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Organic Matter and Fossil Fuel: Kerogen types

• Kerogen
• Composed of very long carbon chains with attached functional groups
• Molecules have very high molecular weight

• Kerogen classifications
• Type I (very petroleum prone)- H/C>1.35, O/C<0.15
• Type II (petroleum prone)- 1<H/C<1.35, 0.03<O/C<0.18
• Type III (natural gas prone) – 0.5<H/C<1, O/C upto 0.3
• Type IV (inert) - H/C<0.5, 0.2<O/C<0.3

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Organic Matter and Fossil Fuels (cont.)

• Higher hydrogen and lower oxygen contents in kerogen correspond to greater

petroleum-generating potential
• Sapropelic coal (Only exception that can produce petroleum)
• Coal formed from algal material in oxygen-depleted ponds, lakes, and lagoons
• Can produce kerogen
• Also called boghead or cannel coal
• It contains waxes and fat with high hydrogen content
• Kerogen buried in the surface heats up
• Long Kerogen chains start to break down at depth and produces crude oil
• Compositions can vary widely

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Organic Matter and Fossil Fuels (cont.)

• Crude oil and natural gas windows

• Oil window is the depth region where
crude oil is produced
• Oil window at a particular place on
earth depends on both the
temperature gradient and the rate the
organic-rich sediments were buried

• Typical oil window= 2-5 km

• Above 2 km (no oil release from
Kerogen) and below 5 km (kerogen
breaks to gases)
• Gas window= 3- 6.5 km
• Below 6.5 km= only carbon (graphite)

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Organic Matter and Fossil Fuels (cont.)

• Fingerprinting oil
• Technique where crude oil is identified by the uniqueness of its composition
of different organic molecules
• Helps oil companies identify the source reservoirs from which oil is taken
• Provides forensic evidence in oil spill cases to prove or disprove a particular
tanker or oil platform as the source of a spill

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Gas Chromatography
Of course you may have wondered how petroleum compositions and
structures are determined. By far the most common method is gas
chromatography, which, supplemented with mass spectrometry, makes
identification accurate and fast.

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

The large peaks are paraffins, while the smaller ones belong to naphthenes.

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Methods of Petroleum Source Rock Evaluation

• Vitrinite reflectance (VR)

• Most commonly used organic maturation indicator
• Accurate, quick, nondestructive, and inexpensive
• Vitrinite forms in organic matter during burial and thermal alteration of six
member carbon rings in coals and to a small extent in kerogens.
• Reflectance, %R0 , is the percentage of light reflected from the sample
surface, calibrated against a mirror (100% reflectance)
• Onset of crude oil generation typically corresponds with a VR of 0.5 to 0.6%R0

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Methods of Petroleum Source Rock Evaluation (cont.)

• Van Krevelen (atomic H/C vs. O/C)
diagram
• Best way to evaluate the quality and
maturation state of kerogen as well as
coal in the subsurface and relate it to
VR
• Bacteria transform hydrogen and
oxygen in kerogen to H2O, which is
released, causing the H/C and O/C
ratio to decrease
• Bacterial-produced CO2 is also lost
leading to H/C increase

Adapted from Hunt, J. M., 1996, Petroleum Figure: Van Krevelen diagram showing the pathway of maturation
Geochemistry and Geology, Freeman and Co.,
New York, 743 p. for the four different types of kerogen with burial.
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Source: North, F.K. (1985) Petroleum Geology, Allen & Unwin

Kerogen Types & Maturation

Sapropelic kerogen
(algae)

Lipid-rich kerogen
(phyto- and zooplankton)

Humic kerogen
(land plants)

“Van Krevelen diagram”

TAI, VR: Maturation indicators

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Methods of Petroleum Source Rock Evaluation (cont.)

• Rock-Eval pyrolysis
• Used to identify the type and extent
of maturity of the OM in a rock by
programmed heating of the rock in
a pyrolysis oven

• Very heavy hydrocarbons are

volatilized and some nonvolatile Figure: Typical Rock-Eval
organic matter is volatilized by pyrolysis plot showing loss of
cracking, producing the S2 peak hydrocarbons as a function of
timed heating.

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Kerogen Cracking

Existing HC

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Rock-Eval Pyrolysis
• Rock-Eval pyrolysis involves heating a rock sample in an inert
atmosphere and measuring the hydrocarbons and CO2 released at
different temperature stages.
• Sample: crushed powder

First Heating Stage (S1 Peak):The sample is heated to about 300°C in

an inert atmosphere (usually helium or nitrogen).
• This stage measures the free hydrocarbons already present in the sample,
which are volatilized without breaking down the kerogen. The amount of
hydrocarbons released is recorded as the S1 peak.

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Rock-Eval Pyrolysis
• Second Heating Stage (S2 Peak): The temperature is then increased
to about 600°C at a controlled rate (usually 25°C per minute).
• During this stage, kerogen (the solid organic matter) is thermally decomposed
(pyrolyzed) to release hydrocarbons. The quantity of hydrocarbons generated
from the thermal breakdown of kerogen is recorded as the S2 peak.

• CO2 Measurement (S3 Peak): The CO2 released during the pyrolysis of
the organic matter is also measured. This is often recorded as the S3
peak

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Rock-Eval Pyrolysis
Oxidation:
• After pyrolysis, the residual carbon (remaining after S2) is further
oxidized in the presence of oxygen to measure the remaining organic
carbon content.
• This oxidation stage helps in determining the Total Organic Carbon
(TOC).

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Rock-Eval Pyrolysis: Key parameters

S1 Peak (mg HC/g rock):
Represents the amount of free hydrocarbons present in the sample that can be readily evaporated
without pyrolysis.

S2 Peak (mg HC/g rock):

Indicates the quantity of hydrocarbons generated from the thermal decomposition of kerogen. This is
a crucial parameter for evaluating the hydrocarbon-generating potential of the rock.

S3 Peak (mg CO2/g rock):

Measures the amount of CO2 released during the pyrolysis, which indicates the oxygen content of the
organic matter.

Total Organic Carbon (TOC, wt%):

The total amount of organic carbon present in the rock sample, determined after the oxidation stage.

Tmax (°C):
The temperature at which the maximum amount of hydrocarbons is generated during the S2 peak.
Tmax is used as an indicator of the thermal maturity of the organic matter. Higher Tmax values
indicate more mature organic matter.

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Rock-Eval Pyrolysis: indexes

• Hydrogen Index (HI):
• Calculated as S2/TOC×100. It represents the amount of hydrogen-rich
hydrocarbons generated relative to the organic carbon content.
• Oxygen Index (OI):
• Calculated as S3/TOC×100. It indicates the oxygen content relative to the
organic carbon content.
• Production Index (PI):
• Calculated as S1/(S1+S2) . It provides an es mate of the extent of
hydrocarbon generation and expulsion. Higher PI values indicate a more
mature stage of hydrocarbon generation.

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Rock-Eval Pyrolysis: Interpretation

• Kerogen Type:
• The HI and OI values can help in identifying the type of kerogen present (Type
I, II, III, or IV), which in turn indicates the type of hydrocarbons that might be
generated (oil or gas).
• Maturity:
• Tmax and PI values provide insights into the thermal maturity of the organic
matter.
• Hydrocarbon Potential:
• The S2 peak gives a direct measure of the potential hydrocarbon yield from
the sample, which is crucial for assessing the rock’s ability to generate oil or
gas.

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Assignment

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Crude Oil Deposits: characterization

• In most profitable reservoirs, 40% or more of the pore fluids must be

hydrocarbons
• Crude oil is usually characterized by its density as given by the API
gravity number expressed in degrees (°)
• Oil floats on water at greater than 10° and sinks at less than 10°
• The lighter an oil, the higher its API gravity

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Crude Oil Deposits (cont.)

• Determining the API number
• Formula: API = 141.5 - 131.5


• API: degrees of API gravity

• ρ: crude oil density in g/cm3 at 60 oF
(15.6 oC)
• Light crude: API > 31.1°
• Medium crude: API of 22.3°to
31.1°
• Heavy crude: API < 22.3°

• Sweet crude (S<0.5%)

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