Two commonly used maturation indices are:
• 1) Thermal maturity index (TTI)
• 2) Level organic maturation (LOM)
• TTI is calculated from a formula that integrates
temperature with the time spent in each temperature.
• LOM is based on the assumption that reaction rate
doubles for each 10oC increment of temperature.
• LOM values of 7 – 13 (oil generation occurs), LOM = 13-
18 (gas generation occurs).
 Maturation of Kerogen
• Techniques for determining temperature:
• Paleothermometers: two major groups of techniques are
used:
• 1. Chemical Paleothermometers
a) Organic
i. Carbon ratio
ii. Electron spin resonance
iii. Pyrolisis
b) inorganic
i. Clay mineral diagenesis
ii. Fluid inclusion
 Maturation of Kerogen
• 2. Biological Paleothermometers
a) Pollen coloration
- measure the color of organic matter (spores and
pollen)
- essential colorless and then change to yellow,
orange and brown.
b) Vitrinite reflectance
- used a reflected-light microscope to measure the
degree of reflectivity of vitrain (coal maceral).
Maturation of Kerogen