The Petroleum System:
Source Rocks
Reading
1. Peters, K. E., and M. R. Cassa, 1994, Applied Source
Rock Geochemistry
2. Chapter 3 (partial) from Organic Geochemistry by
Waples
3. Page 53, from Petroleum Geology by North
4. Source Rocks, Chapter 10 by Hunt?
1
Petroleum Source Rock: Definition
A petroleum source rock is any rock that
has the capability to generate and expel
enough hydrocarbons to form an
accumulation of oil or gas
Hunt,
1996
A rock
that has, or once had, the chemical
precursors of hydrocarbons and could
expel, or has already expelled,
hydrocarbons due to thermal maturation
Dispersed Organic Matter
(DOM) in Shale
Immature Shale Minerals ~1-10+%
~90+%
Kerogen
Organic Matter (Insoluble)
Asphaltene &
Resin
Bitumen
(also pyrobitumens Aromatic HC
Saturated
which are HC
insoluble)
2
Heterogeneity
(Stratigraphic)
Source
rock
propertie
Are not
s here. . .
the same
as source
rock
propertie Figure Provided by David
Thul
5 s here
Heterogeneity
(Geographic)
Source Are not
rock the same
propertie as source
s here . . . rock
propertie
s here
Figure Provided by David Thul; Modified from Finn and Roberts (2005); after Roberts & Kirschbaum
(1995)
3
Geologic Origins of Petroleum
• Burial by sediments must be rapid to prevent
oxidation or waters must be anoxic.
• Sediments bury the organic matter to depths of
several kilometers.
• At these depths, it is hot (~60-175 C; ~140-350 F).
• The heat and pressure break down (crack) the
organic matter (kerogen) to form petroleum.
• Heating must remain “at the temperature of a
HOT cup of coffee” for ~1 million years or so.
Thermogenic Hydrocarbons
• Hydrocarbon generation requires heat
• Geothermal gradient
<1 to 11 ºF per 100 ft
Typical sedimentary basins: 1.0 -
1.7 ºF per 100 ft
A good average ~1.2 ºF per 100 ft
4
Transformation of Organic Matter
• Tissot (1977) defined 3 successive stages of
organic metamorphism with increasing burial
depth and temperature:
1. Diagenesis occurs in the shallow subsurface near
normal T and P. It involves biogenic decay (aided
by bacteria) and other reactions. Methane, CO2, and
water are generated by the organic matter (with an
associated decrease in oxygen content), leaving the
complex hydrocarbon called kerogen.
2. Catagenesis
3. Metagenesis
Transformation of Organic Matter
• Tissot (1977) defined 3 successive stages of
organic metamorphism with increasing burial
depth and temperature:
1. Diagenesis
2. Catagenesis occurs deeper in the crust as burial
continues and T & P increase. Petroleum is generated
from the kerogen – first oil and later gas. The H:C
ratio declines.
3. Metagenesis
10
5
Transformation of Organic Matter
• Tissot (1977) defined 3 successive stages of
organic metamorphism with increasing burial
depth and temperature:
1. Diagenesis
2. Catagenesis
3. Metagenesis occurs with deep burial and high T &
P. The last hydrocarbons, generally only methane,
are generated. The H:C declines until only carbon
remains (as graphite). Porosity and permeability are
negligible.
11
Transformation of Organic Matter
Organic Compounds CH4
Kerogen
C34H54 C16H18
C7H13 C3H16
API Gravity
Thermogenic Methane
Methane CH4
Graphite C
The onset and range of hydrocarbon generation varies
with the type of organic matter
12
6
Organic‐rich source rocks
Presence
Thickness
Aerial Extent
Effectiveness
Kerogen Type
Richness (Quantity)
Maturity
Mineralogy
13
Kerogen – the precursor to Petroleum
• Kerogen consists of the
fossilized carbonaceous
remnants of plants and
animals of both aquatic
and terrestrial origin,
and is insoluble in
organic solvents.
Occurs only in
post Silurian‐age
rocks
14
7
Kerogen Type
• Four types based on maceral content:
1. Algenite (algal or sapropelic; oil prone)
2. Exinite (mixed; lipid rich)
3. Vitrinite (woody or humic; gas prone)
4. Inertinite (inert; dead carbon)
EOD is important:
• The kerogen type reflects the original organic matter
• Timing and range of petroleum generation/expulsion varies by type
• The type and yield of petroleum varies by kerogen type
15
Kerogen - Maceral Types
• Botryococcos (Type I)
• Fat-secreting,
planktonic green
algae
• Type II, Kimmeridge
clay amorphous
organic matter “AOM”
• T
y
p
e
16 II
I,
W
o
o
d
8
y
Van Krevelen Diagram
Alginite (algal; oil prone)
Developed by van
Krevelen (1961) to
analyze changes Exinite (lipid rich; oil / gas)
in coal
composition
during burial Vitrinite (woody;
gas
(coal maturation) prone)
Adopted by
Tissot et al.
Inertinite
(1974) for
kerogen
Graphite
Modified from
North (1985)
17
Kerogen Type
• Four types based on maceral content:
• Alginite (Type I) has a high H:C ratio
but a low O:C ratio.
• It is oil-prone, with a high yield (up
to 80%; yield is the volume of
hydrocarbon generated for a given
volume of source rock).
• It is derived mainly from an algal
source, which formed in lacustrine
and/or lagoonal environments (an
algal-prone source). Also known as
algal kerogen.
18
9
Kerogen Type
• Four types based on maceral content:
• Exinite (Type II) has intermediate
H:C and O:C ratios.
• It is oil- and gas-prone, with yields
of 40-60%.
• The source is mainly lipid-rich (fat
and wax) membranous plant debris
(waxy coatings of spores, pollen,
and leaf cuticles), and
phytoplankton (e.g., marine algae)
and bacterial microorganisms in
marine sediments (a mixed /
intermediate source).
19
Kerogen Type
• Four types based on maceral content:
• Vitrinite (Type III) has a low H:C
ratio and high O:C ratio.
• It forms a low yield kerogen,
principally generating gas.
• The primary source is lignin of
higher woody plant debris like
those found in coals (a wood-
prone source). Also known at
humic kerogen.
20
10
Kerogen Type
• Four types based on maceral content:
• Inertinite (Type IV) has a very low
H:C ratio and high O:C ratio.
• It has no effective potential to yield
oil and gas and is often called a
“dead-carbon”.
• The primary source could be the
same as any of the other kerogen
types.
21
Kerogen Types – methods to
evaluate
Three ways to
evaluate kerogen
Van Krevelen
type:
Diagram
Elemental
Analysis
Pyrolysis
Microscopy
Pseudo or Modified
Van Krevelen
EA is the most accurate but it
Diagram
is expensive and time
consuming.
Pyrolysis is the fastest and
cheapest, but most subject to
22 error.
Visual is somewhere in the
middle.
11
Peters & Cassa in Magoon & Dow, 1994
Kerogen / Organic-matter Richness
The quantity of organic matter defines its
“richness”, which relates to its petroleum
potential in 2 ways – the richer the source:
1. Greater volume of hydrocarbons
can be generated
2. Greater efficiency of hydrocarbon
migration
Quantity of organic matter is expressed as
the
TOC in wt.%
23
Expulsion Efficiency
Arango (2019)
24
12
Influence of Organic Matter
e.g., Type II
e.g., Type III
Arango (2019)
25
Influence of Source Rock Contact
Area
Expulsion efficiency is greater with more contact
area between source and carrier beds
26 Arango (2019)
13
Richness - Total Organic Carbon
TOC is measured in weight
percent of total rock.
The two most common
methods are:
LECO TOC- Acidize to eliminate
Carbonate, then combust
Pyrolysis TOC- Heat sample in
an inert atmosphere, then
combust the remainder
LECO is “most accurate”,
Pyrolysis results are 10-20%
less than LECO results
Jarvie after Espitalie, 1982 in Peters & Cassa in Magoon &
Merrill, 1991 Dow, 1994
27
Maturity
There are optical and analytical techniques to judge thermal maturity ‐
How cooked is the source rock?
• Optical:
• Thermal Alteration Index (TAI)
• Conodont Alteration Index (CAI)
• Vitrinite Reflectance (Ro) ‐ measure of the percentage of incident
light reflected from a polished surface of vitrinite maceral at 500X
magnification in oil immersion
• Bitumen Reflectance (Rb)
• Analytical:
• Rock‐Eval Pyrolysis (Tmax)
• SRA Pyrolysis (Tmax)
• Gas Isotopes
• Biomarkers
Generally accepted that Ro is the “Gold Standard”
Ro is the most commonly used scale
Other analytical results are correlated to this scale and reported
to management
28
14
Thermal Maturity – An Analogy
Roasting coffee beans is analogous to burying a source rock, as
each becomes more “cooked” oils are released from the organic
matter
29
Thermal Maturity – An Analogy
Roasting coffee beans is analogous to burying a source rock, as
each becomes more “cooked” oils are released from the organic
matter
30
15
Thermal Maturity – Optical
Vitrinite Reflectance (%Ro) ‐ measure of the percentage of
incident light reflected from a polished surface of vitrinite
maceral at 500X magnification in oil immersion
(Vitrinite reflectance value is an average of many 31
31
measurements)
Maturity Scales
• None of
these
values is
exact, this
is a “global
average”
• Typical color
scheme for
maps:
Immature is blue
Oil mature is
green
Wet gas
mature
orange or pink
32 Dry gas mature is
red
Senfelte & Landis in Merrill, 1991
16
Three Basic Types of
Analysis • Well
• Quantitative
• Gamma
Logs
Geochemistry
R?
R M
• Rock-Eval ™
• Instrumented
R
Ray
O? analyses: M
Pyrolysis R
M
• Delta Log
R M
R
O?
• SRA ™ Pyrolysis R
• LECO ™ TOC • Density
M?
OM • Elemental Analysis
M
• Gas Chromatograph R – Richness
• Gas Chromatograph
Mass Spectrometer M - Maturity
• Visual
• Instrument / Interpreter O - Organic
• Visual Kerogen
Analysis Matter Type
O Assessment
M
M • Vitrinite Reflectance
(Ro)
• Other Maceral
Reflectance
33
Rock‐Eval Pyrolysis
• Successful petroleum exploration relies on detailed analysis of the
petroleum system in a given area.
• Rock‐Eval pyrolysis allows the identification of potential source rocks,
their maturity, Kerogen parameters, and their regional distribution.
• It is a rapid screening technique (30‐60 min) and requires only small amounts
of sample material (100 mg). Core as well as cuttings can be used.
• The technique has been routinely used for about 30‐35 years and has become
a standard tool for hydrocarbon exploration.
• The method was developed at the French Petroleum Institute
(IFP) (Espitalié et al. 1977).
Rock‐Eval 6 Analyzer
34
17
Rock‐Eval Pyrolysis
Parameters measured by Rock‐Eval Pyrolysis
S1: Measure of Free Hydrocarbons in the rock
sample (Hydrocarbon compounds < C33)
S2: Measure of remaining Hydrocarbon generative potential of rock
sample (measure of Hydrogen content in the rock)
S3: Measure of amount of Oxygen in rock sample
Tmax: Measure of rock maturity; temperature S2 reaches its apex
TOC: Total Organic Carbon in rock sample
Measured parameters reflect the properties of the
present-day rock sample!
Values do not necessarily reflect the characteristics of an
equivalent immature source rock
i.e., a source rock before the start of thermal maturation
and Hydrocarbon generation
35
Rock‐Eval Pyrolysis
Parameters derived from Rock‐Eval Pyrolysis
S1/TOC: Measure of Free Hydrocarbons in rock sample normalized by TOC
HI: Hydrogen Index, measure of remaining Hydrocarbon generative
potential of the rock sample (measure of Hydrogen content in sample)
OI: Oxygen Index, measure of Oxygen content in the rock sample
VReTmax: Maturity of rock sample expressed as Vitrinite Reflectance
Equivalent
based on Tmax
Measured parameters reflect the properties of the
present-day rock sample!
Values do not necessarily reflect the characteristics of an
equivalent immature source rock
i.e., a source rock before the start of thermal maturation
and Hydrocarbon generation
36
18
Rock‐Eval Pyrolysis – Analytical Procedure
Programmed Pyrolysis Cycles – Overview
Sample is exposed to temperature‐programmed heating (pyrolysis).
Small amount of powdered rock (100 mg) is heated sequentially in
two different ovens:
• In Oven 1, sample is heated under an inert atmosphere, e.g.
nitrogen.
=> S1, S2, S3, Tmax, Pyrolyzed Carbon to obtain TOC
• After sample cools, moved to Oven 2 ‐ sample heated and
combusted under an oxygen‐containing atmosphere, e.g. air.
=> Residual Carbon to obtain TOC
Oven 1
S4 Oven 2
&
37
Rock‐Eval Pyrolysis – Analytical Procedure
Programmed Pyrolysis Cycles – Oven 1
During pyrolysis in Oven 1 (inert atmosphere e.g. nitrogen),
the temperature program is as follows:
• After reaching 300 ⁰C, Oven 1 and sample are kept isothermally
at 300 ⁰C for 3 minutes.
• Before and during this time the Free Hydrocarbons in the sample
are volatilized (organic compounds lighter than C33).
• Free Hydrocarbons are measured and recorded as the S1.
Oven 1
S4 Oven 2
&
38
19
Rock‐Eval Pyrolysis – Analytical Procedure
Programmed Pyrolysis Cycles – Oven 1
In Oven 1, temperature increased: 300 to 550 ⁰C (at 25‐50
⁰C/min)
• Volatilization of heavy Hydrocarbon compounds and cracking of
nonvolatile organic matter to Hydrocarbons (organic compounds
>C33).
• Hydrocarbons released are measured and recorded as S2.
• Temperature at which S2 peak reaches its apex is measured
and recorded as Tmax. Oven 1
S4 Oven 2
&
39
Rock‐Eval Pyrolysis – Analytical Procedure
Programmed Pyrolysis Cycles – Oven 1
In Oven 1, during temperature increase from 300 to 550 ⁰C,
a second set of measurements are recorded.
• CO2 and CO are generated during Kerogen cracking of the
sample
• Oxygen and Pyrolyzed Carbon are measured and recorded as S3
(temp. limits: CO2:<400 ⁰C; CO:<500 ⁰C).
Oven 1
S4 Oven 2
&
40
20
Rock‐Eval Pyrolysis – Analytical Procedure
Programmed Pyrolysis Cycles – Oven 2
After sample from Oven 1 cools, introduced into Oven
2 (oxygenated atmosphere, e.g. air), heated to 650 ⁰C
(sometimes 850 ⁰C for carbonate content).
• CO2 and CO are produced during combustion (burning) of
remaining sample.
• Residual Carbon is measured and recorded as S4.
Oven 1
S4 Oven 2
&
41
Rock‐Eval Pyrolysis ‐ Parameters
S1: measure of free Hydrocarbon in the rock
[mgHC/gRock]
• Free Hydrocarbons can be natural gases (C1 ‐ C7 ) or
oils (C7 ‐ C33)
• The measured amount of S1 in a source rock,
depends on it thermal maturity.
o An immature source rock will have no free
Hydrocarbons. With increasing maturity the S1
Increasing Thermal Maturity
value will increase (see figure).
o At higher maturities some of the Hydrocarbons
might be expelled and the S1 might not increase
significantly further.
o At very high maturities the oil cracks to gas, which
can more easily escape from the rock (undisturbed
location in the subsurface ; actual sample)
resulting in lower S1 values.
• Depending on the sample material (cuttings vs.
core) or sample handling and storage, the free
Hydrocarbons in a sample can decline with time
especially the very light volatile fractions (C1 ‐ C7 ).
42
21
Rock‐Eval Pyrolysis ‐ Parameters
S1/TOC: measure of free Hydrocarbon in the rock
[mgHC/gTOC]
• S1/TOC represents a normalized S1 value. If not
normalized, the S1 values is biased towards high
TOC rocks, i.e. rocks with high TOC tend to have
higher S1 values relative to rocks with low TOC,
even though they have the same thermal maturity
and the same Kerogen type. More TOC generates
Increasing Thermal Maturity
more Hydrocarbons.
• Similar to the S1 value, the measured amount of
S1/TOC in a source rock, depends on its thermal
maturity.
• S1/TOC is very high for Hydrocarbon reservoirs,
where Hydrocarbons have migrated into a TOC lean
reservoir rock.
43
Rock‐Eval Pyrolysis ‐
Parameters Oil prone, e.g. lacustrian
S2: remaining Hydrocarbon generative
potential of the rock
[mgHC/gRock]
HI: Hydrogen Index, remaining
• In nature, organic matter
Hydrocarbon (Kerogen,
generative resins,of
potential heavy
the Oil & Gas
Hydrocarbons, asphaltenes) is progressively prone (e.g.
rock marine)
cracked during thermal evolution. It generates
( HI = S2/TOC x 100 [mgHC/gTOC] )
hydrogen‐rich Hydrocarbons, while the remaining
Kerogen is depleted of its hydrogen content (i.e.
HI). The remaining Kerogen becomes more and
more condensed until a sub‐graphite stage is
obtained. Hydrocarbons can only be generated Lacustrian (Green River Basin, Eocene)
as long as the Kerogen contains hydrogen! Marine Shale (Saudi Arabia, Jurassic)
• The original HI, i.e. the HI of the immature source Marine Shale (France, Toracian)
rock represents the original Hydrocarbon Coal (Greenland, Tertiary)
generative potential of the Kerogen. It is therefore
a measure of Kerogen quality. The Hydrogen Gas prone (e.g.
Index, i.e. the hydrogen content in a Kerogen Coal)
depends on the organisms from which the Kerogen
is derived, e.g. bacteria, algae, woody material, etc.
• The HI is used to classify the Kerogens in the Inert
Pseudo van Krevelen Diagram. ( Type I, II, III, IV).
Sub‐Graphite
44
22
Rock‐Eval Pyrolysis ‐
Parameters Oil prone, e.g. lacustrian
S2: remaining Hydrocarbon generative
potential of the rock
[mgHC/gRock]
HI: Hydrogen Index, remaining
52
Hydrocarbon generative potential of the Oil & Gas prone
HI =
rock
TOC
( HI = S2/TOC x 100
x 100
[mgHC/gTOC] )
(e.g. marine)
=
m g HC
g Ro c k
HI = x 100
Lacustrian (Green River Basin, Eocene)
Marine Shale (Saudi Arabia, Jurassic)
g C Marine Shale (France, Toracian)
g Ro c k
x100 Coal (Greenland, Tertiary)
Gas prone (e.g. Coal)
m g HC m g HC Inert
HI = =
Sub‐Graphite
g C
45
g TOC
Rock‐Eval Pyrolysis ‐
Parameters Oil prone, e.g. lacustrine
S3: Measure of Oxygen content in the
rock [mgCO2/gRock]
OI: Measure of Oxygen content in the
rock ( OI = S3/TOC x 100
[mgCO2/gTOC] ) Oil & Gas prone
(e.g. marine)
• The S3 peak represents oxygen‐containing
compounds that are set free during heating. S3 is
only recorded below 400 ⁰C, because of early
decomposition of some carbonate minerals such as Lacustrian (Green River Basin, Eocene)
siderite. (Calcite and dolomite start to decompose above 600 Marine Shale (Saudi Arabia, Jurassic)
⁰C). Marine Shale (France, Toracian)
• S3 depends upon both the Type of organic matter Coal (Greenland, Tertiary)
and its thermal maturity. S3 is low for Type I and
decomposed.
Type II Kerogens. It is higher for Type III
• The original OI, i.e. the OI of the immature source
Kerogens, but decreases rapidly with thermal
rock represents the original oxygen content of the
evolution, as Gas prone (e.g. Coal)
Kerogen. It is therefore a means to classify
Kerogens. OI is used together with HI in the Pseudo
van Krevelen Diagram to identify Kerogen Types.
Inert
High OI values are characteristic for humic coal.
Sub‐Graphite
46
23
Rock‐Eval Pyrolysis ‐ Parameters
From these analyses you can obtain TOC
Total Organic Carbon (%) in the rock [gC/gRock ] x
100
Total Organic Carbon (TOC)
TOC = Pyrolyzed Carbon + Residual Carbon
Oven 1
S4 Oven 2
&
47
Rock‐Eval Pyrolysis ‐ Parameters
TOC: Total Organic Carbon (%) in the rock [gC/gRock ] x 100
• The amount of Original TOC is a function of:
a) Organic matter production
b) Organic matter preservation
c) Organic matter dilution, by means of mineral matter deposition
• Amount of measured TOC depends on the thermal maturity of the rock.
• TOC in the source rock declines with maturity as Kerogen is converted into Hydrocarbons.
• Measured TOC in highly mature/over mature source rock is not zero, because not all TOC
in a source rock can be converted into Hydrocarbons. Residual carbon stays behind
(pyrobitumen, dead carbon, sub‐graphite).
• The fraction of the Original TOC that can be converted into Hydrocarbons depends on
the amount of Hydrogen in the Kerogen, i.e. the Hydrogen Index, HI.
Original / Immature HI ranges
Type I: HI≈ 800‐1200 mgHC/gTOC Convertible fraction of TOC ≈ 70‐
80% Type II: HI≈ 450‐600 mgHC/gTOC Convertible fraction of TOC ≈
45‐50% Type III: HI≈ 50‐150 mgHC/gTOC Convertible fraction of TOC
≈ 10‐25% Type IV: HI≈< 50 mgHC/gTOC Convertible
fraction of TOC ≈ 0%
48
24
Rock‐Eval Pyrolysis ‐
Parameters
Tmax: Temperature in [⁰C ] at which the S2
curve reaches it apex, a measure of
maturity Tmax
VReTmax: Maturity of the organic matter, expressed
as Vitrinite Reflectance Equivalent
• Tmax
VRe varies as a function of thermal maturity and
Tmax= (Tmax * 0.018) ‐ 7.16 [%Roeq]
theJarvie,
Kerogen
2001) Type. Mature organic matter, which is
Increasing Thermal Maturity
(Dan Tmax
more condensed, is more difficult to pyrolize. It
requires higher activation energies, i.e. higher
temperatures to generate additional
Hydrocarbons. Tmax
• The calculation of VReTmax is a quick method to
convert Tmax into Vitrinite Reflectance Equivalent.
The equation is valid primarily for maturities in the
oil window (VR ≈ 0.2 ‐1.1 %Ro, Tmax ≈ 410‐460
⁰C). Tmax
Tmax
49
Rock‐Eval Pyrolysis ‐ Hydrocarbon Generation
• The onset and range of the
Hydrocarbon generation is a function of
the Kerogen Type (e.g. Type, I, II, III).
• Type II but especially Type I Kerogens
are known to have organic compounds
with relatively simple and more uniform
molecular structures compared to Type
III Kerogens.
• This implies that Kerogen Types I & II
have narrower distribution of cracking
activation energies and smaller
temperatures ranges than Type III
Kerogens.
50
25