Petroleum Systems Overview

Petroleum Systems
Heriot-Watt University 2015

Andrea García Bruno
NOTE: chapters 1 and 2 are not required for the exam, but include several basic concepts that will be used during
the whole course.
1. INTRODUCTION TO PETROLEUM SYSTEMS ANALYSIS

1.1 Petroleum system definition
A petroleum system consists of the essential elements and processes and all
genetically-related hydrocarbons that occur in petroleum shows, and accumulations
whose provenance is a single pod of active source rock.
- Elements
o Source rock: a rock with abundant hydrocarbon-prone organic matter.
o Reservoir rock: a rock in which oil and gas accumulate. It is
characterized by high porosity (which controls the volume of
hydrocarbons that the reservoir can store) and permeability (which
controls the passageways through which hydrocarbons will flow).
o Seal rock: a rock through which oil and gas cannot move effectively.
o Migration route: avenues in rock through which oil and gas moves from
source rock to trap.
o Trap: the structural and stratigraphic configuration that focuses oil and
gas into an accumulation.
- Processes
o Generation: burial of source rock to temperature and pressure conditions
sufficient to convert organic matter into hydrocarbons.
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o Migration: movement of hydrocarbons out of the source rock (i.e.

expulsion) toward and into a trap.
o Accumulation: a volume of hydrocarbon migrating into a trap faster than
the trap leaks, resulting in an accumulation.
o Preservation: hydrocarbon remains in reservoir and is not altered by
biodegradation or by interaction with oxygenized waters (i.e. water-
washing).
o Timing: trap forms before and during hydrocarbon migration.
The following map illustrates a petroleum system at time of expulsion/migration, and its
corresponding cross section. The lowest cross-section illustrates the petroleum system at
present day. Note that an extensional deformation phase and the associated normal
faults have compartmentalized the reservoir.
In the corresponding burial curve, the critical moment is indicated. The critical
moment is the time of highest probability of entrapment and preservation of
hydrocarbons in a petroleum system. It comes after trap formation and
hydrocarbons migration and accumulation into a reservoir. It marks the beginning of
preservation in a viable petroleum system.
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1.2. Source rock

A petroleum source rock is characterized by containing sufficient organic matter to
generate and expel commercial quantities of petroleum if buried (i.e. minimum 0.5%
TOC). This organic matter accumulation is basically due to a high productivity and low-
oxygen conditions.
The source rock is evaluated in terms of:
- Quantity and quality of organic matter

- Thermal maturity: heat flow history
- Timing of generation & expulsion (relative to trap formation)
- Volumetrics: prospect evaluation, including characterization of source kitchen
and migration pathways.
Kerogen is the portion of organic matter occurring in the source rock that is
nonextractable using organic solvents. (i.e. HCl and HF). The soluble portion is called
bitumen or Total Soluble Extract (TSE). When heated, kerogen thermally cracks to
oil and/or gas. Roughly, algal kerogen is hydrogen-rich and cracks to oil, whereas
woody terrestrial kerogen is hydrogen poor and cracks to gas.
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1.3. Geochemical characterization of petroleum.

The role of temperature is essential in the oil and gas generation. The oil window is
a temperature dependent interval in the subsurface where oil is generated and expelled
from the source rocks. The oil window is often found in the 100-150 ºC interval (aprox.
2-4 km depth), while the gas window is found in the 150-230 ºC interval (3-6 km
depth). At very high temperatures and pressure the inert kerogen (i.e. the kerogen
portion that does not yield to hydrocarbons) can transform into graphite.
The oil and gas windows can be related to maturity, which indicates the amount of heat
energy that has been supplied to the source rock. Vitrinite reflectance is the main
indicator of thermal maturity.
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1.4. Secondary migration

Hydrocarbon migration consists of four stages: primary, secondary, tertiary, and
remigration. The list below contains their definitions.
- Primary Migration—Process of loss of hydrocarbons from the source rock.

- Secondary Migration—Migration from source to reservoir along a simple or
complex carrier system. Includes migration within the reservoir rock itself.
- Tertiary Migration—Migration to the surface, either from a reservoir or source
rock. Also called dismigration.
- Remigration—Migration from one reservoir position through an intervening
section into another reservoir position in the same or a different reservoir.
The driving force for expulsion is the oil and gas expansion, whereas secondary
migration is driven by buoyancy (density differences between petroleum and water) and
hydrodynamics (water flow). The restricting force is capillary pressure (i.e. the
pressure difference across the interface between the invading petroleum and the water in
pores of the carrier system).
1.5. Reservoir geochemistry

Reservoir geochemistry aims to analyzing fluids heterogeneities within the reservoir. It
is used during several phases of the exploration and production process:
- Exploration (e.g. direction of fill, migration distance

- Appraisal (e.g. reservoir continuity, fluid contacts)
- Production (e.g. tubing leakage, flow assurance, injected water breakthrough)
2. WHAT IS PETROLEUM?
2.1. Definitions of petroleum, oil and gas

Petroleum is generally defined as any subsurface material which can be produced to
yield oil and gas:
- Oil: petroleum which is in the liquid phase at Standard Temperature and

Pressure (STP). In geochemical terms, oil refers to the C5+ compounds of
petroleum.
- Gas: petroleum which is in the gas phase at STP. In geochemical terms, gas
refers to the C1-C4 compounds of petroleum.
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The main controls on the physical state of petroleum are composition, pressure and
temperature.
Pressure in petroleum provinces within sedimentary basins ranges up to 100 MPa.,

whereas temperature in petroleum provinces within sedimentary basins ranges up to
200°C. Under these PT conditions molecules which are gas at STP dissolve in oil;
molecules which are liquid at STP dissolve in gas. Condensate is the fraction of a
subsurface petroleum mix that exists as gas at reservoir conditions, but condensates to
liquid as it goes up to surface.
2.2. Chemistry of an oil

Chemistry of oil is influenced by:
- Type of organic matter in the source rock

- Environment of deposition
- Age of the source rock
- Maturity of the oil
- Migration distance (P&T changes)
- Alteration processes (mainly in reservoir)
- Oil-oil correlation (relationship with other oils)
The following chart illustrates the elemental composition of typical petroleum. Sulphur
varies from 0.1 to 10%, with most between 0.5 and 2%. When sulphur content is very
high, oil tends to be heavier. Carbonate-sourced oils are generally richer in S than
clastic sourced oils. Nitrogen varies from <10ppm to nearly 1%.
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2.2.1. Petroleum composition
Because the structure of different hydrocarbons can vary so drastically, the properties of
each class of molecule vary greatly as well. In order to help categorize the properties of
hydrocarbons, they are broken up into several basic types.
 Alkanes – These are referred to as saturated hydrocarbons, since they only

contain single bonds between all carbon atoms. Alkanes are the basis of
petroleum fuels and are found in linear and branched forms.
 Unsaturated Hydrocarbons – Those hydrocarbons that have one or more

double bonds between carbon atoms are called alkenes. Those with one or more
triple bonds between carbon atoms are called alkynes. These are mixed with
alkanes in petroleum.
 Cycloalkanes – Any hydrocarbon containing one or more ring structures.
 Aromatic Hydrocarbons – This class of molecules has specialized ring

structures where bonds between carbon atoms are an intermediate between
single and double bonds. Molecules in this class include the industrial solvent
benzene.
 Resins –Poorly defined fraction comprising large aromatic structures and with
relatively high abundance of heteroatoms or NSO (not C and H).
 Asphaltenes –Operationally defined as the fraction of oil which precipitates on

addition of n pentane. In high abundance will form tar mats, which are
hydrocarbon horizons with high viscosity that are very difficult or even
impossible to be produced and may form permeability barriers.
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The structure, hydrogen to carbon ratio, and the length of a particular hydrocarbon
determine its properties. In general, small linear hydrocarbons will be gases while
medium sized linear hydrocarbons will be liquids. Branched hydrocarbons of
intermediate size tend to be waxes with low melting points. Long hydrocarbons tend to
be semi-solid or solid.
Finally, NSO (Nitrogen, Sulfur, Oxygen and heavy metals) are petroleum compounds
that are not hydrocarbons. They are higher in immature and degraded oils, as illustrated
by the following comparison charts. While the left-hand-side one corresponds to a
typical oil, mostly composed of saturates and aromatics, the right-hand-side chart
corresponds to a heavy tar-like petroleum.
2.2.2. API gravity

A widely used property of a crude oil is its API gravity. This is an arbitrary scale based
on the specific gravity of oil at 60°F, and is defined as:
°API = (141.5/Specific Gravity) – 131.5
An oil with a specific gravity of 1 (same as water) has an API gravity of 10. Oils are
described as heavy, medium or light depending on their gravities.
The following chart illustrates a classification of petroleum-derived materials on the

basis of their boiling points. Higher API oils yield more material with high boiling
points.
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3. SOURCE ROCK FORMATION
3.1. Controls on production and preservation of organic matter in the

ocean
Source rocks are characterized by having high organic matter content. This organic
matter accumulation is basically due to a high productivity and low-oxygen conditions.
3.1.1. Oxygen deficiency

Preservation of organic carbon in fossil fuels generally associated with sub-anoxic to
anoxic, bacteria-deficient environments. To reach this oxygen deficiency, oxygen
consumption must exceed oxygen (re)supply. Oxygen consumption depends on the
flux of metabolisable organic matter, whereas oxygen (re)supply is due to wind mixing
and photosynthesis and/or lateral advection (most important in oceans).
To reach this dysoxia-anoxia we need to increase the flux of organic matter (to enhance
oxygen consumption) and/or restrict vertical and lateral water circulation.
3.1.1.1. Watermass stratification

To restrict vertical oxygen resupply, the watermass must be stratified. This implies a
vertical segregation into 3 distinct layers:
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- Mixed layer: an upper, low-density layer that is homogenized by turbulent wind

mixing.
- Pycnocline: a transition zone characterized by a strong density gradient. If this
density change is caused by salinity it is called halocline, whereas if it is caused
by temperature, it is called thermocline.
- Lower layer: this bottom water is the densest one. It is relatively uniform and its
stability increases with increasing thickness. This layer can ensure organic
matter preservation, since it is prone to dysoxia-anoxia, especially when thin.
3.1.2. High productivity

Upwelling currents are dense, cooler and usually nutrient-rich water masses that move
upwards to the ocean surface, replacing the warmer, usually nutrient-depleted
superficial waters.
This enhances the primary productivity at the top water layers, and yields to a higher
carbon flux, which exceeds the capacity of the system for organic-matter
decomposition. The result is an intermediate oxygen minimum zone. Typically, low
oxygen conditions will only exist below pycnocline, since the upper layers are
resupplied by water mixing. However, true shelf anoxia can be reached if upwelling is
temporarily reduced.
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Therefore, high primary productivity avoids the degradation of the organic carbon
during its descent through the water column towards the sediment–water interface,
where other factors that come into play can increase the efficiency of burial and
preservation of the organic carbon in the geological record.
3.2. Epeiric sea black shales

Epeiric seas are shallow seas that cover central areas of continents during high-sea-
level periods. There were several examples during Mesozoic and Paleozoic, but no
modern analogues exist.
Really extensive black shales were formed in these seas during major transgressions.
They are characterized by high TOC and high HI, and they are oil-prone when
immature, mostly Type II (or II S). The origin of the organic carbon is associated with
normal marine nekton or plankton, a fact that makes one think that a strong halocline
would be very unlikely. Therefore, oxygen deficiency was more probably caused by
regional thermal stratification of deeper sub-basins, as illustrated by the sketch below.
Most of the classic major source rocks are epeiric black shales.
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3.3. Lacustrine source rocks

Many of the richest source rocks are lacustrine. They are formed by the accumulation of
oil-prone plankton, leading to type I kerogen, characterized by a high HI. Lacustrine
source rocks are typically associated with rift basins, in which permanent, deep lakes
can form. Meromictic lakes (i.e. lakes that have layers of water that do not intermix
for long periods) are especially favourable for lacustrine source rocks formation. They
develop because the basin is unusually deep and steep-sided, and/or because the lower
layer of the lake is highly saline and denser than the upper layers of water.
KEY POINTS FOR EXAM

- High organic matter accumulation is due to a high productivity and low-oxygen
conditions.
- Watermass stratification leads to a restricted water circulation. Three layers are
developed: an upper, mixed layer; a transition zone with high density gradient
(pycnocline, which can be thermocline or halocline), and a sub-anoxic to anoxic
bottom layer.
- Upwelling currents can cause an enhanced primary productivity in the shallow
waters, leading to a higher C flux that exceeds the capacity of the system for
organic-matter decomposition. The result is an oxygen minimum zone that
allows the preservation of organic matter while it descends towards the seabed.
- Epeiric black shales are formed in protected sub-basins or in the centre of a deep
basin, below the thermocline. Most of them are classic major source rocks.
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4. TOTAL ORGANIC CARBON (TOC)
4.1. General features

Total Organic Carbon (TOC) is the usual way of determining the abundance of
organic matter (OM) in rock. It is expressed as a relative concentration, that is, a weight
percentage of whole rock. Therefore, it is influenced by amount of sediment as well as
amount of OM. Only part of the OM is organic carbon, there is also hydrogen, oxygen
and minor S and N. For example, the carbon percentage of modern marine OM is in the
range of 60-80%.
4.1.1. TOC and source rocks

TOC is an essential parameter for determining richness of potential or actual rocks.
However, it does not prove source potential itself, since we also need to know the type
of OM and volume of the source rock unit.
Most hydrocarbon provinces are associated with areas where sediments have more than
1% TOC, generally 2-3% for most petroleum systems (‘excellent source potential’). The
minimum TOC for carbonate source rocks is 0.3%, whereas for siliciclastic source
rocks is 0.5%.
4.1.2. TOC and grain size

TOC has a good correlation with sediment grain size, being higher for higher
concentration of fine and very-fine particles (<63µm). This is mainly explained by the
hydrodynamic balance, that is, OM and silt and clay particles have a similar behavior
during transport and deposition, since these are a function of density and size. Then,
OM is deposited in low-energy, mud-dominated environments.
Other factors causing this relationship are:
- The greater deposition of OM in fine-grained sediments results in more reducing

sediments, since OM degradation depletes oxygen, and thus a better
preservation.
- Muddy sediments have much lower permeabilities, and are thus more reducing.
Dissolved oxidant supply (i.e. O2, SO4) is diffusion-limited, inhibiting OM
degradation.
- Finer sediments have higher mineral surface areas and can thus adsorb more
dissolved organic carbon.
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4.2. Controls on TOC

NOTE: the following equation is not required for the exam, but it is important to know the factors involved in it.
TOC will be controlled by three processes: primary productivity, Carbon Delivery Flux
(CDF) and burial efficiency. Although they are difficult to quantify, an equation was
developed to express the influence of these processes as three different factors (plus
maturity):
Wt.% TOC = [(I  P) / (D + (I  P))]  100
- Input: mass of supplied carbon. Plankton productivity leads to autochthonous C

flux, whereas if C has a terrestrial origin and has been transported into the basin
it is said to be allochthonous.
- Preservation: percentage of carbon finally preserved, since during its descent
through the water column part of carbon flux is degraded. When it reaches the
seabed, other controls during early-diagenesis will determine burial efficiency
and its preservation in the geological record.
- Dilution: dilution factor is calculated as the ratio between the mass of supplied
OM and mass of inorganic sediment (i,e. diluents). Part of the OM suffers
dilution, such that the highest productivity does not always produce the highest
TOC. Plankton input is often inherently associated with biogenic mineral
diluents (CO3 and biogenic opal), resulting in “autodilution”. Additionally, high
sedimentation rates cause that more of the OM supplied degrades inside the
sediment, and increases the probability of dilution by clay minerals.
- Maturity: as more heat energy is supplied to the sediment, part of the deposited
OM is reduced. This loss may reach 50% weight for type II kerogen (i.e. oil-
prone, formed by marine algae accumulation in siliciclastic basins).
4.2.1. Input
Primary productivity or phytoplankton productivity varies over three orders of
magnitude:
- Open ocean (oligotrophic): 50-60 gC/m2/a

- Continental shelf (mesotrophic): 100-230 gC/m2/a
- Coastal upwelling (eutrophic): 300-1,000 gC/m2/a
In order to form source rocks with high TOC, primary productivity levels must be very
high, since much of the CDF is chemically and biologically degraded during settling
through the water column. For water depths higher than 200m CDF decreases by 10 for
every 10 increase in depth. For this reason, very deep waters (i.e. abyssal basins) are not
the best depositional environments to form rich source rocks, even under anoxic
conditions. At depths where most source rocks were formed, DF rarely limits the TOC.
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4.2.2. Preservation
There are different ways to enhance preservation, all of which result in more of the
degradation occurring under anoxic conditions, and upward movement of O2:H2S
interface within sediment. These ways are:
- Increase CDF (i.e. increase primary productivity).

- Increase Linear Sediment Accumulation Rate (LSAR), so more of DF is buried.
However, this pathway involves a dilution penalty.
- Decrease dissolved oxygen, which depends on CDF and water circulation, and
determines type and efficiency of bacterial degradation.
The following charts show that burial efficiency reaches a maximum with LSAR, but
after that peak TOC starts decreasing due to dilution.
Oxygen deficiency has a stronger influence at low LSAR. Subsequently, best modern
source rocks might be forming in zones affected by upwelling, with anoxic conditions
and high sedimentation rates. In contrast, best ancient source rocks were formed in
anoxic conditions with slow sedimentation rates.
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4.2.4. Source rocks and system tracts

Good source rocks can be formed during deposition of any system tract if sub-anoxic to
anoxic conditions are provided and sedimentation rate is low to moderate. However,
these constrictions are more common to find in surfaces associated to rising-sea-level
periods (Maximum Flooding Surfaces and Transgressive Surfaces).
KEY POINTS FOR EXAM

- TOC indicates richness of source rocks.
- TOC depends on three processes: primary productivity, CDF and burial
efficiency. The input-preservation-dilution equation estimates TOC on the basis
of these processes.
- There are different ways to enhance preservation: increase CDF, increase LSAR
and/or decrease oxygen.
- High sedimentation rates might increase burial efficiency, but they involve a
dilution penalty. At low sedimentation rates, oxygen deficiency will be
especially determinant.
- Very deep basins are not suitable for source rock formation, since organic matter
will descend through a larger water column, and thus degradation losses will be
higher.
5. SIMPLE SOURCE ROCK VOLUMETRICS

NOTE: there is a spreadsheet on VISION created to solve out the volumetrics exercise we did in class. Since this
could be a more practical than theoretical question, only the very basic equations and concepts of Rock Evaluation
are explained here.
5.1. Estimation volume of petroleum in trap

The estimation of the amount of petroleum entrapped after migration is made by
calculating the difference between volumes of petroleum expelled minus migration
losses (see figure in the next page).
5.2. Evaluating source rock potential with Rock-Eval

The hydrocarbon generation potential of a source rock is a calculated volume that
utilizes multiple rock properties including gross rock volume, total organic carbon,
kerogen type, and pyrolysis parameters.
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5.2.1. Pyrolysis
Pyrolysis is the decomposition of organic matter by heating in the absence of oxygen.
Organic geochemists use pyrolysis to measure richness and maturity of potential source
rocks. In a pyrolysis analysis, the organic content is pyrolyzed in the absence of oxygen,
then combusted. The amount of
hydrocarbons and carbon dioxide
released is measured. The most widely
used pyrolysis technique is Rock-Eval.
In Rock-Eval pyrolysis, a sample is

placed in a vessel and is progressively
heated to 550°C under an inert
atmosphere. During the analysis, the
hydrocarbons already present in the
sample are volatized at a moderate
temperature. The amount of
hydrocarbons are measured and
recorded as a peak known as S1. Next
pyrolyzed is the kerogen present in the
sample, which generates hydrocarbons and hydrocarbon-like compounds (recorded as
the S2 peak), CO2, and water. The CO2 generated is recorded as the S3 peak. Residual
carbon (i.e. inert kerogen) is also measured and is recorded as S4.
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S1 and S2 together will indicate the potential yield of the source rock in terms of mass
of expelled hydrocarbons. S1 increases with maturation, whereas S2 decreases. Both
together will start to reduce when expulsion commences. Both parameters are
normalized to TOC in order to obtain two main parameters that characterize source
rocks:
- Hydrogen Index, HI: (S2/TOC)*100

Measured in mgHC/gTOC, it is then correlated with atomic H/C ratio. High HI
indicates good source rock potential. It ranges from 20 to 1100 mg/g, but in
order to have oil potential values higher than 200 are needed. For example,
kerogen type II typically exhibits a HI around 600 mg/g.
- Oxygen Index, OI: (S3/TOC)*100
Measured in mgOC/gTOC, it is then correlated with atomic O/C ratio. It is not
very reliable as it can be influenced by high temperature breakdown of carbonate
in rock matrix. Values range from <10 mg/g to several hundred in latter,
organic-poor oxidized sediments. For example, OI for kerogen type II typically
falls in the range interval 20-60 mg/g.
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Further parameters can be obtained through RockEval:
- Tmax (°C): temperature at which peak generation of S2 occurs. However, it is

an experimental number and therefore it does not reflect the real Tmax at which
the source rock has been buried.
- Production Index (PI=S1/(S1+S2)): The production index is the ratio of
already generated hydrocarbon to potential hydrocarbons. Low ratios indicate
either immaturity or extreme postmature organic matter. High rations indicate
the mature stage or contamination by migrated hydrocarbons. Difference in HI
with maturity largely reflects change in S2
5.3. Kerogen types

Van Krevelen modified diagram plots HI vs. OI in order to assess origin and maturity
of the kerogen. It shows bulk composition of sample, which changes with maturation
(loss of H and O) or oxidation (loss of H, gain of O). Four types of kerogens are
identified on the basis of their organic inputs and chemistry, and their idealized
maturation tracks can be obvserved in the Van Krevelen modified diagram.
RockEval results diagrams and the position on Van Krevelen diagram are a product of
organic matter source, organic matter preservation state and maturation. However,
results are not absolutely diagnostic, since the same S2 can be obtained by different
ways.
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5.3. Volumetrics
Basic Rock Eval data (S2, TOC, HI) can be used to calculate the volume of
hydrocarbons that may be produced and expelled from a given volume of source rock
present in a basin.
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The required parameters are the following ones:
- S2, HC generated per kg/t of rock

- Thickness of source rock unit (m)
- Bulk density of rock unit (kg/m3)
- OM content and porosity
- Gas fraction of HC (from initial HI)
- Petroleum expulsion efficiency, EE (also estimated from the initial HI)
- Trapping and recovery efficiencies
Example 1: North Sea Kimmeridge Clay Formation, 10x10x0.1 km3 source rock
S2 = (500/100)*6 = 30 kg/tonne
Density of rock = 2450kg/m3
Petroleum Expulsion Efficiency = 0.8
Petroleum density = 700kg/m3
1m3 = 6.29 bbl
Reservoir area = 4km by 4km
Reservoir Porosity = 20%
Area source (m2) 1.00E+08

Volume source (m3) 1.00E+10
Mass source (kg) 2.45E+13
Mass source (tonne) 2.45E+10
Hydrocarbons generated (kg) 7.35E+11
Expelled Hydrocarbons (kg) 5.88E+11
Expelled Hydrocarbons (m3) 8.40E+08
Expelled Hydrocarbons (bbl) 5.28E+09
Porous area of reservoir (m2) 3200000
Potential column height (m) 263
KEY POINTS FOR EXAM

- Pyrolysis is the decomposition of organic matter by heating in the absence of
oxygen. Pyrolysis parameters are used to evaluate richness and maturation of
source rocks.
- Peak S1 corresponds to hydrocarbons already present in the sample, peak S2
corresponds to hydrocarbons produced from kerogen after complete generation.
Both parameters are used to determine source rock potential.
- HI is obtained as (S2/TOC*100) and plotted against OI (S3/TOC*100) on the
Van Krevelen modified diagram. Both vary with maturation and oxidation. 4
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variation idealized patterns are identified, which correspond to the 4 types of

kerogen.
- HI is an indicator of source rock potential and oil-proneness. It is higher for
algal kerogens (types I and II) and lower for woody, terrestrial kerogens (types
III and IV).
- Basic Rock Eval data (S2, TOC, HI) can be used to calculate the volume of
hydrocarbons that may be produced and expelled from a given volume of source
rock.
6. BIOMARKERS
NOTE: Specific biomarkers names and reactions are not required for the exam. If the professor asks something about
this topic, it will be a general brief question.
6.1. General features

Biomarkers are a group of compounds, primarily hydrocarbons, found in oils and rock
and sediment. Biomarkers are structurally similar to, and are diagenetic alteration
products of compounds produced by living organisms. Many biomarkers occur in a
range of organisms (“general”), while others are restricted to a specific organism
(“specific”).
6.1.1. Applications and limitations

Since biomarkers retain all or most of the original carbon skeleton of the original
product, they can provide information about the depositional environment of the source
rock and the origin of the organic matter. We can also use them for maturity assessment,
and as oxicity indicators, since biomarkers undergo characteristic structural changes
associated to oxygen conditions and heat supply during burial. Additionally, they are
helpful to correlate oils and their corresponding source rock.
Use of biomarkers has also several limitations that should be considered.
- Biomarkers are only a small proportion of the sample (not always found).
- Biomarkers undergo modification during burial.
- Some biomarkers do not survive.
- Biomarkers can only be related to natural products in present day organisms.
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KEY POINTS FOR EXAM

- Biomarkers are structurally similar to, and are diagenetic products of natural
compounds produced by organisms. They undergo structural changes during
burial which give information about maturity.
- They can provide information about source rock biological origin and
depositional environment, oils and source rock correlations and maturity.
7. MATURITY
7.1. Thermal maturity concept

Thermal maturity measures how much heat energy has been supplied to the sediment,
as an integral of time and temperature. Therefore, a source rock can be mature enough
to generate hydrocarbons if it has been exposed to a very high temperature during a
short time period or a lower temperature during a longer time period.
Thermal maturity is a primary control on petroleum generation from source rocks. It can
be measured by different methods, being vitrinite reflectance the most widely used.
7.2. Vitrinite reflectance (VR)

Vitrinite is one of the primary components of coals and most sedimentary kerogens. It
is a type of maceral derived from the cell-wall material or woody tissue of the plants
(therefore, vitrinite is not found in sediments prior to Ordovician).
The study of vitrinite reflectance (VR), expressed as percentage of light reflected

(%Ro), was first studied by coal explorationists attempting to diagnose the thermal
maturity of coal beds. More recently, it has been increasingly used as a tool for the
study of organic matter metamorphism from kerogens to hydrocarbon. The key
attraction of VR in this context is its sensitivity to temperature ranges that largely
correspond to those of hydrocarbon generation. This means that, with a suitable
calibration, VR can be used as an indicator of maturity in hydrocarbon source rocks.
Although some other macerals show similar alterations during maturation, change in
VR is much more regular.
7.2.1. VR and maturity

VR at surface is about 0.2%. Generally, the onset of oil generation is correlated with a
reflectance of 0.5% (palaeotemperature ca. 100ºC), the peak oil generation with
reflectance of 0.7-0.8 % (ca. 125-140 ºC) and the termination of oil generation with
reflectance of 1.1% (ca. 160ºC).
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VR (and thus maturity) is mainly a function of maximum temperature and heating rate
near maximum temperature. VR is incremental and unidirectional (i.e. it can only
increase, never decrease). Increases require greater burial or heating, or longer time at a
given temperature. Uplift ‘freezes’ the VR values; rock need to be reburied even deeper
than before if the VR value is to increase again.
7.2.2. VR and depth

As wells frequently terminate (‘TD’) before the oil window is reached, we often need to
extrapolate observed VR trend to determine the depth at which it begins. This is a
difficult issue because, due to compaction and rate of change in VR with temperature
gradient, VR trend with depth is curvilinear. To solve this out, we represent VR vs.
depth in a semi-log plot, obtaining a straight line that is easier to extrapolate. Examples
of both linear and semi-log plots are given below.
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For normal geothermal gradients (~25°C per km) statistical studies show that VR
increases by about 0.15 per km (in top 4 km). However, geothermal gradients show
great variations that are also reflected by variation in VR depth trends.
The following VR vs. depth semi-log plot shows a “break” followed by a change in
slope. This kind of breaks can be explained by faults or magmatic intrusions, but the
most typical cause is an uplift event, followed by erosion and re-burial. As previously
nmentioned, ‘uplift’ freezes VR, so the sediment must be re-buried at even higher
depths (hotter temperatures) to show an increase. Change in slope is then associated to a
different thermal history, so “after-break” data do not show the real maximum
temperature experienced by the sediment.
7.2.3. VR and associated technical problems

Abimodal distribution or a large spread in the range of measured values produces a
mean Ro value that does not accurately represent the maturity of the rock sample.
Variations or errors in VR measurements may be caused by different problems,
including cavings, recycled vitrinite and lignite additives.
Cavings are associated with drilling process, and may cause immature kerogen to cave
into the bore-hole and mix with drill cuttings originally containing sparse amounts of
vitrinite. Recycled vitrinite is a similar issue, since it refers to a mixture of reworked,
allochthonous vitrinite population with the native organic matter of a sample that may
be in a different maturity stage.
7.3. Spore color

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SCI (spore coloration index) is an alternative maturation indicator that measures the
color of palynomorphs. Most palynomorphs are
liptinite, and thus should show similar maturation to
Amorphous Organic Matter (AOM, the main source
of oil).
Color changes as a function of maturity, from yellow,

almost colorless when immature, to dark brown,
almost opaque when overmature. The SCI
and TAI scales have been standardized to the
VR maturity scale.
KEY IDEAS FOR EXAM

- Maturity is a measure of heat energy supplied to sediment.
- Maturity is a time-temperature integral.
- Vitrinite Reflectance (VR) is a key measure parameter, since its sensitivity to
temperature ranges largely correspond to those of hydrocarbon generation.
Therefore, its evolution can be modelled as a function of time and temperature.
- VR is unidirectional (i.e. it only increases)
- ‘Uplift’ freezes VR, and in order to increase again, sediment must be re-buried
at deeper depths. This can be associated to the breaks that occur sometimes in
semi-log VR vs. depth semi-log representations.
- Spore colour and conodont reflectance are other optical maturity parameters.
- Biomarkers can also be used to assess maturity in source rocks and oils.
8. KINETICS MODELS OF PETROLEUM

8.1. Basic kinetics
Kinetic models of petroleum generation are based on two principles: first order kinetics
and Arrhenius Law.
- First order kinetics: it states that the rate at which the concentration of kerogen
degrades with time is proportional to the concentration. To put it simply, the
more kerogen there is, the faster it goes.
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Petroleum Systems
𝑑𝑐
= −𝑘𝑐
𝑑𝑡
- Arrhenius equation: the rate constant, k, that participates in the previous

equation is described by Arrhenius as:
𝑘 = 𝐴𝑒 −𝐸/𝑅𝑇
Where:
A is the Arrhenius Constant or frequency factor in m/s. It relates to rate
of bond breakage frequency. It is assumed as constant for geological
heating rates.
E is the activation energy in J/mol. It reflects the strength of chemical
bonds.
R is the universal gas constant (8.3145 J/mol/K).
T is the absolute temperature (ºK).
RT measures thermal energy.
The main issue when applying this kinetics basis is that these equations can be easily
applied for one reaction, but kerogen degradation or cracking of oil are complicate
processes where thousands of reactions are involved. Thus, to make a model consistent
with a multicomponent reaction system, governed by a series of reactions taking place
at the same time, we replace a single equation with a series of equations:
𝑑𝑐𝑖
= −𝑘𝑖 𝑐𝑖 𝑘 = 𝐴𝑒 −𝐸𝑖/𝑅𝑇
𝑑𝑡
Where the subscript i denotes the i-th component within the reaction scheme.
8.1.1. Activation energy distributions

Activation energy distributions can be described using two models which are essentially
equivalent:
- Linear combination of independent first order reactions.

- Gaussian/normal distributions for an infinite number of reactions.
The following figure contains normal activation energy distributions for two different
kind of samples, one immature and one mature, and their respective temperature
distributions. It can be observed that the left hand side of the diagrams corresponds to
low temperature reactions by which weaker bonds are broken. As burial advances and
thermal stresses become higher, degradation accelerates and distribution of remaining
energies becomes skewed to higher levels (right hand side). The function is “less peaky”
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because, according to first order kinetics, the rate of kerogen degradation (i.e. y-axis,
dm/dT) has decreased as less kerogen is remaining in the sample.
8.2. Organofacies
Pepper and coworkers purposed a simple and universal classification model based on
two kerogen fractions: oil generative and gas generative. In order to classify these
reactive kerogen fractions six parameters are used: A, Emean, and σE. Five organofacies
were developed, and liked to the forming environments, source rock properties and
related fluid types.
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Petroleum Systems
8.2.1. Organofacies geochemical characteristics

Some of the main geochemical characteristics of the Pepper’s organofacies are listed
here:
- A,B & C are dominated by aquatic, algal- and bacteria derived precursor lipids,
and have different diagenetic pathways
- A & B are both marine, but A is higher in sulphur
- C is associated to lacustrine environments. It has lipid precursors from
freshwater algae and experiences sulphate free diagenesis
- D, E & F are non-marine. D/E is classified as waxy and has a higher proportion
of plant/bacteria derived lipids, and F as wax poor.
8.2.2. Optimum values for kinetic parameters

Pepper’s model purposes for each organofacies and for each kerogen model optimum
values for kinetic parameters (A, Emean, and σE). Note that, in general, with increasing
mean activation energies standard deviation decreases. This is reflected in hydrocarbon
generation graphs as steeper curves, since the range of generation temperature curves is
tighter.
Lowest Emean for A is believed to be caused by the high content of sulphur, since C-S
bonds are weaker than C-C bonds. The higher Emean of F relative to D/E may result from
a greater lignin content, increasingly aromatic structures or enrichment of D/E in wax.
30
Petroleum Systems
8.3. Kinex outputs: oil and gas generation and expulsion curves for
different organofacies
Kinex is an easy source rock modelling tool which, by choosing one of the source rock
organofacies, plots relative fractions of oil and gas generated and expelled as a function
of temperature.
In all generation curves we will see that oil (gas line) generation occurs at lower
temperatures than gas (red line) generation due to lower activation energies.
Additionally, gas generation curve is typically gentler than oil’s because gas generation
occurs over a wider temperature range than oil due to wider range of activation energies
(except from organofacies D/E, where ranges for both fluids are very similar, although
oil generation occurs at lower temperatures).
Note that in KinEx outputs we always talk about oil and gas as compounds (C6+ and
C1-5 respectively), not phases.
8.3.1. Oil and gas generation, organofacies B and C

In the figure below the hydrocarbon generation curves (green for oil and red for gas) for
organofacies B and C are provided. As a basic observation, there is an obvious change
in slope. This is because the activation energies distribution for organofacies B is wider
than C. However, note that for C the hydrocarbon generation index is higher, due to its
higher HI.
If we plot also the total hydrocarbon (i.e. oil and gas) generation curve for organofacies
B (see figure below, curve 2), we can see that it is closer to the oil curve (number 1 in
the figure). This is because organofacies B are oil-prone, and majority of the fluid
generated is thus oil.
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Petroleum Systems
8.3.2. Oil and gas generation, organofacies A and F

Generation curves for organofacies A and F have similar shapes, but A curves are
shifted to the left side of the plot. Organofacies A is typically enriched in sulfur in
comparison with other organofacies, and C-S bonds are weaker, so the activation
energies (and generation temperatures) are lower. Additionally, organofacies F has a
terrestrial, woody origin evidenced by its high lignin content, which requires very high
temperatures to be degraded.
32
Petroleum Systems
8.3.3. Effect of heating rate: comparison of organofacies A and F

Although we have seen that activation energies for organofacies A and F are different,
the effect of increasing or decreasing heating rate, expressed as a lateral shift of the
generation curves toward higher or lower temperatures respectively, is the same for
both. Temperature of midpoint reaction increases (decreases) by ca. 15°C; whereas at
the beginning and end of reaction the effect is ca. 5 °C, due to the curves two-fold
shape.
8.4. Kinetics for oil and gas cracking

Oil and gas cracking kinetic models are governed by the same approach as for kerogen
degradation, based on first order reaction kinetics and the Arrhenius equation.
33
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Different oils crack at different rates.

Organofacies A, B and E, with moderate
to high HI values, generate oils rich in
saturated compounds; whereas
organofacies D, E and F, with poorer HI,
generate aromatic-rich oils. Saturated oils
have lower cracking rates than aromatics
(i.e. cracking starts at lower temperatures
for lower HI). This difference is reflected
by the spread of activation energies,
which decreases with higher HI (i.e.
function becomes more ‘peaky’),
meaning that oil cracking will occur
during a narrower temperature range.
The adjacent figure illustrates the effect

of source rock HI on oil cracking.
Organofacies with low HI (e.g.
organofacies F) have very high activation
energies for oil generation, but they have
also faster cracking rates, as previously
explained. Therefore, a major overlap
will occur between generation and cracking temperature ranges. This is the reason why
organofacies F is gas-prone. Oil generates at very high temperatures, and then cracks
rapidly to gas, even before expulsion starts.
Cracking threshold refers to the temperature at which 10% of oil has already cracked
to gas. As represented by the previous graph, for source rocks with HI < 300, it varies
between 115 and 145°C, assuming 2°C/Ma heating rate. For source rocks with HI0 >
600 it is effectively constant at 155°C. Oil deadline for source rocks with HI > 300 is
also constant and around 205ºC.
8.5. Petroleum expulsion and retention

Expulsion, according to Pepper terminology, is the transport of petroleum out of the
kerogen, and primary migration is the movement of petroleum through the inorganic
small pores of fine-grained rocks. This is the definition assumed by KinEx, although in
common terminology we usually refer to expulsion as the movement of petroleum out
of the source rock.
Petroleum and OM concentration (expressed as TOC) are closely related, and thus
expulsion efficiency depends on HI, being source rocks with lower HI less efficient
expellers. This is related to kerogen threshold (expressed in mg/g), a concept used in
34
Petroleum Systems
many expulsion models, such as the one assumed by Kinex. Increasing amounts of C6+
and C1-5 are generated as temperature increases and adsorbed by the kerogen network.
At some point the amount of C6+ that the kerogen can adsorb is reached, so the kerogen
is then saturated in oil. In simple models, it is assumed that expulsion occurs
instantaneously once this kerogen sorption threshold is reached.
Source rocks with higher HI have a more continuous kerogen network, so kerogen gets
rapidly saturated in oil. In source rocks with low HI, the oil diffusion through kerogen
network is less efficient, so they need to be more mature to overcome the kerogen
sorption threshold. In organofacies F, with HI values that can be lower than 200 mg/g
and fast cracking rates, oil is generated but cracks to gas before being expelled, so
kerogen sorption threshold is never reached. This is the reason why the oil retained
curve generated by Kinex does not follow generation curve, as observed in the
following figure
HC6+ Generation Index (/mass)

Residual HC6+ (/mass)
0.8 Cumulative HC6+ Expelled (/mass)
0.6
0.4
0.2
0
80 100 120 140 160 180 200 220 240
Temperature (C)
The next graph includes generation, cumulative expulsion and retention curves for both
oil and gas in organofacies F. Oil expulsion never occurs, but gas expulsion does when
gas sorption threshold is reached. Note that more gas being retained than is being
generated from the kerogen; the rest is coming from oil-gas cracking. Once gas is being
expelled, gas retention decreases slightly as a result of decreasing amounts of kerogen to
sorb the gas. Relatively large fraction of gas is retained as proportion of “inert” carbon
in low HI kerogens is high.
35
Petroleum Systems
HC6+ Generation Index (/mass)

HC1-5 Generation Index (/mass)
0.8 Residual HC6+ (/mass)

Residual HC1-5 (/mass)
Cumulative HC6+ Expelled (/mass)
Cumulative HC1-5 Expelled (/mass)
0.6
0.4
0.2
0
80 100 120 140 160 180 200 220 240
Temperature (C)
8.5.1. Controls on primary migration

Mean pore sizes over the depth range of most petroleum generation (>2 Km) are
generally in the 1-10 nm range. Capillary pressures of small pores are very high and
will not be exploited by migrating petroleum unless the pore system is oil wet. Fractures
can enhance the permeability of rocks and represent preferential petroleum fluid
conduits in tight carbonate-rich source rocks.
Kerogen transformation to hydrocarbon involves a positive volume change that causes

an increase in pore pressure. This oil and gas expansion is the main mechanism that
drives expulsion, and not buoyancy.
KEY IDEAS FOR THE EXAM

- Kinetic models of petroleum generation are based on two principles: first order
kinetics and Arrhenius Law.
- Pepper et al. developed a kinetics model where reactive kerogen was classified
in 5 different organofacies (A, B, C, D/E, F) associated to different depositional
36
Petroleum Systems
environments, with distinct kinetics parameters that are consistent with their
chemical properties.
- Activation energies for oil generation increase systemically in the order A-F,
expressed as an increase in the temperature ranges over which oil generates.
- The narrower the range of activation energies is, the steeper the generation curve
will be.
- An order of magnitude increase in heating rate increases temperatures at which
petroleum is generated by ca. 15 ºC.
- Source rocks with a higher HI (organofacies A, B, C) generate saturated oils that
have a slower gas cracking rate, where lower HI source rocks (organofacies D/E,
F) lead to aromatic oils, which cracks faster to gas. Due to this, low HI source
rocks generation temperatures overlap and cracking temperatures.
- A kerogen sorption threshold must be overcome to expel oil. Organofacies F,
with a very low HI, this threshold is never reached, because of the overlap
between cracking and generation temperatures. Oil is generated, but cracks
instantaneously to gas.
- Oil and gas expansion (and not buoyancy) is the driven mechanism for
expulsion.
37

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Petroleum Systems Overview

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Petroleum Systems

Heriot-Watt University 2015

1. INTRODUCTION TO PETROLEUM SYSTEMS ANALYSIS

o Migration: movement of hydrocarbons out of the source rock (i.e.

1.2. Source rock

The source rock is evaluated in terms of:

- Quantity and quality of organic matter

1.3. Geochemical characterization of petroleum.

1.4. Secondary migration

- Primary Migration—Process of loss of hydrocarbons from the source rock.

1.5. Reservoir geochemistry

- Exploration (e.g. direction of fill, migration distance

2.1. Definitions of petroleum, oil and gas

- Oil: petroleum which is in the liquid phase at Standard Temperature and

Pressure in petroleum provinces within sedimentary basins ranges up to 100 MPa.,

2.2. Chemistry of an oil

- Type of organic matter in the source rock

2.2.1. Petroleum composition

 Alkanes – These are referred to as saturated hydrocarbons, since they only

 Unsaturated Hydrocarbons – Those hydrocarbons that have one or more

 Cycloalkanes – Any hydrocarbon containing one or more ring structures.

 Aromatic Hydrocarbons – This class of molecules has specialized ring

 Asphaltenes –Operationally defined as the fraction of oil which precipitates on

2.2.2. API gravity

°API = (141.5/Specific Gravity) – 131.5

The following chart illustrates a classification of petroleum-derived materials on the

3. SOURCE ROCK FORMATION

3.1. Controls on production and preservation of organic matter in the

3.1.1. Oxygen deficiency

3.1.1.1. Watermass stratification

- Mixed layer: an upper, low-density layer that is homogenized by turbulent wind

3.1.2. High productivity

3.2. Epeiric sea black shales

3.3. Lacustrine source rocks

KEY POINTS FOR EXAM

4. TOTAL ORGANIC CARBON (TOC)

4.1. General features

4.1.1. TOC and source rocks

4.1.2. TOC and grain size

Other factors causing this relationship are:

- The greater deposition of OM in fine-grained sediments results in more reducing

4.2. Controls on TOC

Wt.% TOC = [(I  P) / (D + (I  P))]  100

- Input: mass of supplied carbon. Plankton productivity leads to autochthonous C

- Open ocean (oligotrophic): 50-60 gC/m2/a

- Increase CDF (i.e. increase primary productivity).

4.2.4. Source rocks and system tracts

KEY POINTS FOR EXAM

5. SIMPLE SOURCE ROCK VOLUMETRICS

5.1. Estimation volume of petroleum in trap

5.2. Evaluating source rock potential with Rock-Eval

In Rock-Eval pyrolysis, a sample is

- Hydrogen Index, HI: (S2/TOC)*100

Further parameters can be obtained through RockEval:

- Tmax (°C): temperature at which peak generation of S2 occurs. However, it is

5.3. Kerogen types

The required parameters are the following ones:

- S2, HC generated per kg/t of rock

Area source (m2) 1.00E+08

KEY POINTS FOR EXAM

variation idealized patterns are identified, which correspond to the 4 types of

6.1. General features