Simple kinetic models of petroleum formation

Part III: modelling an open system

Andrew S. Pepper & Peter J. Corvi

Abstract
The movement of petroleum from organic-rich source beds to potential
carrier beds is the net result of two processes: expulsion - the release of
generated petroleum from kerogen within the source bed; and primary
migration - flow of a petroleum phase through the inorganic void networks
of the source bed and all other intervening fine grained rocks.
Expulsion is by far the more important process within the source bed.
ORGAS, a simple zero-dimensional model of the source rock as an open
system, explicitly models expulsion, concurrent with oil and gas generation
and oil-gas cracking, as a storage/threshold problem. Oil and gas are
retained (adsorbed / absorbed) within kerogen until their concentrations
exceed the respective sorptive capacity of the residual organic carbon (0.1
and 0.02 g gCK-1). Initial Hydrogen Index (HI0) controls the important
balance between potential sorbate (petroleum) and sorbant (residual
carbon).
Using simple geochemical measurements, we divide initial organic
carbon into: initial oil, inert kerogen, and oil- and gas-generative (reactive)
kerogen components. Reactive kerogens are assigned to one of five global
kinetic Organofacies with pre-determined kinetic parameter sets governing
separately rates of oil and gas-generation. Kinetic parameters governing
rates of oil cracking within the source rock are predicted from HI0. The two
most important determinants of source rock behaviour are Organofacies
and HI0.
At a reference constant heating rate 2 oC Ma-1, the projected oil
expulsion threshold for typical Organofacies members increases in the
order A-DE: 100, 110, 120, 135 oC; F typically expels no oil. An order of
magnitude increase (decrease) in heating rate increases (decreases) these
thresholds by ca. 15 oC. Typical cumulative gas mass fractions in their
ultimate expulsion products are (A-F): 0.25, 0.3, 0.25, 0.65 and 1.0 g g-1.
200 mgHC gC-1 is an approximate minimum HI0 pre-requisite for oil
expulsion, irrespective of absolute petroleum potential (P0). As a family,
coals vary dramatically in their expulsion behaviour since their HI0 ranges
both above and below this value.
Primary migration is efficient: for expulsive source rocks, movement
within the source bed is limited only at low P0. A source rock's total
genetic potential (P0, thickness) becomes important during migration
outside the source bed: it potentially restricts the primary migration

distance, and the excess of petroleum available for secondary migration

and entrapment. We evaluate primary migration approximately using a
small migration loss factor (no more than about 10% saturation of porosity
or 1 mg/g), coupled with an understanding of fluid potential gradients
which determine migration direction within the stratigraphic architecture.
Ultimately, kerogen degradation and oil-to-gas cracking in the source rock
are the rate-limiting processes in petroleum accumulation.
Keywords: source rock; coal; coal-bed methane; modelling; generation;
oil-gas cracking; kinetics; sorption; expulsion; primary migration;
petroleum; oil; gas; hydrocarbons; Central Sumatra Basin.

Introduction
In exploration, quantitative petroleum geochemistry aims to predict the mass,
composition and timing of petroleum charge reaching the trap, and the phase
state of the emplaced petroleum. During appraisal, reservoir studies can also
benefit from an understanding of how, when and from where petroleum entered.
Reservoir filling rates are ultimately limited by rates of processes in the source
bed (England et al., 1991).
There are three fundamental intra-source processes (Figure 1):
Part I of this trilogy, in this issue (Pepper and Corvi, 1995), describes a
kinetic model for generation of petroleum (oil and gas) from sedimentary
organic matter (SOM);
Part II, also in this issue (Pepper and Dodd, 1995), described a kinetic
model for oil-to-gas cracking;
this third Part describes how these are integrated with a model of
petroleum release from the source bed, involving the processes of
expulsion (Pepper, 1989 and 1991) and primary migration.
Comprehensive models of petroleum formation require quantitative
understanding of the complex mutual interplay of physical and chemical
processes involved in this seemingly simple reaction scheme. However, these
processes are arranged in order of decreasing understanding and consensus
among petroleum geochemists.
Generation rates are most easily and reliably quantified, since field and
laboratory data can be combined in the calibration (Part I). Fortunately for the
petroleum industry, source rocks are to a greater or lesser degree open systems;
however this means that oil-gas cracking can only be studied in the laboratory
(Part II): results must be extrapolated to the field. Petroleum release is the most
difficult process to model because realistic laboratory simulation is difficult and
proposed mechanisms are almost as numerous as the field observations
themselves. Despite these obvious uncertainties, the need for open system
modelling is compelling: in conventional petroleum exploitation (i.e. excluding oilshale and coal-bed methane), the prize is represented by the petroleum that
leaves the rock, not that which remains within it.

Figure 1 General scheme of processes governing petroleum charge from a

source rock; expulsion in our model is defined specifically as release of
petroleum into the inorganic void space.

Earlier BP models developed by Cooles et al. (1986), Quigley et al. (1987)

and Quigley and Mackenzie (1988) were deliberately simple, forming an integral
part of a geochemical prospect evaluation methodology intended for use by the
non-specialist (Mackenzie and Quigley, 1988). This paper presents the ORGAS
(oil or gas?) model, developed in 1988-89 at the BP Research Centre. ORGAS
remains essentially simple: in our exploration experience, complex models
requiring many input variables, many of which end up being "guessed", are of
limited value.
The paper has five main sections. Because ORGAS differs in approach
from many published alternatives, Sections I and II review the processes
involved in release of generated petroleum from source beds: expulsion and
primary migration. Section III describes the open system (expulsion) model:
important inputs; simple parts of the algorithm required to understand the basic
concepts; resulting projections of source rock behaviour; and model testing. We
also revisit a published case history, assessing the petroleum prospectivity of
some Indonesian coals. Section IV discusses primary migration, which is
evaluated outside the ORGAS model.
Studies of petroleum release
Past approaches to the problem have been both heuristic and deterministic.

Heuristic approaches attempt to establish simple rules from observations (Cooles

et al., 1986; Mackenzie and Quigley, 1988): various case studies have estimated
source beds' petroleum release efficiency (PRE; our terminology) using a carbon
mass balance which compares mature source samples with their immature
equivalents (Cooles et al. 1986, Larter, 1988; Rullkoetter et al., 1988; Pepper,
1991). Some oil-generative source beds can have release efficiency of 0.8 - 0.9
(i.e. 80-90%).
Cooles et al. (1986) studied ten thick and relatively homogeneous aquatic
source rocks and found an apparent dependency of release efficiency upon initial
petroleum potential P0 (= [S10 + S20] or [P10 + P20]) yield from Rock-Eval type
pyrolysis of immature SOM; Espitalie et al., 1977). Mackenzie and Quigley
(1988) formalised these observations (Figure 2a):

PRE is high (commonly exceeding 0.6 during oil generation) when P0

exceeds ca. 0.005 g g-1 (i.e. 5 mg g-1 or kg tonne-1);
release is inefficient (PRE less than 0.4 during oil generation) when P0 is
less than 0.005 g g-1.

Empirical correlations are often unreliable outside the calibrant data range:
Pepper's (1991) expanded study of 20 source rocks, including coals (Figure 2b)
showed that the correlation apparent in Figure 2a does not extend to very high
P0. Rather, on Figure 2c there is a more robust correlation with initial Hydrogen
Index HI0 (= S20 normalised to organic carbon). Ironically, the significance of
this observation may have been overlooked because during the last two decades
petroleum geochemists - for sound economic reasons - have focussed study on
rich and high quality source rocks which release their petroleum efficiently,
0
0
providing little insight as to the underlying controls (i.e. P or HI ?). Thus
apparent trends in release efficiency (Figures 2a and c) provide, in isolation,
rather ambiguous insight into petroleum release mechanisms. In order to clearly
identify the critical processes, we need to make more specific observations - and
test resulting deterministic models against them.
Deterministic approaches attempt to forward-model petroleum release from
first principles. They are limited by our ability to quantify geophysical and
geochemical processes. Widely alternative models persist today, each assigning
differing relative importance to the various processes potentially governing
release efficiency, because so far the critical observations have not been clearly
laid out.
In the following two sections we explore two deterministic approaches, both
of which are conventional in the sense that petroleum is generated by kerogen
and eventually migrates to the secondary carrier bed via an inorganic
pore/fracture (void) system, as a discrete bulk phase driven by fluid potential
gradients.

Figure 2 Comparison of trends in petroleum release efficiency (PRE) calculated

0
by carbon mass-balance): (a) Mean PRE vs. P for ten source rocks (Mackenzie
0
0
and Quigley, 1988); (b) Mean PRE vs. P and (c) Mean PRE vs. HI for twenty
source rocks (Pepper, 1991).

Figure 3 Petroleum release from the source bed is a multi-step process, where
the slowest rate limits the overall rate. Model 1: generation kinetics (Kg) control
petroleum delivery rate to the inorganic void system; fluid flow rates govern
subsequent primary migration (Kpm). Model 2: considers intermediate storage of
petroleum between the point at which bonds are broken in kerogen and the
appearance of a petroleum phase in the inorganic void system. Expulsion rate
(Ke) is limited by Kg, but only after storage criteria are met within the kerogen.
Our observations identify Ke and thus ultimately Kg, as the overall rate-limiting
process: hence ORGAS considers only generation and storage of petroleum
within kerogen; we also therefore simplify primary migration to a storage
problem.
Figure 3 summarises the difference between the two approaches. Although
common usage of the terms expulsion and primary migration implies they are

synonymous, our conceptualisation of petroleum release draws important

distinctions. Firstly, generated petroleum is expelled from kerogen. We will
show this to be the more significant retarding process during release from the
source bed, although most models to-date have ignored it completely. Primary
migration begins when petroleum eventually enters the inorganic void network. It
has been the focus of most modelling effort to-date; however we will show it to be
generally a limiting process only if significant vertical migration outside the source
bed is required. Sandvik et al. (1992) and Okui and Waples (1992) also
recognised the distinction as important.
Below we summarise abundant geochemical and geophysical evidence
linking petroleum and kerogen concentrations in source beds; much obtained by
stepping outside 'conventional' petroleum geochemistry into coal and coalbed
methane science. Speculation on the relationships between coals and oil
deposits dates back at least to Erasmus Darwin in 1791 (Torrens, 1994) but
many petroleum geochemists over the last two decades have been content to
classify coals rather unhelpfully as "Type III" kerogen, which is usually taken to
imply a gas-prone type of release behaviour. Others (Durand and Paratte, 1983;
Pepper, 1991) saw no such rigid distinction between coals and 'conventional'
petroleum source rocks. Coals are uniquely defined by organic richness rather
than chemistry: the latter is reflected in a variation of lithotypes from inertinites to
torbanites. Torbanites share a common kerogen type with lacustrine oil-shales
(freshwater algal-bacterial OM), and, since both are retorted as commercial oil
sources, must be accepted as 'conventional' oil source rocks. This very
admission negates the argument used to preclude humic (vascular plant-derived)
coal lithotypes as effective oil source rocks based on excessive organic richness
per se (e.g. Katz et al., 1990).

I: EXPULSION - PETROLEUM RELEASE FROM KEROGEN

The idea that kerogen might influence petroleum release from source beds
is not new (Philippi, 1965; Young and McIver, 1977; Jones, 1980; McAuliffe,
1980). Interest in the idea waned through the 1980's, but the end of the decade
saw a revival. Kerogen has been recognised as a potential impediment to
release (Barker, 1987; Talukdar et al., 1988; Behar and Vandenbroucke, 1988;
Pepper, 1989; Wang and Barker, 1989; Wang, 1990; Katz et al., 1990; Noble et
al., 1991; Sandvik et al., 1992). Others have invoked it as a potential pathway
(Stainforth, 1988; Stainforth and Reinders, 1989 and 1990; Thomas and Clouse,
1990 a, b and c). Pepper (1991) and Okui and Waples (1992) emphasized that
quantitative understanding of kerogen's role is important in petroleum resource
assessment.

Figure 4 Differing conceptual models of the organic-inorganic relationship in

source rocks: (a-c) drawn at the correct scale, the load-bearing nature of kerogen
is easily appreciated. (1) macro- and microfractures may penetrate both the
organic and inorganic matrices; contrast this with (d) a conceptualisation by
Barker (1980) portraying kerogen particles smaller than the mineral grains, in
dispersed locations which are not load-bearing.
Properties of rocks which control expulsion
Petroleum storage in kerogen
Scale. The first volumetric impediment to petroleum release from a source bed is
provided by the originating kerogen particle. Continuous kerogen bodies range in
size from coal seams to dispersed particles; even the latter are orders of
magnitude larger than particles in the enveloping inorganic matrix (Figure 4a-c).
Kerogen is readily examined in the visible light spectrum; mud-sized mineral
grains are not - but note that even this rather basic observation is violated by
cartoons which have located kerogen particles inside the inorganic void network
(Figure 4d)!
Thus kerogen is load-bearing (Du Rouchet, 1981; Palciauskas, 1991). If
kerogen were an organic solid with no porosity, subjected to lithostatic pressure,
generated petroleum could only exist as a transitory fluid phase within it. Using
an analogy with crustal melts, Palciauskas (1991) has gone so far as to suggest
that fractional petroleum volumes within kerogen should therefore not exceed
0.02. We find this analogy inappropriate since kerogen has microporosity
capable of absorbing petroleum and since storage could also occur by adsorption
onto its internal surface area.
Organic "microporosity": absorption / molecular sieving. Coals have an
aperture-cavity type of 'porosity' which is well studied (Rightmire, 1984);

comparatively little is known about its equivalent in conventional petroleum rocks

though Lindgreen (1987) described 'organic lined pores' with molecular sieving
properties in a marine source rock. Coal 'pores' can be thought of as a series of
organic molecular cages ranging down to sub-nannometer, i.e. molecular scale
(Gan et al., 1972; Harris and Yust, 1976; Majahan and Walker, 1978). Differing
sizes of aperture and cavity can sieve and trap molecules of a characteristic size:
small molecules (including gases) are sieved by coal 'micropores' with diameters
in the 0.4-1.2 nm range (van Krevelen, 1961; Hanbaba et al., 1968; Peters and
Juntgen, 1968; Gan et al., 1972; Given et al., 1986). Total coal porosity,
estimated from moisture content, may be around 8-10% during oil generation
(Stach et al., 1982).
Internal surface area: adsorption. Coals can store gas by adsorption onto their
huge internal surface area: one gram of coal can have a CO2 area of hundreds
of square metres (Thomas and Damberger, 1976; Majahan, 1991). However,
access to potential surface area within micropores is restricted when sorbate
molecules are larger than the pore aperture (Debelak and Schrodt, 1979;
Debelak and Schrodt, 1979; Majahan, 1982). Some coal pore throats are only
open to helium (molecular diameter 0.26 nm; Harrison, 1975): the 'helium area' of
a coal is much greater than its 'N2' or 'CO2 area'.
There are many additional factors. Molecules of similar size such as N2 and
CO2 may simply differ in their tendency to sorbe (Patching, 1965; Gan et al.,
1972). Cross-sectional area and density of molecules in the adsorbed state can
differ from their conventional values (van der Sommen et al., 1955; Majahan,
1982). Small increases in moisture, up to the level of 2%, inhibit the methanesorbing capacity of dry coal by about a third (Kim, 1977; Wyman, 1984) probably
because water and gas molecules compete for access to surface area (Taber et
al., 1974). Larger increases in moisture content have little additional effect,
however (Wyman, 1984).
Thus porosity and surface area of coal are not fixed quantities: they depend
on the investigative medium. Additionally, it is difficult to distinguish the
processes of adsorption and pore filling in coal micropores, where gas may
occupy both surface area and volume (Majahan and Walker, 1978; Marsh,
1987). This dictates that our working definition of the petroleum stored in
kerogen must be a loose one: we will refer to all petroleum in kerogen as sorbed,
whatever the precise mechanism.
Coals can sorbe enough methane to be considered as commercial gas
reservoirs (Satriana, 1980; Rightmire, 1984; Wyman, 1984; Choate et al., 1986;
Ayers and Kelso, 1989; Ayoub et al., 1991; Kruuskraa et al., 1992.) Ethane
through butane are sorbed even more strongly than methane (Figure 5a;
Friedrich and Juntgen, 1972; Ruppel et al., 1972; Kim, 1973; Kravtsov et al.,
1983).
Comparatively little is known about sorption of oil (C6+) molecular weight
range petroleum heavier than hexane (Van Krevelen, 1961). Pepper (1991)
reasoned that, if small, simple gas molecules with low dieletric constants can

sorbe effectively, then increasingly large, complex, and polar oil molecules
should have even higher sorbing tendencies. Sandvik et al. (1992) have
investigated data obtained from solvent chemistry and swelling of coals and
organic polymers (Figure 5b), which provide a chemical basis for the ideas we
promote in our model of petroleum release.

Figure 5 Organic sorption: a) Results of simple experiments allowing rocks of

various TOC to equilibrate with methane and n-butane at ambient temperature
and atmospheric pressure (previously unpublished proprietary data).
Proportionality between gas uptake and TOC, together with minimal positive
intercepts at zero TOC, imply sorption by kerogen. n-butane is sorbed much
more strongly than methane, as observed in coal beds. (b) Solubility parameters
for various organic compounds, bulk petroleum compound classes, and kerogen
(Sandvik et al., 1992). The total solubility parameter for a compound has three
components: del H, del P, and del D, attributed to hydrogen bonding, polarity and
dispersion, respectively. Aromatic, then polar molecules / compound classes are
increasingly similar to, and hence are increasing soluble in, kerogen.
Petroleum movement through kerogen
Oil is mobile through kerogen (Allan and Larter, 1983; Given et al., 1986;
Stainforth, 1988; Stainforth and Reinders, 1989 and 1990; Thomas and Clouse,
1990a, b and c). A number of transport mechanisms are possible.
Diffusion through kerogen. Small petroleum molecules move through coal
by activated diffusion (van Krevelen, 1961). This concept has recently been
applied to 'conventional' petroleum source rocks (Stainforth, 1988; Stainforth and
Reinders, 1989 and 1990; Thomas and Clouse 1990a, b and c). Kerogen
behaves as a liquid medium for diffusion (Thomas and Clouse, 1990b): in
continuous 'model' networks, diffusion rates can be two orders of magnitude
faster than in an aqueous phase (Thomas and Clouse, 1990a).
Viability of diffusive transport depends on the presence of a continuous
network. Stainforth and Reinders (1990) suggest 1% TOC as a minimum prerequisite for a continuous kerogen network; Thomas and Clouse (1990c) suggest
2 - 2.5 %, a limit which would exclude many source rocks with established oil

release capability (Cooles et al., 1986; Pepper, 1991). Furthermore, the

mechanism is also unhelpful in explaining migration through an organic-lean
interburden.
Microfracturing.
Any petroleum phase forming via amalgamation of
desorbed molecules within a collapsing kerogen network will experience a
lithostatic load. Microfracturing is the likely result. Although the natural 'cleat' or
fracture system in coals is volumetrically insignificant in terms of petroleum
storage capacity (Meissner, 1987; Hvoslef et al., 1988), it represents an
important fluid release pathway (Meissner, 1987).
During the uplift-erosion cycle, fractured coals may be exhumed to shallow
depths (< 1 km), where confining pressure is low. Economic coal bed methane
extraction under these conditions requires cleat that is sufficiently frequent and
permeable to allow pressure draw-down and desorption from the kerogen
reservoir on a commercial production timescale. Under hydrostatic pressure,
cleat permeability decreases with depth due to increasing confining pressure
(Figure 6). If trends are extrapolated to depth, cleat permeabilities in the 10-7 to
10-6 Darcy range are projected - higher than reported for inorganic void networks
in mudrocks (e.g. 10-10 to 10-7 Darcy to oil; Sandvik and Mercer, 1991). Thus
fractures, particularly when propped open by lithostatic internal pressure during
petroleum generation, should also provide efficient, rapid drainage of a petroleum
phase forming within OM during burial.

Figure 6 Fracture permeability versus confining pressure for cleats (fractures) in

coal (data from Patching, 1965).

Observations of expulsion
Extraction; microscopic analysis

10

Common geochemical measurements of oil yield are organic solvent extract

(Durand, 1980) and pyrolysis thermal volatilate S1 (Espitalie et al., 1977) - the
latter sometimes misleadingly referred to as 'free' hydrocarbons. In fact, these
yields in themselves tell us nothing about the location or mobility of petroleum in
a source rock.
Associations between petroleum and OM are well known from studies of:
humic acids (Khan and Schnitzer, 1972); coals and other OM-rich rocks using
n.m.r. (e.g. Given et al., 1986); progressive extraction with solvents of increasing
strength (e.g. Marzec et al., 1979; Sandvik et al., 1992); repeated extraction after
acidification (Behar and Vandenbroucke, 1988; Stainforth and Reinders, 1990);
and even repeated extraction with a mild solvent (e.g. Durand et al., 1987).
Horsfield et al. (1988) and Noble et al., (1991) proposed that aromatic
hydrocarbons, generated by perhydrous vitrinite and resinite macerals, can
deactivate sorptive sites in Indonesian coals, thereby enhancing expulsion
efficiency of the saturated hydrocarbons in which coal-sourced oils are enriched.
(Again, this mechanism negates arguments that coals which generate aromaticrich hydrocarbons cannot be a source of saturate-rich oil; Katz et al., 1990). The
fluorescence of exinite and perhydrous vitrinite macerals under U.V. light
(Teichmueller, 1974; Stach et al., 1975; Radke et al., 1980) suggests a capacity
to sorbe aromatic oil.
As in the case of coalbed gas, we will use a loose definition of the term
'sorbed' to describe any oil which we can demonstrate to be OM-associated,
whether actually adsorbed or physically trapped within kerogen. For example, in
low ash coals, which are essentially pure kerogen bodies, S1 yields up to 44 mg
g-1 (Khorasani, 1987) and 57 mg g-1 (Katz et al., 1990) can be interpreted as a
sorbed oil content of ca. 5 % (mass).

Figure 7 Oil yield vs. organic carbon for two oil source rocks at various depths:
(a) S1 vs. TOC for Kimmeridge Clay Formation (KCF) source beds in UK North
Sea Basin wells (depths in km); (b) Extract yield vs. TOC for Toarcian source
beds in three Paris Basin wells (data from Tissot et al., 1971). Note the strong
linear covariance between S1/extract and TOC at all stages of maturity. There is
no absolute ceiling value of S1/extract in expulsive sections (KCF at 4.1 and 4.5
km; Toarcian in Montmirail well); in contrast these sections record a maximum TI

11

(S1 or extract vs. TOC gradient) which is controlled by the sorptive capacity of
residual organic carbon.

Dependency between oil yield and TOC

However, our most persuasive demonstrations of sorbed oil content are not
based on coals, but on marine source rocks relatively unperturbed by lateral and
vertical variation in OM type, which exhibit persistent correlations between
indigenous petroleum concentration and residual TOC.
Figure 7a illustrates remarkably linear correlations between S1 and TOC in
the Kimmeridge Clay Formation (KCF), UK North Sea. Covariance is strong
irrespective of maturation level (burial depth). Transformation Index TI (in this
case S1/TOC gradient) increases with increasing maturity from the pre-expulsive
section at 3.4 km, to the expulsive sections at 4.1 and 4.5 km, where a limiting TI
is reached which averages 106 mgHC gC-1 in a number of wells (Pepper, 1991).
Figure 7b plots extract yield vs. TOC for three Toarcian mudstone source
beds from the Paris Basin (data from Tissot et al., 1971). Two pre-expulsive
sections (Der, Dontrien wells) display linear gradients with high correlation
coefficients (equivalent TI ca. 0.1 gO gC-1). A section from the deepest,
expulsive well section Montmirail displays a higher TI, ca. 0.2 gO gC-1 also with
high correlation coefficient.
Figure 7 suggests that petroleum and OM concentrations are closely related
in both pre-expulsive and expulsive source rocks. Co-variance during early
maturation is a normal consequence of first-order kinetic behaviour (Part I): the
amount generated is proportional to the amount of reactant kerogen. However,
persistent co-variance at all maturity levels, including during petroleum release,
can be explained only if (sorption by) residual kerogen continues to limit the
residual petroleum yield. Depending on the sorbate a limiting value of TI is
observed (c.f. coalbed methane). We use such data to estimate the sorptive
capacity of kerogen for oil.
Borehole geophysical logs
Organic-rich clastic rocks and low ash coals show the same progression in
electrical resistivity during maturation: both are conductive at low thermal stress,
increasing in resistivity during oil generation. Since low-ash coals lack an
inorganic void system, these resistivity changes must result from increasing oil
and decreasing water content of the kerogen itself. Thus (Pepper, 1991) high
electrical resistivity does not in itself imply high petroleum saturation in the
inorganic void system of mature clastic source beds, as is commonly assumed.
Rather, resistivity logs confirm the same associations between petroleum
and kerogen which we have demonstrated using geochemical data (e.g. Meyer
and Nederlof, 1984; Mann et al. 1986; Pepper, 1991; Creaney and Passey, 1993;
Figure 8). In our experience, high resistivity readings within fine grained rocks
are always associated with, and broadly proportional to, organic carbon content.

12

Sorption-fractionation effects
Gas fractionation. Coal beds produce a hydrocarbon gas mix dominated by
methane (Kim, 1973), quite dissimilar to most petroleum gases which have
varying but significantly higher proportions of heavy gases (Clayton, 1991).
However, this is an artifact of fractionation under the low pressure / temperature
regime of currently exploited coal beds.

Figure 8 Partial geophysical and geochemical log from a Paris Basin well
(located close to the Montmirail well; Figure 7b), showing the lower Toarcian
'Schistes Carton' oil source rock (2100-50 m) which has expelled oil in this basin
centre location. Gamma and sonic logs show a regionally persistent 'funnel'shaped log motif: organic richness and petroleum potential increases downwards
through the source bed, as confirmed by S2 data. The gamma ray motif is

13

replicated / sonic log is mirrored by the resistivity log: petroleum exists in a

concentration proportional to the OM content (c.f. Figure 7b).

Binary sorption experiments (combined methane and ethane) by Ruppel et

al. (1972) provide insight into the way that gases (and other petroleum molecular
classes, i.e. those in oils) might be partitioned between the sorbed and fluid
phases in source beds, as a function of pressure and temperature. Their results
(Figure 9) suggest that at high temperatures (e.g. during thermogenic gas
generation) ethane and - we speculate - higher homologues are likely to be
desorbed much more readily than in the near-surface coal-bed analogue.

Figure 9 Binary sorption of methane and ethane on a bituminous coal with TOC
78.7% (dry ash-free basis). Experimental data from Ruppel et al. (1972).
Increasing pressure causes ethane to be preferentially concentrated in the
adsorbed phase (weak dependency over the pressure range 1 - 40 atm; 0.1 - 4.0
MPa; 0 - 400 m hydrostatic) but increasing temperature (0 - 50 oC) causes
methane to be preferentially concentrated in the adsorbed phase (strong
dependency over the same pressure range).

These experimental results support a number of qualitative field

observations: the increasing proportion of C2+ gases observed with increasing
isothermal pressure draw-down on a production time-scale (Iannacchione and
Puglio, 1979 and 1980; Rieke and Kirr, 1984; Wyman, 1984); and the tendency

14

for shallower coals, brought closer to the surface due to uplift and erosion on a
geological timescale, to produce more C2+ from the outset (Choate et al., 1984).
Thus, the composition of conventionally-reservoired thermogenic gases,
though different to coalbed gases, could simply reflect phase partitioning during
desorption under a higher pressure-temperature regime, coupled with first order
effects (i.e. varying initial proportions of hydrocarbon gases generated).
Oil fractionation also occurs during petroleum release. Initially, fractionation was
inferred from consistently recognised differences between compound class
distributions in source rock extracts and reservoired oils (Hunt and Jamieson,
1956; Bray and Evans, 1965; Tissot and Pelet, 1971; Young and McIver, 1977;
Combaz and Matharel, 1978; Price et al., 1984). Increasing confirmation came
from direct examination of source beds, close to source-carrier bed boundaries
(Tissot and Pelet, 1971; Vandenbroucke, 1972; Deroo, 1976; Barker, 1980;
Figure 10) or across basin pressure transition zones (Vandenbroucke et al.,
1983).

Figure 10 Relative release efficiency of oil components from an Algerian

Devonian clastic source bed in contact with a reservoir bed. Based on extract
data in Tissot and Pelet (1971), manipulated using techniques developed and
applied in more recent KFA case studies. Fractionation occurs according to oil
component polarity (c.f. Figure 5b).

This approach was refined by workers at KFA, Juelich, Germany and

implemented in numerous case studies during the last decade. Consistent
observations, some of which have been verified experimentally (Lafargue et al.,
1990), can be summarised:

15

source rocks release hydrocarbons preferentially to non-hydrocarbons

(Figure 10; Tissot and Pelet, 1971; Mackenzie et al., 1987; Leythaeuser et
al., 1987a and 1988a; Wilhelms et al., 1990; Lafargue et al., 1990);
o
within the non-hydrocarbons, the polar/NSO/resin fraction is released
preferentially to asphaltenes (Figure 10; Tissot and Pelet, 1971);
o
within the hydrocarbons, saturates are released preferentially to aromatics
(Leythaeuser et al., 1983; Vandenbroucke et al., 1983; Leythaeuser et al.,
1984a and b; Mackenzie et al., 1987 and 1988; Leythaeuser et al., 1987a,
1988a and b; Lafargue et al., 1990; Littke et al., 1990);
o
within the saturates, n-alkanes are released preferentially to branched
alkanes (Mackenzie et al., 1983; Leythaeuser et al., 1983; Leythaeuser and
Schaefer, 1984; Leythaeuser et al., 1984a and b; Leythaeuser and
Schwarzkopf, 1986; Lafargue et al., 1990);
o
'Type III' (low HI0) source beds release n-alkanes preferentially in order of
decreasing chain-length from nC35-15 (Mackenzie et al., 1983;
Leythaeuser et al., 1983; Vandenbroucke et al., 1983; Leythaeuser and
Schaefer, 1984; Leythaeuser et al., 1984a and b; Hvoslef et al., 1988).
During release from "Type II" (high HI0) source rocks, such as the KCF and
its Norwegian equivalent, fractionation occurs according to chain length
among the short- (< C10) rather than long- (> C15) chain n-alkanes
(Mackenzie et al., 1987 and 1988; Leythaeuser et al., 1987a and 1988a;
Wilhelms et al., 1990).
o
In the Brae KCF, redistribution of the light hydrocarbons (e.g. C5 n-alkanes)
perturbs the otherwise monotonous concentration gradients towards the
source rock edges (Mackenzie et al., 1987 and 1988; Leythaeuser et al.,
1987a and 1988a).
Most of the source beds in Figure 2 were thick and relatively homogeneous,
so the additional depletion which accompanies these fractionation effects at
source-carrier bed contacts has a relatively minor impact on bulk release
efficiency.
Many workers have recognised fractionation behaviour consistent with
component polarity - some emphasizing the role of liquid-solid interaction or
"geo-chromatography" (Silverman, 1965; Vandenbroucke, 1972; Barker, 1980;
Mackenzie et al., 1983; Leythaeuser and Schaefer, 1984; Leythaeuser et al.,
1984a, 1984b and 1988b; Lafargue et al. 1990). However, most invoked
inorganic minerals as the sorbant phase.
Clays and clay-rich rocks can adsorb and fractionate petroleum under dry
experimental conditions (e.g. Eltantawy and Arnold, 1972; Espitalie et al., 1980
and 1984; Tannenbaum et al., 1986; Krooss, 1991 and references therein).
However, detrital clay minerals are wetted from the moment of aqueous
transport. More realistic physical experiments involving sequential permeation of
already water-wet clays (Krooss, 1991 and references therein) and clay-rich soils
(Fernandez and Quigley, 1985) show that hydrocarbons with low dielectric
constants can not compete with water molecules (with high dielectric constant)
for sorptive sites on clays. Most silicate minerals are initially hydrophilic (Benner

16

and Bartell, 1941); although carbonate reservoir rocks are more frequently oil-wet
than clastic ones (Treiber et al., 1972), they are not analogous to carbonate
source facies. Reviews by Krooss et al. (1991) and England et al. (1991)
conclude that the evidence in favour of geo-chromatography is, at best,
ambiguous.
More recently, the trend has been increasingly to attribute chain-length
fractionation in 'Type III' source beds to petroleum phase-separation effects: this
requires a gas phase to form in the source rock, which preferentially 'strips'
lighter components from the overall molecular mix (Vandenbroucke et al., 1983;
Mackenzie et al., 1987 and 1988; Leythaeuser et al., 1987a, 1987b, and 1988a;
Hvoslef et al., 1988; Price, 1989). Leythaeuser and Poelchau (1991) developed
an elegant numerical simulation of n-alkane fractionation. Price (1989) wishes to
extend the mechanism to a "Type II" source rock, i.e. the Bakken Shale.
However, we doubt whether this process is responsible for the fractionation
effects observed during petroleum release from source rocks because neither
experimental nor natural phase segregation (Larter and Mills, 1991; Phillips et al.,
1991) induce strong fractionation between normal and branched alkane isomers.
Additionally, on mass-balance grounds, a major constraining factor is gas supply:
our pyrolysis-GC database (Part I, Figure 2) shows that even "Type III" kerogens
are not primarily gas-generative. Intra-source cracking under high thermal stress
could provide the required gas:oil ratio (Price et al., 1983), but under this high
P,T regime, phase behaviour is more likely to be supercritical: fluid composition
may evolve continuously without segregation into distinct oily and gassy fluid
phases (Part II). Furthermore, at the basin scale of observation, petroleum pools
charged from "Type III" source rocks are not exclusively gas-saturated.
Classical diffusion offers a mechanism for fractionation of only the light nalkanes (e.g. n-C5; Mackenzie et al., 1987). Stainforth and Reinders (1989 and
1990) used a model of thermally-activated diffusion through kerogen to match
various observations in the Brae KCF dataset (Mackenzie et al., 1987 and 1988;
Leythaeuser et al., 1987a and b, 1988a and b). However, experiments by
Thomas and Clouse (1990c) showed diffusion of compound classes through
kerogen in the opposite order to that observed in nature, i.e. aromatics >
napthenes > alkanes, .
We find it surprising that, with the notable exceptions of Thomas and
Clouse (1990c) and Sandvik et al. (1992), only occasional passing references
have been made to the potential role of organic matter in fractionation (e.g.
Leythaeuser et al., 1988b). Concentration gradients near source-reservoir bed
contacts could represent desorption gradients, regulated by the pressure
gradient between overpressured source bed (pressure source) and reservoir
(pressure sink). We find the analogy with coalbed methane intriguing: just as
methane is released before ethane on progressive pressure draw-down of a coal
'reservoir', oil fractionation within source beds would be expected according to
the differing sorptive capacity for each compound class (c.f. Figure 5b) and the
pressure gradient experienced. Such a process might operate both on the scale
of source-reservoir interbeds, and on a much larger scale across major basin
pressure transition zones (e.g. Vandenbroucke et al., 1983).

17

Thomas and Clouse (1990c) conclude that organic solid-fluid phase

partitioning is probably more important than diffusivity in explaining fractionation
effects. We agree. Katz et al. (1990) highlighted the paradox: how can poor
quality (saturates-poor) source rocks be the source of high quality (saturatesrich) oils? Figure 11 illustrates the potential consequences of organic sorptionfractionation in source rocks of varying initial organic quality. The high quality
(HI0) OM in "Type I and IIS" source rocks e.g. the Green River Shale (Hunt et al.,
1954; Tissot et al., 1978), Senonian Bituminous Rock of the Dead Sea Basin
(Tannenbaum and Aizenstat, 1985) and Monterey Formation (Orr, 1986), easily
overcomes its internal sorptive capacities: even asphaltenes are available in
excess, for expulsion. Thus expelled oils can be poor in quality (saturate-poor,
polar, heavy and viscous). In contrast, source rocks with progressively poorer
quality (lower HI0) OM have successively higher expulsion thresholds, permitting
increasingly selective release of only the higher quality (saturate-rich, light,
mobile) generation products. In the extreme case, OM with quality approaching
the sorption limit will retain all but the least sorbant oil products (e.g. Westphalian
coals, Southern North Sea Basin). Light saturated hydrocarbons will comprise
the small C6+ component expelled; this is ultimately reservoired in highly
undersaturated gas-phases and produced as a very low yield of high gravity
condensate. Condensates of this type may have been sufficiently fractionated to
constitute a 'naturally refined' petroleum product suitable for direct use as a fuel
on remote gas production facilities.

Figure 11 Likely effect of sorption-fractionation on expelled oil quality. Five

exclusively oil-generative synthetic source rocks have equal TOC0 and generate
the same mix of petroleum compound types, but differ in HI0 (i.e. they are
different mixtures of inert and oil generative kerogen). HI0 determines the ease
with which organic sorption is overcome (e.g. arrowheads show oil concentration
required to exceed sorption coefficient = 0.2 g gCK-1 at full maturity). If generated
oil compound types sorbe in order of increasing polarity / molecular weight range
(c.f. Figure 5b), expelled oil quality will vary inversely with HI0 (e.g. saturate
fractions annotated at top of each bar). Relative compound proportions in the
modelled expulsion products conform broadly to those observed in nature.

18

Figure 11 is an illustrative cartoon: reality will involve differing generative

and sorptive capacities for differing compound types, differing generation
temperatures and, at higher stages of maturity, effects of oil-gas cracking. More
realistic simulation of sorption-fractionation would require complex equations of
state describing how compound mixes partition between the desorbed and
sorbed states (c.f. Figure 9, showing only binary mixtures!). Given the simplicity
of our current compositional model of petroleum (gas: C1-5; oil: C6+) and current
data limitations, such complexity remains to be addressed in future generations
of model.
Quantifying expulsion: sorption coefficients
Having summarised the evidence for organic sorption during petroleum expulsion
from kerogen. We now present simple equations, and estimate global parameter
values, required to predict the sorbed oil and gas contents of source beds.
Important variables governing sorption are pressure, temperature, surface area
of the sorbant phase and chemical properties of the sorbate phase.
Gas sorption coefficient aG
Volume, surface area and mass. The coal bed methane and coal mining
industries use a technique known as the Direct Method to estimate the
undisturbed gas content of coal seams (Kissell et al., 1973; McCulloch et al.,
1975; Diamond and Levine, 1981). This involves laboratory desorption, crushing

19

(to release physically trapped gas), and an extrapolation to estimate gas losses
during sampling and handling. Its relative accuracy is regarded as high (within +
30 %; Kim, 1977). Although an absolute reference is hard to obtain, these data
provide a closer approximation to in-situ gas content than is possible using
standard petroleum industry techniques - although we note that Sokolov et al.
(1971) designed apparatus for the purpose.
Coal gas yields are expressed as a surface volume of gas per unit mass,
usually in cm3 g-1 or ft3 ton-1 (Rightmire, 1984); coal mass is usually taken DAF
(dry, ash-free basis) i.e. net of water (moisture) and mineral matter (ash). Such
units are useful in resource estimation; but they are inappropriate if adsorption
s.s. is regarded a surface phenomenon reflecting internal area. Variations in
facies and maturity (rank) cause coals to have widely differing carbon content,
even on a DAF basis. Thus rank-, lithotype- or even seam-specific adsorption
isotherms are required to predict methane resources (Kim, 1977; Eddy et al.,
1982; Lamberson and Bustin, 1993).
We simplify this undoubtedly complex problem by making use of the known
proportionality between coal internal surface area and carbon content, for a given
sorbate (Nandi and Walker, 1971; Gan et al., 1972). After normalising coalbed
gas yields to carbon mass, we can extrapolate the sorbed gas content of source
beds with any given TOC (c.f. Figure 5a).
Since kinetic models predict petroleum mass, we first convert methane
volume yields to mass using an STP density, i.e. 670 g m-3 (although the actual
pressure base at which methane volumes are measured is not always reported).
Now the gas content is expressed in units [ggas gC-1] useful to us in estimating a
gas sorption coefficient aG. We found abundant published field data (e.g.
Diamond, 1979; Kissell et al., 1973; McCulloch et al., 1975; Iannacchione and
Puglio, 1979 and 1980; Diamond and Levine, 1981; Eddy et al., 1982; Rightmire
et al., 1984; Wyman, 1984; Meissner, 1984 and 1987; but experimental data at
high pressure and at differing temperatures more limited (e.g. van der Sommen
et al., 1955; Ruppel et al., 1972).
Depth, pressure and temperature.
One approach to determining aG is purely empirical: plots of methane yield vs.
logarithmic burial depth have high correlation coefficients for individual coal
measures (e.g. Figure 12) or coals of common rank (Eddy et al., 1982).
However, our depth range of interest is far outside this calibrant pressure /
temperature regime - extrapolation is highly unreliable. It would be better to
understand and quantify the underlying pressure-temperature dependency.
Methane sorption on dry coal increases with increasing pressure and
decreasing temperature: this forms the basis of theoretical adsorption algorithms
used by the coalbed methane industry (e.g. Ruppel et al., 1972; Kim, 1977).
Again, these models are well calibrated within the pressure-temperature regime
typical of current economically and technically feasible coal-bed methane
developments < ca. 1.1 km (3500'; Eddy, 1984). However, when extrapolated to

20

depth, published correlations predict sharp reversals in gradient, and negative

values for aCH4.

Figure 12 Depth-logarithmic trend in sorbed methane content of Pennsylvanian

Hartshorne Coal, Arkoma Basin, Oklahoma (data from Iannacchione and Puglio,
1979 and 1980). Conversion to mass carbon units assumes a coal bed TOC of
70%.

A further frustration arises when using published correlations based on

shallow coal beds which, on a production timescale, remain static in the
sedimentary column: gas yields are invariably projected as low temperature
adsorption isotherms (Kim, 1977; Eddy et al., 1982). Conventionally, even high
pressure experiments useful to us have been carried out at low isothermal
temperature (e.g. up to 50 MPa, equivalent burial depth 5 km at hydrostatic
pressure but at 25 oC; van der Sommen et al., 1955).
In the following projection of aCH4 to depth we combined experimental
results from van der Sommen et al. (1955) to estimate pressure dependency,
with data from Ruppel et al. (1972) to estimate temperature dependency.
Pressure: Figure 13a shows a regression of high pressure isothermal data at 25
oC. The pressure dependency is linear up to pressures of 10 MPa, which at this
temperature represents a critical pressure beyond which no further methane can
sorbe: the coal's internal surface area is saturated. At 25 oC, aCH4 is given by:
aCH4 = c + 9.4*log(P)

21

(1)

where: aCH4 has units [cm3 gCOAL-1]; c is an intercept value which is not of
interest since we only seek the gradient value; and P is pressure (MPa). No
carbon content was given for the coal, but for a TOC of 67% (typical of a low ash
coal) yields in units [cm3 gCOAL-1] are simply 1000 times the yield in units [g gC1].
Temperature: Figure 13b shows three sets of isothermal data, fitted with curves
of slope established in Equation 1. At 0 oC, aCH4 is given by:
aCH4 = 6.7e-3 + 9.4e-3*log(P)

(2)

where aCH4 now has units [g gC-1]; P is again pressure [MPa].

At constant pressure, sorption decreases with increasing temperature. This
correction is derived from the shift in y-intercept of the 30 and 50 oC isothermal
curves:
aCH4 = - 6.2e-5*T

(3)

T is in [oC]. Substitution into equation (2) gives:

aCH4 = 6.7e-3 + 9.4e-3*log(P) - 6.2e-5*T

(4)

Figure 13c makes projections for a range of geological pressuretemperature regimes. At shallow depth, the curves have similar form to
empirically-derived trends (e.g. Figure 12): the decreasing rate of increase in
aCH4 with depth results from competing effects of increasing temperature and
pressure - a competition which temperature is predicted to 'win' at greater depth.
However, the reversals projected at depth remain hard to substantiate due to
lack of deep calibration.

22

Figure 13 Estimation of pressure and temperature dependency of methane

sorption in coal: (a) isothermal (25 oC) pressure dependency from data for the
Emma VIII seam (van der Sommen et al., 1955); (b) temperature dependency
established by superimposing the gradient from (a) on three isothermal (0, 30,
50 oC) experimental sets on dry coal (Ruppel et al., 1972); (c) Predictions of coal
bed methane content using Equation (4) for geological extremes of P,T gradient
(lithostatic at 20 oC km-1; hydrostatic - probably unreasonable given our earlier
comments about internal pressures in kerogen - at 40 oC km-1). Plotted for
comparison, aG values for 367 coal seams, calculated from data in Diamond and
Levine (1981). In conversion to mass carbon units, TOC was back-calculated
using standard DAF fixed carbon values corresponding to coal rank: 64.1%
(Lignite); 69.2% (Sub-C); 71.5% (Sub-B); 75.2% (HVB-C); 78.6% (HVB-B);
82.2% (HVB-A); 86.6% (MVB); 89.0% (LVB); 94.4% (Anthracite). Also plotted
are data from Figures 5 and 12. Many of the coals plotting below the projected
range are of too low rank for gas content to be controlled by an expulsion limit.
Range of projections is consistent with data from coals at 2.6 km with methane
yield 15 cm3 g-1, recovered from anorganic rich section between 1.55-3.55 km in
the Elmworth Field, West Canada (Wyman, 1984).

Though aCH4 varies widely with depth, it changes most rapidly at shallow
depth: from its vanishingly small near-surface value (Figure 5a) down to ca. 2 km
(20 MPa at hydrostatic pressure gradient). Within this interval, thermogenic gas
generation is proceeding at insignificant rates during the burial cycle. (However,
it might be important in understanding biogenic gas expulsion.) Over most of the
2-10 km depth range (20-100 MPa at hydrostatic pressure gradient), aCH4
remains between 0.01-0.02 g g -1. Figure 13c also predicts that kerogen will
C

expel gas more efficiently in hot, low-pressured basins than in cold, highly
overpressured basins. However, the absolute effect of the change in aG - about
0.01 g g -1 - is small and probably untestable using field data. However, there is
C

a clear danger in estimating aCH4 using trend-fitting of field data only, since the
uplifted and eroded basins from which coal gas is produced often have lower
pressure and cooler geothermal regimes than actively subsiding basins.
Since there are obvious limitations in the data we used to make these
projections, we continue to assume a global constant aG value of 0.02 g gC-1
(Pepper, 1991) - a value which accounts for an additional contribution from C2+
gas sorption (Figure 9).
Oil sorption coefficienl aO
Values of aO are more difficult to demonstrate since we lack laboratory
experimental data. Currently we base our estimates on field samples (Table 1;
Figure 7).

23

Table 1 Table 1 Potential values of oil sorption coefficient

derived from geochemical measurements

Rock

Method

Max. TI*

aO**

(mg gC-1)

(g gC-1)

Reference

Douala
Toarcian
Green River
Saharan

Extract
Extract
Extract
Extract

125
200
150
140

0.14
0.24
0.18
0.16

1
2
1
1

W. Canadian

Extract

160

0.18

KCF, Brae

Extract

180

0.21

0.2

0.13
0.10
0.09
0.12
0.11

5
3
6
4, 6
6, 7, 8

0.1

'Global'
Various
KCF, Brae
Lias, Paris Basin
KCF, UK N. Sea
Tertiary coals

HC Extract
HC Extract
S1
S1
S1

120***
ca. 90
ca. 80
106
98

'Global'

Notes: * TI (Transformation Index) = (Extract or S1) / TOC; ** Calculated using Equation (5); *** Represents
upper bound of quoted range.

References: 1)

Tissot and Welte (1984); 2)

Tissot et al. (1971);

3)

Mackenzie et al., 1987; 4) Pepper (1991) and Figure 7; 5) Philippi (1965); 6) BP proprietary data; 7)
Katz et al. (1990); 8) Khorasani (1987).

The value of aO will depend on the geochemical measurement used and the
type of oil (sorbate) it quantifies (c.f. coalbed gas sorption). Extracts and thermal
volatilates measure different types of 'mobile' organic matter: some of the high
molecular weight material measured by solvent extraction may actually appear in
the S2 (P2) rather than S1 (P1) yield of an unextracted sample subjected to
pyrolysis (e.g. Tarafa et al., 1988); some samples still yield S1 (P1) after solvent
extraction (e.g. Katz et al., 1990).
Philippi (1965) made the first such estimates, argueing that hydrocarbon
extract yields ranging between 30-120 mgHC gC-1 were sorbed by organic
carbon. Sandvik et al. (1992) reviewed these data together with total extract
yield data in Hunt and Jamieson (1956), Hunt (1967) and McAuliffe (1980),
concluding that the potential values range from 30-180, averaging 60-90, mgO
g -1. Pepper (1991) argued for a higher value ca. 200 mg g -1, consistent with
C

24

the TI maximum observed in the Paris Basin (Figure 7b) and with maxima
reported in other proven oil-expulsive source rocks. This implies an 'oil window'
value for aO, when derived for polar-rich oils characterised by total extract yields,
ca. 0.2 gO gC-1 (Table 1). However, because ORGAS defines 'oil' using S1 (Part
I), an appropriate aO value must be redetermined.
In the North Sea KCF, the TI maximum averages 106 mg g -1 (Figure 7a;
HC

Pepper, 1991). This lower value is reasonable since hydrocarbons measured in

the S1 (P1) yield should be less strongly sorbed than largely non-hydrocarbon
(polar and asphaltenic) petroleum dominating the extract yield. Converting to a
ratio of oil to carbon in kerogen [units gO gCK-1], i.e. excluding the carbon in the
oil itself:
aO = S1 / (TOC - S1*WO)

(5)

where all quantities are given in fractional SI units and WO is the average mass
fraction of carbon in oil (i.e. S1 yield). (Because gas yields as a fraction of TOC
are so small, this correction can be neglected in determining aG). Substituting
0.85 g g-1 for W in Equation (5) results in an aO value of 0.116 g g -1.
C

CK

We currently lack data on the P,T dependency of aO. If it is similar to the

behaviour of aCH4 (Figure 13), it will change relatively little within the P,T regime
over which oil is present in source beds (Parts I and II). Additionally, the
decrease in molecular weight and polar content of oils retained in source rocks
as thermal stress increases might offset the effect on aO of an increasing
pressure / temperature regime. Some natural variation in aO might also be
expected between Organofacies which generate different oil types (Part I): note
the differences between aO derived from S1, HC extract, and total extract yields
(Table 1).
Given such uncertainties, we use a global constant value for aO, of 0.1 g
g -1. Okui and Waples (1992) arrived at a similar value 'more or less by
CK

guesstimation', while Sandvik et al. (1992) found reasonable agreement with field
data using 10g liquid per 100g solid organic matter (i.e. the same value).
II: PRIMARY MIGRATION - MOVEMENT THROUGH INORGANIC VOID
NETWORKS
'Primary migration' involves movement of petroleum through the inorganic porefracture systems of both source beds and the non-source beds which separate
them from potential secondary carrier beds. During the last decade geochemists
reached overwhelming agreement that this process requires flow of petroleum in
a discrete bulk phase (Ungerer et al., 1984; Doligez et al., 1986 and 1987; Heum
et al., 1986; Tissot, 1987; Ungerer et al., 1987; Mann et al., 1988; Welte and
Yalcin, 1988; Ozkaya, 1989; Burnham and Braun, 1990; Sandvik and Mercer,

25

1990; Ungerer et al., 1990; Forbes et al., 1991; Burrus et al., 1991;
Dueppenbecker et al., 1991; Braun and Burnham, 1992).
While we do not challenge this general concept, the evidence above
persuades us that petroleum release from source beds cannot be solely a fluid
flow problem, in which generated petroleum is immediately available within the
inorganic void network (Figure 3, Model 1). Yet such an approach continues to
be popular (e.g. Rudkiewicz and Behar, 1994) especially in 'basin modelling' (e.g.
Burrus et al., 1993), despite mounting realisation elsewhere that it is only a part
of the story (Stainforth and Reinders, 1990; Sandvik et al., 1992; Okui and
Waples, 1992). In our view, fluid flow within the source rock is an extremely
efficient process which in many cases, to a first approximation, can be neglected
when considering source bed behaviour (Pepper, 1989 and 1991).
Properties of rocks which control primary migration
Currently accepted primary migration concepts suffer, in our view, from too-close
an analogy with the petroleum reservoir or aquifer rocks from which they were
essentially borrowed. This is despite long-recognised differences in the inorganic
matrix and void systems of fine and coarse grained rocks (Dickey, 1975).
There are mineralogical dissimilarities: fine grained clastics have a mineral
matrix rich in clays. In carbonate systems, source rocks commonly occur in low
energy clay-rich carbonate / marly facies quite atypical of carbonate reservoir
rocks (Kwak, 1981; Brosse et al., 1988; Talukdar et al., 1988). Clays present a
much larger surface area to volume ratio than quartzo-feldspathic or carbonate
grains predominant in reservoir rocks: a much greater proportion of the pore fluid
is in contact with the pore surfaces.
Petroleum and water-mineral interaction
For reasons we explained during discussion of fractionation effects, we agree
with Mackenzie et al. (1988), Price (1989) and England et al. (1991) and
Dueppenbecker et al. (1991), that already wet mineral surfaces are an unlikely
sorbant phase for migrating petroleum: clays can be considered an oleophobic
component and petroleum- mineral phase interaction neglected.
However, clays do influence the behaviour of pore water: they present an
enormous specific area for sorption of water, often referred to as 'bound' or
'structured' (Drost-Hansen, 1969; Low, 1976; Barker, 1980; Hinch, 1980; Magara,
1980; Honda and Magara, 1982; Talukdar et al., 1988; Price, 1989). The more
pore volume occluded by bound water (i.e. the higher the irreducible water
saturation), the less petroleum will be required to attain the high local saturations
required for bulk-phase percolative flow within remaining 'effective' void space
(Dickey, 1975; Pepper, 1991).
Scale of the inorganic matrix void network
Pores and pore-throats of source rocks are orders of magnitude smaller than
those of reservoir rocks. Mean pore sizes over the depth range of most
petroleum generation (> 2 km) are generally in the 1-10 nm range (Figure 14a;

26

Momper, 1978; Borst, 1982), with corresponding bulk permeabilities in the microto nanno-Darcy range (e.g. 10-7 to 10-8 Darcy at ca. 4 km in the Brae KCF;
Leythaeuser et al., 1987b).
Clastic source rocks' pore size distributions are typically skewed, with a
modal population of very small, nannometer range pores and a subordinate 'tail'
of larger ones (Figure 14b; Borst, 1982). In the Brae KCF, mean pore diameter
is 6 nm with the 10th percentile at 100 nm (Leythaeuser et al., 1987b). The
critical factor limiting petroleum flow here will be the minimum pore throat size
involved in the interconnection of the larger pores. If this critical size is at the
10th percentile in the distribution, then of the 12% total porosity in the KCF
(Figure 14b), only 1.2% will be effective, involved in through-going petroleum
flow. This way, low overall saturations (e.g. 1-10% of total porosity, equating in
this example to 0.12-1.2% of rock volume; Dickey, 1975) can still provide enough
oil for high local oil saturation (10-100%) in the 'effective' pore network: the
continuous petroleum pathways necessary for discrete-phase flow could only
form if primary migration were highly localised within these larger pore networks.
That is, similar to the invasion-percolation mechanism by which secondary
migration occurs (e.g. England et al., 1987; Winter, 1987; England et al., 1991).
The remaining matrix void space would remain occluded by bound water and
overall irreducible water saturation would be high. Overall saturations of this
order are unlikely to present a significant volumetric impediment to petroleum
release: given a porosity around 5%, pore saturations of 1-10% equate to a rock
volume fraction of 0.1-1%, and a mass fraction of 0.1-1 mg g-1 (Figure 15).

27

Figure 14 Pore sizes: (a) mean pore size vs. depth for US Gulf Coast mudstones
(data from Borst, 1982); (b) pore diameter distribution determined by mercury
injection of a KCF mudrock from 3129m (porosity 12%; TOC 22%), Magnus
Field, UK North Sea (c.f. mean pore diameter 6 nm and 10th percentile 100 nm
and porosity 2-3% at ca. 4000m, Brae Field area; Leythaeuser et al., 1987b),
plotted for comparison alongside organic pore diameter distribution derived by
CO2 adsorption on a coal (data from Debelak and Schrodt, 1979).

Fractures can enhance the bulk permeability of rocks with low matrix
permeability and may represent preferential petroleum fluid conduits in tight
carbonate-rich source rocks (Talukdar et al., 1988) as well as clastic source
rocks (Martinez et al., 1988; Lewan, 1987); and coals (Figure 6; Patching, 1965;
Taber et al., 1974). Since fractures typically account for less than 2% of rock
volume (Meissner, 1987; Hvoslef et al., 1988; Palciauskas, 1991) they constitute
potential low-volume, high permeability conduits for efficient fluid transfer,
supplementing and linking the more permeable avenues within the matrix pore
network (Figure 4a-c).

28

Figure 15 Conversions between oil yield (i.e. S1 or extract yield in mg/g or

kg/tonne rock) and pore-space saturations (percentage of total pore space
occupied by petroleum) assuming a subsurface oily phase density of 7*105 g m3 (approximate surface GOR 500 scf bbl-1), for rocks of differing porosity (%).

Capillary pressure
Capillary pressures required for a petroleum phase to enter the average or
below-average pore throats in source rocks (e.g. Figure 14b) will be enormous; a
further reason why most of the total inorganic porosity will not be exploited by
migrating petroleum. Within the 'effective' void network, capillary pressures will
be lower, especially within the additional space created if auto-fracturing results
from pressure build-up during generation and / or oil cracking (Ungerer et al.,
1983; Barker, 1988).
Multi-phase flow, relative permeability and irreducible water saturation
In a two-phase fluid system, the volumetrically subordinate phase will not flow
until it occupies some critical fraction of void space. In the petroleum reservoir,
two-phase flow is handled empirically using relative permeability (Longeron,
1987).
Thus, primary migration will also require build-up of a critical saturation
within the effective void network (Dickey, 1975; Durand, 1983; Durand and
Paratte, 1983; Durand et al., 1987; Mackenzie et al., 1987; Leythaeuser et al.,
1987a; Mackenzie and Quigley, 1988). A major problem arises in assessing
relative permeability behaviour (e.g. for input to 'basin models'; Doligez et al.,
1986; Burrus et al., 1991 and 1993). Since it is an experimentally-derived
property, lacking strict theoretical foundation (Ungerer et al., 1984), and can not
be measured in compacted fine-grained (including source) rocks, this introduces
the need to guess, assume simple analogy with the petroleum reservoir, or
extrapolate behaviour from other datasets.
Setting aside pure guesswork, there are many difficulties in the analogy with
petroleum reservoir rocks: wettability and sense of displacement are important.
The oil phase is recovered from a water-wet reservoir by imbibition: displacement
of the non-wetting petroleum phase by a wetting aqueous phase - a process
accelerated by water flooding. At start-up, such reservoirs flow oily and aqueous
phases at equal rates when the oily phase occupies about one third to one half of
void space (Schowalter and Hess, 1982; Pepper, 1991). However, water-wet
source rock pores experience increasing petroleum saturation as water is initially
displaced. This is drainage: the displacement of a wetting phase by a nonwetting phase. So although simple analogy with a water-wet reservoir might
initially seem appropriate, the expulsion process is actually analogous to the
converse situation during oil production - i.e. water flooding of an oil-wet
reservoir!
Pepper (1991) argued that relative permeability to petroleum should be
comparatively high at low petroleum saturations in source rocks, while Okui and
Waples (1991 and 1993) made significant progress towards relative permeability

29

estimation. By studying relative permeability data on a wide range of coarsergrained rocks (Morgan and Gordon, 1970) they established relationships
between relative permeability and absolute permeability / grain size,
subsequently extrapolating down to the mudrock grain size range. Their most
important projections were of: low oil saturation required for preferential flow in a
typical oil-mature mudrock (Figure 16); and irreducible water saturation
approaching 80%, consistent with observations that mudstones with porosity
lower than 15% contain dominantly 'bound' water (Honda and Magara, 1982).
Even clay-rich soils with porosity up to an order of magnitude higher than
compacted source rocks, little of which will contain 'bound' water, can be
permeated by simple hydrocarbons at only 10% saturation (Fernandez and
Quigley, 1985). Thus, perhaps it should not surprising that net permeability to oil
in compacted mudrocks can be quite high (e.g. 10-10 to 10-7 Darcy; Sandvik and
Mercer, 1990) at low saturation.
There is similarity with the gas-water system in draining coal cleat:
permeability to the gas phase increases almost immediately as gas saturation
increases from zero; irreducible water saturation is high (Figure 16; Kissell and
Edwards, 1975; Taber et al., 1974).

Figure 16 Possible relative permeability curves for source rocks: typical reservoir
behaviour from Schowalter and Hess (1982); projected effect of decreasing water
saturation in oil-water system of a typical mudstone source rock with absolute
permeability 10-7 Darcy (modified from Okui and Waples, 1993); measured effect
of decreasing water saturation in gas-water system of a Pittsburgh coal draining
under 200 psi overburden pressure (modified from Taber et al., 1974).

30

Observations of primary migration

Almost all of the various independent observations we listed under 'Observations
of expulsion' are difficult to reconcile with a 'primary migration' model of
petroleum release (Table 2):Table 2 Estimates of oil saturation in fine grained rocks
________________________________________________________________
Author(s)
Host
Fractional
Basis of
rock
saturation
estimate
________________________________________________________________
Conceptual
Dickey (1975)

mudstone

0.01-0.1

Analogy
Leythaeuser et al. (1987a)

0.4

Analogy with reservoir

0.1

permeation experiments

< 0.08

S1 / porosity

pressured mdst

0.11-0.19

Extract / porosity

Hitra

0.03-0.09

Extract / fracture volume

Various

0.4

Extract / porosity

Forbes et al. (1991)

Spekk

0.5

S1 / porosity

Forbes et al. (1991)

Are

0.8

S1 / porosity

Leythaeuser et al. (1987a)

KCF

0.67-1.0

Extract / porosity

Measurements in organic-lean beds (primary migration pathway)

Fernandez & Quigley (1985)
Pepper (1991)

soils
above Draupne
Fm., Ula Field

This paper

GOM hard-

Measurements in coal cleat

Hvoslef et al. (1988)

Measurements in organic-rich source beds

Mackenzie and Quigley (1988)

________________________________________________________________

Bulk petroleum release efficiency. The observation set of ten source rocks
shown in Figure 2a is often cited as evidence of a dependency between release
efficiency and P0: richer source rocks supposedly generate more petroleum in
excess of the saturations required for preferential petroleum flow in the inorganic
void network. However, an extended observation set (Figure 2b) refutes this
apparent dependency, which we explain as a result of the indirect relationship
between HI0 and P0 commonly seen in aquatic source rocks;
Fractionation effects. We summarised above many observations which
show that interactions between bulk petroleum and water-wet inorganic mineral
phases are not important in petroleum fractionation. For example, Leythaeuser
et al. (1983 and 1984a) observed that fractionation did not occur when a

31

migrating bulk oil phase impregnated a fine-grained organically lean lithology

(siltstone).
Oil yield vs. TOC plots. Small positive S1 or extract yield intercepts (<1 mg
g-1) on Figures 7a and b indicate that little of the indigenous oil in source beds is
associated with the inorganic void system. Furthermore, we have never
observed a situation where S1 and extract yields in expulsive source rocks are
constrained by an absolute ceiling (e.g. 5 mg g-1) imposed by the inorganic void
system. Our experiences strongly support Stainforth and Reinders' (1990)
conclusion that most of the oil in mature source beds is retained within kerogen.
Electrical resistivity as an indicator of petroleum saturation. We have not
observed high resistivity in organically lean rocks penetrated during primary
petroleum migration: the process is efficient, involving little intermediate storage
(residual petroleum left en route).
Quantifying primary migration: pore saturations
Estimates of petroleum saturations required for discrete phase petroleum flow
during primary migration span two orders of magnitude, from 1% to 100% (Table
3). One reason for their poor consistency could be that the process of primary
migration is tremendously complex and unpredictable. We would argue not.
Setting apart those which have been simply guessed, reasoned, or assumed,
these inconsistencies originate because the values are calculated by normalising
oil yields to porosity in organic-rich rocks, without justification for the implicit
assumption that the measured solvent extract or S1 yield actually resides in the
inorganic void system! On the contrary, data in Figure 7 and elsewhere (e.g.
Espitalie et al., 1988) clearly show that in source beds, yields record petroleum
sorbed on kerogen; only a small additional component (<1 mg g-1) is attributable
to the inorganic void system.
Table 3 Observations pinpointing critical petroleum release mechanism
Pore saturation
exclusively
(most current
models);
e.g. "5 mg/g
rule"

Sorption dominant,
pore saturation
low:
"200 mg/gC
plus 1 mg/g rule"

Efficient oil release from rich, high quality source beds (oil prone)

Yes

Yes

Inefficient oil release from lean, low quality source beds (gas prone)

Yes

Yes

Oil sourcing from some coals; dry gas from others

No

Yes

Proportionality of oil content to TOC in source beds

No

Yes

Borehole geophysical log patterns in source beds

No

Yes

Petroleum release phenomenon

32

Oil expulsion-fractionation by compound polarity

No

Yes

Oil expulsion-fractionation normal > branched alkanes

No

Yes

Oil and gas expulsion fractionation by n-alkane chain length

Yes

Yes

(if gas phase

present)

Low oil yield observed along primary and tertiary migration pathways

No

Yes

Regional vertical migration through significant interburden rock

No

Yes

thickness

(or limited)

Analysis of primary migration routes.

Further, unambiguous confirmation can be obtained from "control experiments"
which measure petroleum concentrations along a primary migration pathway
through organically lean rocks.
We have never observed high residual
saturations in this situation (Table 3). The process is very efficient: even in highly
porous near-lithostatic ("hard") pressured Gulf of Mexico mudstones, primary
migration saturations are < 20%.
Our first example (Figure 17) is from an East Java Sea well penetrating an
overpressured reservoir leaking oil through its organically lean caprock.
Production Index (PI = S1 / [S1 + S2]) in the caprock shows that oil
concentrations are abnormally high compared to the low levels attained in overand underlying sediments (Figure 17a). This confirms the presence of migrant
petroleum (Espitalie et al., 1977) witnessed during wellsite screening. However
(Figure 17b), extremely low S1 yields in the leakage zone (0.1 - 1 mgS1 g-1)
demonstrate that absolute oil losses incurred in establishing this migration
pathway are trivial. In contrast, the coals, though premature for expulsion,
already have ca. 10 - 20 mgS1 g-1 "in store".

33

Figure 17 Partial geochemical log showing leakage of oil from an overpressured

oil-bearing sandstone reservoir (S: ca. 8100' or 2470m) through an organically
lean caprock into a potential thief zone limestone (L: ca. 6900' or 2100m). Oil
shows recorded while drilling are annotated: solid circles = oil stain; open
diamonds = fluorescence. (a) PI is abnormally high (>0.1) over the leakage
zone, confirming wellsite observations, but (b) absolute S1 yields are very low,
showing that migration through the caprock is very efficient (c.f. Figures 7 and
18). Biomarker analysis confirms that coals between 8800-9600' (2680-2930m)
are insufficiently mature and of the wrong facies to have sourced the oil.

A second example (Figure 18) is from the Snorre Field, North Sea.
Through what Leith et al. (1993) and Caillet (1993) interpreted as a zone of
pervasive caprock failure, the yield attributable to leaked reservoir oil is no more
than about 1 mg g-1; consistent with our observations of low petroleum
saturation in migration routes through organically lean mudstones in the Ula
region of the North Sea (Pepper, 1991), the East Java Sea and Paris Basin.

34

Figure 18 Geochemical analysis of a leakage pathway through the Shetland

Group caprock of the Snorre Field, Norwegian North Sea (based on data from
Leith et al., 1993). Extractable oil concentrations decrease from ca. 2 to 1 mg g1 across the migration front; hydrocarbon contents are relatively low (ca. 30-50%
versus ca. 90% in the reservoir fluid), suggesting that only about half is
indigenous. Thus, migrant oil is present in concentrations no greater than ca. 1
mg g-1 (c.f. Figures 7 and 17). n-alkane ratios (e.g. nC17/(nC17+nC27) remain
constant: there is no fractionation according to chain length during bulk
petroleum flow.

Important parameters in 'primary migration' models

If primary migration were an important limiting factor in petroleum release from
source beds - counter to our arguments - then the complex model required to
describe it (e.g Ozkaya, 1989) would require many input variables including the
rock properties: pore / pore throat size; absolute and relative permeability (Okui
and Waples, 1991, 1992 and 1993) or net permeability to oil (Sandvik and
Mercer, 1990); and absolute petroleum potential P0 (Leythaeuser et al., 1987a;
Mackenzie and Quigley, 1988).
Important fluid properties would include
interfacial tension and viscosity (Palciauskas, 1991).

III: DESCRIPTION OF THE OPEN-SYSTEM MODEL

Expulsion and primary migration: summary and implications for model
design
Expulsion efficiency is an intrinsic property of a source bed, dependent on the
composition (generative vs. sorptive capability) of its internal OM mass; not on its
absolute concentration. Expulsion is governed by HI0 (Figure 2a) because of the
important compositional information provided by this simple parameter (Part I,
Figure 3). 0.1 gOIL gC-1 and 0.02 mgGAS gC-1 must be available (the net result of
generation and cracking processes) for expulsion of oil and gas range molecular
weight petroleum to occur.
Having demonstrated that source beds' internal primary migration losses
are small, we focus our modelling of petroleum release on the process of
expulsion. Primary migration is controlled by the total stratigraphic architecture,

35

and needs to be accounted for outside simple zero-dimensional models such as

ORGAS (see Section V). In this Section we describe the model's components
and input requirements, illustrate some results, and test it against data.
Components of the model
Oil and gas generation module
Part I presented a scheme in which oil- and gas-generative kerogen portions
degrade independently. Required kinetic parameters in the system of Arrhenius
equations governing oil and gas generation rates are provided by A (the
frequency factor), Emean (the mean activation energy) and a gaussian activation
energy distribution comprising five E (standard deviations in activation energy)
about Emean. Global parameter values are assigned for both oil and gas
generation by classifying the source rock as one of five global kerogen kinetic
Organofacies.
Oil to gas cracking module
Part II described the scheme ORGAS uses to simulate concurrent oil generation
and oil-to-gas cracking. The required kinetic parameters in the system of
Arrhenius equations governing oil to gas cracking rates are again provided by A,
Emean and a gaussian activation energy distribution comprising five E about
Emean. Parameter values are derived: A is a global value 1014 s-1; Emean and
E are predicted from HI0 of the OM, which reflects the average saturate /
aromatic ratio of the generated oil and controls its thermal breakdown rate.

Expulsion module
Quantities of oil and gas available (i.e. after the processes of oil and gas
generation and oil-gas cracking have been allowed to take place) are compared
with threshold quantities required for expulsion. The Oil and Gas Expulsion
Threshold (OET and GET, respectively) quantities of oil and gas at any time are
defined relative to the residual organic carbon at that time.
CO(j) < WO * aO * [ CKI + CKO (j) + CKG (j) ]

(6)

CG(j) < WG * aG * [ CKI + CKO (j) + CKG (j) ]

(7)

and:

where: CO(j), CG(j), CKI, CKO(j) and CKG(j) are the carbon concentrations in oil,
gas, inert kerogen and residual oil- and gas-generative kerogen, respectively,
during the jth temperature step; aO and aG are sorption coefficients for oil and
gas, respectively. (N.B. this differs from Pepper's (1991) notation which
considered an earlier model of reactive kerogen.)

36

Equations 6 and 7 imply that expulsion thresholds are controlled partly by

the rates of oil- and gas-generative carbon breakdown and, most importantly, by
the constant inert carbon mass. Except in very good quality source rocks (HI0 >
ca. 600 mgHC gC-1), inert carbon (which is a chemical concept: it is not
synonymous with the petrographic maceral inertinite; Part I) will comprise more
than half of the initial carbon and so will play a major role in determining the
expulsion efficiency at all maturation levels. Even at high levels of thermal
stress, when most of the oil-generative kerogen has degraded, inert (and
subordinate residual gas-generative) carbon will remain to impede oil expulsion
(Pepper, 1991). This is the first of two fundamental reasons for the gasproneness of Type III source rocks sensu Tissot (1984), with low HI0 and hence
high inert kerogen content. (Part II showed the second factor to be that low HI0
kerogens generate aromatic oils which crack readily to gas.)
The ORGAS algorithm: a cycle of events
The results of the kinetic calibrations outlined in Parts I and II demonstrated that
the processes of oil generation, gas generation and oil-to-gas cracking are (at
least to some extent) concurrent processes. Modelling a system which respects
this concurrency, and which is 'open' (in the sense that some of the generated
petroleum can be expelled), is a matter of 'organic carbon book-keeping',
performed in the order:
oil and gas inherited
v
oil and gas generated from kerogen
v
oil cracked to gas
v
oil and gas expelled
Repetition of this cycle in successive small isothermal temperature steps (1 oC)
simulates a continuum. Temperature limits for the cycle would typically be 50300 oC, covering the range of OGW and GGW in sedimentary basins unaffected
by igneous intrusions. Permissible heating rates include those encountered in
laboratory bulk-flow pyrolysis, e.g. 250 - 550 oC at 25 oC min-1 (1.315e13 oC
Ma-1).
Step 1: inheritance involves "carrying forward" to the next temperature step
the residual oil and gas quantities remaining after expulsion during the previous
one, ensuring a mass balance. The model starts up by "inheriting" the initial oil
concentration present in all immature source rocks.
Step 2: generation involves breakdown of some fraction of the residual oiland gas-generative kerogen, producing oil and gas.
Step 3: oil cracking involves breakdown of some fraction of the oil to gas.
Step 4: expulsion evaluates the critical threshold quantities required for
expulsion (Equations 6 and 7). If quantities of oil and gas available (after the oil

37

and gas generation and oil-gas cracking steps) are less than or equal to this
critical threshold, they are carried forward, to be inherited by the succeeding isomaturity slab; they are labelled as Residual quantities. Any excess oil or gas is
labelled as Expelled.
Input data requirements
ORGAS is designed to require only a basic minimum of raw input data: the
Organofacies and initial organic matter composition; and its thermal history.
Starting organic carbon composition
Routine geochemical measurements are used to divide up the initial carbon
quantities in a source rock (Part I, Equations 1-10), including the inert portion
important in modelling the total sorptive carbon mass. Initially, in the immature
source rock, since all quantities are normalised to TOC:
CKI + CO0 + CKO0 + CKG0 = 1

(8)

The required initial parameters are: Transformation Index TI0 (i.e. S10 or TSE0
normalised to TOC0), HI0, and G0 (initial gas fraction in S20). Absolute P0 and
TOC0 are not required. Organofacies and HI0 are the most important inputs to
be known accurately. If TI0 or G0 data are lacking they can be predicted using
global correlations vs. HI0, or defaulted to global values for the relevant
Organofacies (Part I, Figure 2 and Table 6).
Figure 19a contrasts the calculated initial carbon composition of three
different types of coal which reinforces our point (Part I, Figure 3) that the most
significant difference between source rocks lies in the proportion of oil-generative
vs. inert kerogen. Scaling generation profiles for each coal according to total
carbon (Figure 19b-d), rather than to the carbon in P0 (Part I, Figure 18)
emphasises the high sorptive potential of the typical Organofacies D/E, and
particularly F, coals compared to the Torbanite.
In a closed system, with no oil cracking, carbon in generated oil (COK) and
gas (CGK) would increase at the expense of carbon in reactive kerogens CKO
and CKG, respectively. However, to monitor oil-to-gas conversion, further
quantities CGO (carbon in gas derived from oil) and CO (carbon in remaining oil)
are required (Equation 8 of Part II). (Not all these individual quantities are output
- this is merely an internal 'book-keeping' nomenclature). If available quantities
of oil (=CO) or gas (=CGO+CGK) in any time-step exceed the required
thresholds (Equations 6 and 7), excess carbon is labelled as expelled oil (COE)
and / or gas (CGE). Carbon mass in the total system is conserved at any step j
in the temperature history:

CKI + CKO(j) + {CO(j)+ COE(j)} +CKG(j) + {CGK(j) + CGO(j) + CGE(j)} = 1

38

(9)

Thermal history
The temperature-time history of a potential source bed can be simulated in a
number of ways. Following Parts I and II, we will illustrate model results
calculated at a reference constant heating rate of 2 oC Ma-1. To denote this we
use the notation T2. ORGAS can also read a non-linear temperature-time history
from a 1-D or 2-D thermal model.

Figure 19 (a) Initial carbon composition of three coals, calculated using

Equations 1-10 (Part I). (b)-(d) Generation profiles for each, shown on a carbon
basis, including the Inert portion: (b) torbanite / algal boghead coal (Organofacies
C); (c) typical Organofacies D/E humic coal; (d) typical Organofacies F humic
coal; (e)-(g) Mass fraction of gas in petroleum reserves of representative basins
containing Organofacies C, D/E and F, respectively (data from Pepper, 1991;
Macgregor, 1994).
Illustrative model output graphs

39

ORGAS dumps results into a spreadsheet-based graphing package CRICKET

GRAPHTM. Thus the user has flexibility in data presentation, and it is easy to
test model results by cross-plotting against calibrant data imported from other
databases or spreadsheets.
Figures 20a - c show the full range of output fractional concentration
quantities vs. temperature, for a typical Organofacies B source rock (e.g. Upper
Jurassic KCF or Draupne Formations, North Sea Basin).
Oil and gas
concentrations are normalised to P0 [= cO0 + cKO0 + cKG0]. Absolute
quantities are obtained by scaling the y-axis appropriately, e.g. residual oil
concentration cO = 0.1 represents 3 mg g-1 oil in a rock with original potential of
30 mg g-1.

Figure 20 Example ORGAS output for typical high quality Organofacies B (Part I;
Table 6) showing fractional quantities (normalised to P0) vs. temperature, at
heating rate 2 oC Ma-1: (a) generated quantities; (b) residual quantities; (c)
expelled quantities.
Generated quantities: generation profiles
Figure 20a shows four generated quantities:
o
"cO" - an area representing the cumulative oil concentration (= cO / [cO0 +
cKO0 + cKG0] );

40

"cG" - an area representing the cumulative gas concentration ( = cG / [cO0

+ cKO0 + cKG0] );
o
G, the mass fraction of gas in petroleum ( = cG / [cG + cO]), on both an
instantaneous and a cumulative basis.
This is the simplest graph: oil and gas accumulate as the respective kerogens
break down. The upper bound of the oil-plus-gas envelope represents the
cumulative petroleum generated (Hydrocarbon Generation Index HGI of Cooles
et al., 1986; Petroleum Generation Index PGI of Mackenzie and Quigley, 1988).
Two line graphs show the fractional gas content of the generation products on
both an instantaneous and cumulative basis. The instantaneous graph predicts
that very low GOR petroleum is generated over the early generation profile; dry
gas is exclusively generated > 170 oC. The cumulative curve illustrates the
general rule that kerogen-derived gas from "overmature" source rocks is almost
always subordinate to cumulative oil (Part I, Figures 18a-e). If source rocks
behaved as completely open systems (c.f. bulk-flow pyrolysis), retaining no oil
feedstock for cracking to gas, then the quantities on this graph could be re-cast
as expelled quantities. The graph could also present the artificial situation of a
completely closed source rock in which no oil-gas cracking were permitted.
However, source rocks are neither completely closed nor completely open
systems.
o

Residual quantities: retention profiles

Figure 20b provides a more realistic picture of evolving oil and gas
concentrations: a graph of residual quantities derived by allowing some of the
products to be removed while the residual oil is progressively subjected to
cracking at inceasing rates. It shows four residual quantities:
o
'cO': an area representing the residual oil concentration (= cO / [cO0 +
cKO0 + cKG0]);
o
'cG': an area representing the residual gas concentration (= cG / [cO0 +
cKO0 + cKG0]);
o
'G': mass fraction of gas in petroleum, on both an instantaneous and a
cumulative basis (= cG / [cG + cG]).
Petroleum concentrations in source rocks reflect generation processes in
isolation only at low maturity levels, prior to expulsion, and before oil-gas
cracking rates become significant (c.f. similar oil concentration curves on Figures
20a and b at < 110 oC). If expulsion efficiency were zero, then Figure 20b would
be identical to Figure 12b of Part II - illustrating cracking in a closed-system.
However, ORGAS allows the source rock to become 'open' to oil or gas when/if
the residual kerogen is saturated.
In expulsive source rocks, concentrations of residual oil and gas (solid
areas) increase as generation proceeds, reaching inflections which mark the
threshold of oil expulsion (OET) and gas expulsion (GET), respectively. OET is
reached before GET. They then begin a gradual decline which occurs because
the expulsion threshold is calculated by reference to total residual carbon, which

41

decreases as reactive carbon degrades until only Inert carbon remains. An oil
concentration associated with inert carbon would persist at the end of the profile,
but for the effect of oil-to-gas cracking which converts this residual oil to gas.
Thus, a second inflection point occurs, marking an acceleration in the rate of
decline, where oil-to-gas cracking rather than sorption begins to limit the oil
concentration in the source rock. Since gas is not degraded, residual gas
concentrations are always controlled by the expulsion threshold concentration
(e.g. 0.02 g gCK-1), once reached. The G curve monitors the mass fraction of
gas in the residual petroleum.
Expelled quantities: expulsion profiles
Oil and gas concentrations expelled at the end of each cycle are simply those in
excess of the Residual quantities; when summed over the whole temperature
profile they produce the cumulative expelled quantities shown in Figure 20c.
Four expelled quantities are shown:
o
"cOE" an area representing the cumulative oil concentration (= cOE / [cO0
+ cKO0 + cKG0]);
o
"cGE" an area representing the cumulative gas concentration (= CGE / [cO0
+ cKO0 + cKG0]);
o
'G': mass fraction of gas in petroleum (= cGE / [cGE + cOE]), on both an
instantaneous and a cumulative basis.
Expelled quantities (solid areas) begin to register at temperatures corresponding
to inflections in the respective residual curves.
Quantitative expulsion behaviour of typical Organofacies
The use of "typical" Organofacies A-F source rocks helps illustrate some
fundamentally important differences in their retention and expulsion behaviour
(Figure 21).
Typically high quality Organofacies A-C source rocks expel oil readily, after
15-20% of P0 has been converted (PGI 0.15-0.2). Oil expulsion temperature
(T2) thresholds for typical Organofacies increase in the order A-DE: 100, 110,
120, 135 oC. Organofacies D/E typically expel oil at a slightly higher PGI of 0.3,
but at a significantly higher temperature, than A-C, resulting in a narrow oil
expulsion window prior to acceleration of oil-gas cracking rates.
The Organofacies F retention profile illustrates the behaviour of poor quality
source rocks (HI0 < ca. 200 mgHC gC-1) in general, irrespective of
Organofacies. The symmetry of the residual oil curve arises because: the
expulsion threshold concentration of oil is never generated; and / or oil-gas
cracking is fast enough to prevent this threshold concentration from being
reached. Low HI0 source rocks - and those with Organofacies F generation
kinetics in particular - can generate oil but typically can not expel it: they are gasprone as a result of oil-gas cracking in a low expulsion efficiency environment.
Typically high quality Organofacies A-C source rocks will expel the
dominant fraction of their P0 (70-80%) as oil (c.f. Figure 2c). Organofacies D/E

42

typically expels oil, but as a subordinate fraction (ca. 30%) of P0. Thus,
concerning the historical debate about whether "Type III" source rocks - including
coals - can source low GOR petroleum (oil) pools: those with high enough HI0
and Organofacies D/E kinetics can; but even so their cumulative expulsion
products will be gas-dominated.
Typical cumulative gas fractions in the expelled products are, in the order AF, ca.: 0.25, 0.30, 0.25, 0.65 and 1.0 g g-1. These fractions are ultimately
reflected in "basin GOR" (Figures 19e-g). High quality aquatic source rocks such
as the Pematang Brown Shale, Central Sumatra (Longley et al., 1990) give rise
to petroleum provinces dominated by efficiently-expelled oil (e.g. Typical C
expulsion profile, Figure 21); so-called "oil-prone" coals such as the Miocene
Balikpapan Formation coals of the Mahakam Delta, Kutei Basin, Kalimantan give
rise to "oil" provinces which are actually dominated by the gas formed from
cracking of unexpelled oil (e.g. Typical D/E expulsion profile, Figure 21); poor
quality coals such as the Carboniferous of the Southern North Sea Basin release
hardly any of the oil they generate, and yield essentially dry gas deposits (e.g.
Typical F expulsion profile, Figure 21). The high concentrations of gas expelled
from the Typical F source rock is consistent with estimates of 90-95% gas
expulsion efficiency attained in Palaeozoic anthracite rank coals (Stach et al
1982).

Figure 21 ORGAS output showing fractional quantities of oil and gas in: (a)
residual petroleum "retention profiles"; and (b) cumulative expulsion products
"expulsion profiles", for typical Organofacies A-F as a function of temperature, at
reference heating rate 2 oC Ma-1.

Testing against geochemical data

Since ORGAS attempts to quantify two products (oil and gas) resulting from
three partially concurrent processes: generation, cracking and expulsion, our

43

tests compare predicted vs. 'actual' residual or expelled quantities which are
sensitive to these processes.
Figure 22 shows how the model fares in predicting various calibrant organic
geochemical quantities in a thick Monterey Formation source bed. Sulphur-rich
Monterey OM is the source of major oil fairways both on- and offshore California
(Orr, 1986). This marine source rock contains algal / bacterial OM in a matrix
low in detrital clay and rich in carbonate and siliceous / cherty material: the
kinetic Organofacies is A. (Since this was a dataset used in the global kinetic
optimisation in Part I, this is mainly a true 'blind test' of oil cracking and petroleum
release behaviours.) Initial model input parameters (TI0, HI0, G0) are the
average of numerous measurements from the shallow (immature) section of the
well. Carbon-mass balance used these same data as an immature reference.

Figure 22 Model testing in a thick Monterey Fm. source bed. (a) cOE
(concentration of P0 expelled as oil) vs. temperature (heating rate 12.8 oC Ma-1),
using alternately: extract or S1 as measures of oil; S2e and Ge or S2 and G as
measures of residual kerogen, respectively. (b) ORE (oil release efficiency)
versus OGI (oil generation index), predicted and calculated using S1 as a
measure of oil, S2 and G as measures of residual kerogen. (c) Modelled and
observed PI using S1, S2, G and aO as in (b). The data-trend (solid symbols)
can not be matched oby any single model curve (e.g. curves shown for HI0 =
476, 639 and 1106 mg gC-1).

44

Testing against carbon mass-balance results

Generated, residual and expelled quantities output by ORGAS (e.g. Figure 21)
are normalised to P0 and can only be compared with corresponding quantities
derived from geochemical measurements on natural sample suites once these
raw data have been manipulated using carbon mass-balance back-calculations
(Leythaeuser et al., 1980; Ungerer et al., 1988; Cooles et al., 1986; Rullkoetter et
al., 1988; Pepper, 1991). Some caveats in the approach, together with
equations defining additional quantities, are summarised in Appendix A.
Expelled quantities: extract vs. S1 comparison (Figure 22a). In the studied
well, pyrolysis was performed on duplicate samples with and without preextraction. Pre-extraction avoids the problem of 'double-counting' which occurs
when extract and unextracted S2 yields are manipulated together (Cooles et al.,
1986), which is particularly acute in Organofacies A source rocks where extract
yields may be five times larger than the S1 yield for the same sample. The two
resulting datasets comprised: conventional S1 plus S2 yield plus G data; and
extract plus post-extraction S2 yield and G data (denoted S2e and Ge). This
figure tests the performance of different oil sorption coefficients: 'observations'
(point symbols) are well matched by the model (curves) using the appropriate aO
value: 0.1 gO gCK-1 for S1 (solid symbols and unbroken curve); 0.2 gO gCK-1
for total extract (open symbols and dashed line). In each case, observed release
/ predicted expulsion from the Monterey begins at low temperatures (ca. 100-110
oC) even given the high heating rate; it is ultimately efficient (cOE reaching 0.7 0.8). The good agreement we obtained here between predicted expelled
quantities and 'observed' released quantities supports our decision to neglect
primary migration effects in the ORGAS model.
Expelled quantities: ORE vs. OGI (Figure 22b). This diagram compares
predicted and observed ORE (oil release efficiency) versus OGI (oil generation
index). 'Observations' (solid symbols) are matched by the model (solid curve)
using S1 as a measure of oil, and aO = 0.1 g gCK-1: oil release begins during
early generation (before 20% of oil-generative kerogen is degraded: OGI < 0.2).
Thus, expulsion of 'low mature' (heavy, asphaltenic) oils is a characteristic of the
Monterey petroleum system (Orr, 1986).
Calibration using geochemical ratios
Routine geochemical measurements of oil concentration are normalised to
residual organic carbon or residual petroleum potential. ORGAS facilitates
calibration by outputting these residual ratios during each model run:
PI Production Index = cO / [cO+{cKO+cKG}], i.e S1/[S1+S2]. Though widely
used as a maturity index, this pyrolysis-derived ratio has no straightforward
progression: S2 decreases systematically as oil and gas-generative
kerogen are consumed; S1 increases progressively prior to expulsion, but
then decreases due to combined effects of expulsion and / or cracking to
low molecular weight products (which are either themselves expelled or, if

45

HI

TI

remaining, are usually lost during the normal drilling and sample handling
procedures). Depending on the relative rates of generation and cracking,
the net effect on PI at high thermal stress can be an increase or decrease.
(= 1000 * [{cKO + cKG}/W ] / [cO + cKO + cG + cKG + cKI] in mgHC gC-1).
The numerator decreases systematically as reactive kerogen degrades,
while the rate of decrease of the denominator depends on release
efficiency: note the cO and cG terms in the denominator; the TOC of a
source rock which does not expel remains constant. Thus, ratios involving
the term [HI/HI0] (as used by e.g. Forbes et al., 1991) are not reliable
calibrants of petroleum generation.
Transformation Index (= 1000 * [cO / W] / [cO + cKO+ cG + cKG + cKI]); i.e.
{S1 or TSE} / TOC, in mgHC gC-1). Again, the rate at which the

denominator decreases depends on expulsion efficiency. S1 increases

progressively prior to expulsion, but then decreases due to the effects
described for PI.
These residual geochemical ratios provide perhaps the most practical way to test
the model with minimal data manipulation although, again, there are caveats
(Appendix A). Figure 22c compares modelled and observed PI vs. maximum
burial temperature. Here there is crude agreement between model and
observation viz. the overall increase in PI between 100-170 oC, although the
model curve for average HI0 = 639 mg gC-1 is much smoother than the data
trend (solid symbols) which shows consistent excursions (magnitude ca. 0.1)
towards relatively high followed by relatively low PI. These are most likely due to
deviation in original downhole organic matter quality from the reference
(immature tophole average), since their magnitude is consistent with results of
re-running ORGAS with a range of initial source characteristics in the immature
section (HI0 = 476 and 1106 mg gC-1, respectively). This suggests that PI is not
purely a maturation index, since its rate of increase is sensitive to expulsion
efficiency: PI increases most rapidly with maturity in rocks with low HI0 and
hence low expulsion efficiency; in contrast PI will remain low in source rocks with
extremely high HI0, and negligible Inert carbon.

IV: EXPLORATION APPLICATIONS

Potential applications of the ORGAS model range from to the routine - such as
calculations of expelled charge masses in petroleum resource estimation- to the
unorthodox, as we illustrate below.
Calculation of petroleum charge masses
Calculation of the masses of petroleum available for entrapment in a given basin,
or in the drainage area of a given trap, requires understanding of the overall

46

average concentration of oil or gas expelled from the source rock at increasing
levels of thermal stress.
Since ORGAS' output concentrations are normalised to P0, it is easy to
convert concentration of petroleum of type i (oil/gas/total petroleum generated,
instantaneous oil/gas expelled, or cumulative oil/gas expelled) at temperature T(j)
to an absolute mass delivered to the inorganic void system Mi(j) (g):
Mi(j) = ci(j)* P0(j) * rhos(j) * hs(j) * A(j)

(10)

where: ci(j) is concentration of a petroleum component i (e.g. cOE; dimensionless

units); P0(j) is the initial petroleum potential (g grock-1); rhos(j) is the bulk
density of the source bed (g m-3); hs(j) is its thickness (m); and A(j) is the area
(m2), of an 'iso-maturity slab' of source rock experiencing a mean temperature
T(j). Thus P0 is just a volumetric multiplier for fractional concentrations output by
the model; it is neither a model input parameter nor a determinant of expulsion
behaviour.
A basin geothermal profile is used to project isotherms (midpoints of
sections of equal average maximum temperature, known as iso-maturity slabs)
onto a stratigraphic surface representing the source bed (ideally an isopach from
sediment surface to source bed mid-point). In basins with simple thermal
histories (relatively uniform burial rate with no uplift and erosion), the burial rate
prior to attaining maximum temperature can be used to calculate a heating rate.
This eliminates the need for exhaustive 1-D thermal modelling (e.g. Forbes et al.,
1991). Heating rate should never be assessed using the age of the sediments
themselves; early burial and heating rates are irrelevant, since rates of reaction
at temperatures less than about 70 oC are negligible even on a geologic
timescale.
Given homogeneous organic matter quality, the source rock may be
characterised as a whole, simply by averaging required geochemical input data
over the net source interval. Note that this approach becomes less appropriate
as internal heterogeneity of source character increases - a particular problem in
terrestrial source sequences (see below). After running a model for the
appropriate source facies, each iso-maturity slab can be assigned a value of cOE
/ cGE, and Equation 10 used to calculate the total oil and gas mass expelled
within each iso-maturity slab. (Section 5 considers the additonal problem of
primary mgration.)
Predicting petroleum composition and phase
ORGAS' ability to account separately for oil and gas quantities enables prediction
of petroleum composition. G (mass fraction of gas) is monitored throughout the
expulsion cycle, on both an instantaneous and cumulative basis (Figure 23).
Combined with pressure data, these quantities can be used to predict the
instantaneous phase of migrating petroleum, or the evolving phase(s) of a

47

petroleum accumulation. Apart from the usual exploration applications, this kind
of predictive capability can help understand intra-reservoir compositional
variations (England and Mackenzie, 1989; England, 1990), which originate during
reservoir filling due to spatial and temporal variations in charge composition.

Figure 23 Model output for the fractional mass of gas in: (a) instantaneous
petroleum expelled (Ginst.); and (b) cumulative petroleum expelled (Gcum.), from
typical members of Organofacies A-F at a reference heating rate of 2 oC Ma-1.

Heterogeneous source rocks

Although we have illustrated "typical Organofacies" behaviours, we do not
propose another "Type" classification into which individual source rocks are
shoe-horned. Since ORGAS requires only limited input data, individual cases
are rapidly re-run; for example when evaluating the impact of natural source rock
heterogeneity, most importantly HI0. This permits detailed description of the
expulsion behaviour of heterogeneous sequences. This problem is most acute in
non-marine basins with rapid depositional facies variations which impact OM
quality, leading to different generation and expulsion behaviours in different parts
of the resulting source sequence (Demaison, 1987).

48

Figure 24 Modelled effect on (a) Ginst. and (b) Gcum. of a + 200 mgHC gC-1
variation in HI0 for high quality (e.g. typical Organofacies C) and mediocre quality
(e.g. typical Organofacies D/E) potential source rocks.
Vertical variability (Figure 24). The expulsion behaviour of high quality
source rocks will be least impacted by, say + 200 mgHC gC-1, variation in HI0
(e.g. typical Organofacies C). However, where average HI0 is modest (e.g.
typical Organofacies D/E with mean HI0 333 mgHC gC-1), the effect of this same
HI0 variation is much more dramatic: Gcum. ranges from ca. 0.4 (slightly more oil
then gas) to 1 (dry gas source throughout the expulsion profile). In such cases
we would re-run ORGAS as necessary to reflect OM quality variations, and then
re-composite the results into a profile weighted according to relative abundance
of each OM type. These composited results can differ significantly from the
results for the average.
Lateral variability. Many petroleum drainage areas will be large enough that
random lateral variations in initial characteristics are statistically smoothed.
Alternatively, regional variations will systematically affect the composition of
petroleum from one drainage area to the next (Figure 25). In such basins, it may
be necessary to calculate separate local (composited) expulsion profiles, and
contour the resulting cOE / cGE values with respect to facies as well as thermal
stress - quite a laborious process! Pepper (1991) described an Australasian
Angiosperm-dominated coal basin with local developments of exceptionally high
quality coal which expel petroleum at moderate thermal stress (T2 ca. 140 - 160
oC), which is oily enough to form a single subsurface "black oil" phase.
Elsewhere quality is locally poor (mean HI0 ca. 200 mgHC gC-1) and coals retain
and crack much of the oil they generate, expelling only gas and low molecular
weight oil desorbed at higher temperatures (Figure 25a; T2 > ca. 150 oC). This
may have high enough GOR to form single subsurface gas-condensate phases
(Figure 25b). Intermediate quality coals expel petroleums intermediate in
composition which, unless reservoired at very high pressure, form mixed phase
associations (saturated oil phases with gas caps; saturated gas-condensates
with oil rims).

49

Figure 25 Data from an Australasian coal-sourced petroleum province where

lateral variation in coal quality determines maturity and gas-richness of expelled and the phase state of reservoired petroleum (Pepper, 1991). Plotted against
mean HI0 of local coal are (a) thermal stress level of reservoired petroleum
estimated from aromatic biomarkers and (b) G of reservoired petroleum. Large
open circles: subsurface gassy phase; small solid circles: subsurface oily phase;
both: mixed phase. Model curves predict: (a) variation in temperature of OET;
and (b) Gcum, as a function of HI0.

Biogenic gas and "early condensates"

Some gassy petroleums have C6+ molecular chemistry apparently inconsistent
with a conventional high maturity origin. These so-called "early" or "immature"
condensates (Vassoevich et al., 1969; Laplante, 1974; Connan and Cassou,
1980; Snowdon and Powell, 1982; Monnier et al., 1983) supposedly form due to
stripping of low molecular weight C6+ material during expulsion of a thermogenic
gas phase at low thermal stress. Alkane fractionation effects observed in Type III
source rocks are consistent with this mechansm (Leythaeuser et al., 1984a;
Leythaeuser and Poelchau,1991).
Our kinetic parameters (Part I) predict that thermogenic gas generation
rates are very low at the cited thermal stress levels (though perceptible using
sensitive chromatography; e.g. Monnier et al., 1983). So, thermogenic gas
expulsion is delayed by the sorptive kerogen network until T2 > 150 oC (Figure

50

21; Organofacies D/E). However a different result occurs if sorptive sites are
"presaturated" during biogenic gas generation, an idea supported by Friedrich
and Juntgen's (1972) discovery that methane most tightly sorbed on highly
mature coals (1.0-1.25 % Ro) had a biogenic isotopic signature.
Though ORGAS is an exclusively thermogenic model, we can simulate this
situation by setting aG to zero (Figure 26). The result is an initial window of dry
gas expulsion; G falls to a minimum during early oil expulsion, rising later as
thermogenic gas expulsion rates increase. The period prior to the G minimum
might correspond to the "early condensate" window. Even so, this early-expelled
gas charge will be minor compared to the later thermogenic charge.

Figure 26 Possible "early condensate" expulsion phenomenon simulated by "presaturating" kerogen with biogenic gas. Curves show the predicted evolution of
Ginst and Gcum calculated for typical Organofacies D/E OM (Part I, Table 6).
Expulsion during uplift and erosion
Conventionally, the burial cycle is attributed with the driving energy - increasing
pressure and temperature - for petroleum migration. ORGAS responds to
cooling during uplift and erosion like any other kinetic model, by decreasing the
rates of the chemical reactions which provide the expulsion feedstock. However,
if aG and aO are pressure-dependent, this generalisation may break down.
Figures 12 and 14 suggest that gas sorption capacity should decrease rapidly
during at least the last 2 km of overburden removal, consistent with the cooccurrence of coalbed and conventionally-reservoired gas deposits at shallow
depth in uplifted basins (e.g. Iannacchione and Puglio, 1980).
Gas expulsion during "basin-scale desorption" will be limited by the
saturation value of aG (0.02 g gCK-1). This is low compared to expellable gas
potential during burial (i.e. the product [cGE* HI0]). Thus, such an expulsion
mechanism will be volumetrically significant only in highly organic-rich -

51

particularly coal-bearing - sedimentary successions. The methane-rich Elmworth

dry gas field, Western Canada (Masters, 1984) may be a spectacular example.
Welte et al. (1984) showed that gas concentration gradients in the field are best
explained by dynamic charging, i.e. with gas being continuously supplied up to
the present; however this is inconsistent with the burial history of the basin, which
has been substantially uplifted, eroded and cooled since the Oligocene. Our
proposed desorption model offers a solution consistent with these constraints
and also with the methane-richness of the reservoired gas: progressive
desorption of part of the 2.2 X1015 g (116 trillion scf) of methane originally stored
in the basin's recognised164 billion tons of low ash coal (Figure 13c; data from
Wyman, 1984; these projections do not account for other organic-rich beds in the
2 km thick series).
This mechanism also offers an explanation for relict abnormal pressures in
source beds, in uplifted and eroded basins where overpressure generated by
compaction disequilibrium processes has long since dissipated in surrounding
organic-lean beds (e.g. Williston Basin; Burrus et al. 1993).
Case history: Malacca Straits, Indonesia
We conclude this Section by applying ORGAS in an Indonesian coal-bearing
basin: the Malacca Straits area, Central Sumatra, Indonesia. We revisit a
published quantitative case study of charging and migration losses involved in
the pooling of waxy non-marine oils (see Macgregor and Mackenzie, 1986, for
supporting information; also Mackenzie and Quigley, 1988). To ensure a fair
comparison of models, we have ignored all subsequent information in our reevaluation, which concerns only the issue of expelled oil charge.
Assuming Lower Miocene Sihapas Formation coals as the principle source
rock, Macgregor and Mackenzie (1986) defined kitchens using an oil release
window between 120 - 150 oC (Figure 27): a global rule of thumb emerging from
Cooles et al. (1986) study of ten source rocks. This was supported by a carbon
mass-balance calculation for the Sihapas coals. Compare this with ORGAS
modelled expulsion behaviour for a typical Organofacies D/E (i.e. most
Indonesian Tertiary) coal, which predicts oil expulsion > ca. 140 oC at 6 oC Ma-1;
the oil expulsion window is narrow and is soon followed by thermogenic gas
expulsion at ca. 160 oC.

52

Figure 27 Proposed expulsion profiles for coaly Sihapas Fm. potential source
rocks: Macgregor and Mackenzie's (1986) bulk petroleum release curve
projected early (>120 oC) and efficient oil release; ORGAS output (cOE and cGE
area curves) for 'typical' Organofacies D/E OM (initial characteristics TI0 = 7
mgHC gC-1, HI0 = 333 mgHC gC-1; G0 = 0.24; Part I, Table 6) has a high oil
expulsion threshold (>140 oC) and implies a low expulsion efficiency.

These differences can be reconciled: the dataset on which Cooles et al.

(1986) formulated their global rules of thumb did not include coals (Figure 2a);
Macgregor and Mackenzie (1986) did not apply the large corrections which we
believe are necessary to account for losses in the low molecular weight range of
coal samples (Appendix A). The consequences for resource potential of the
Sihapas coals are dire: the extensive and volumetrically significant Sihapas
kitchen (Figure 28a) is replaced by a trivial area of marginal oil expulsion in the
basin axis (Figure 28b).

53

Figure 28 Comparison of oil-expulsive kitchens implied by curves in Figure 27.

Black dots are control wells. Maps derived by superimposing iso-cOE values on
mid-Sihapas isotherms: (a) Macgregor and Mackenzie's (1986) widespread
kitchen; (b) ORGAS-based projection of a kitchen of insignificant area.

Macgregor and Mackenzie (1986) recognised an alternative potential

source for the basin's waxy oil pools, then unproven: the freshwater lacustrine
Pematang Formation, a syn-rift deposit in the adjacent Central Sumatra Basin
(Katz, 1991) which has sourced some 13 billion barrels of oil reserves. Similar
wax-prone Pematang facies have since been drilled in the Malacca Straits and
oil-source correlation studies have confirmed them as the working source rock
(Longley et al., 1990). While this does not invalidate quantitative resource
assessment using charge volumetrics and migration losses, it does serve to
illustrate - retrospectively - an example where ORGAS would have proved more
accurate in assessing the oil resource potential of the coals.

V: PRIMARY MIGRATION AND BASIN ARCHITECTURE

Primary migration occurs when petroleum eventually exploits the more
permeable avenues of the inorganic void systems of fine grained rocks; an
exception may occur where a low-ash coal lies in direct contact with a secondary
migration avenue. The process is very efficient: we estimate losses of the order
1 mg g-1 or less; past estimates ca. 5 mg g-1 confused oil present in the organic
vs. inorganic networks.
Primary migration efficiency is not an intrinsic property of a source bed except where a source bed lies in direct contact with a secondary migration
avenue - since losses will occur in the whole volume of source and non-source

54

lithologies separating kerogen-rich zones from potential secondary migration

avenues.
Primary migration is controlled by the total stratigraphic architecture, so it
needs to be accounted for outside simple zero-dimensional models. Although
rigorous treatment of the problem requires some kind of 1- or 2-D multi-phase
fluid flow modelling approach, we have found it useful for the purposes of
resource estimation to treat it as a mass balance problem. We apply a primary
migration loss factor, just as secondary migration losses may be handled in
geochemical resource assessment (Mackenzie and Quigley, 1988).
Thus, before product masses from Equation 10 are summed over the
expulsion kitchen for the play fairway or prospect, as appropriate, losses
occurring during primary migration must be accounted for. Equation (10) can be
modified:

Mi(j) = [(ciE(j)* P0(j) * rhos(j) * hs(j))

- (si * rhom(j) * hm(j))] * A(j)

(11)

where quantities were defined in Equation 10 except: the fractional loss factor si
[g grock-1; sO lies in the range 0.0001 to 0.001]; rhom(j) which is the bulk density
of rocks along the primary migration route [g m-3]; and hm(j) which is the height
of vertical migration. Limits on vertical migration distance can be evaluated by
rearranging Equation (11) with Mi(j) set to zero.

hm(j) =

ciE(j) * P0(j) * rhos(j) * hs(j)

___________________
(12)
i
s * rhom(j)

Furthermore, the potential distance of primary oil migration (provided expulsion

has occurred) will be constrained by a source bed's ultimate genetic potential
(UGP) - the numerator of Equation 11 evaluated when ciE has its PGI=1 value.
The lower the UGP, the shorter the permitted distance between source and
secondary migration avenue; internal losses may not be overcome in the worst
cases.
Resource potential: implications of different models
Most extant approaches treat petroleum release as a primary migration /
inorganic void saturation problem or else simply relate petroleum release
efficiency to maturation level, without any attempt to be deterministic. In this final
section of the paper we use Figure 29 - a quality / yield matrix - to compare their
implications for petroleum resource potential (e.g. critical P0 ca. 5 mg g-1) with
those of our organic sorption based model (critical HI0 ca. 200 mgHC gC-1).

55

Figure 29 Location of five illustrative source rock fields on a quality (HI0) vs.
richness (P0) matrix: (1) rich, high quality marine source rocks; (2) rich, high
quality lacustrine oil shales and boghead coals; (3) humic coals; (4) source rocks
with modest richness and quality; (5) lean, poor quality source rocks.

Fields 1 and 2 represent aquatic source rocks, rich in high quality algal /
bacterial biomass: Field 1 contains the marine source rocks which have sourced
most of world's oil resources (Klemme and Ulmishek, 1991); Field 2 contains
lacustrine source rocks which are economically important in the Far East (Katz,
1990 and 1991). Due to combined richness and quality (P0 >> 5 mg g-1 and HI0
>> 200 mgHC gC-1) high oil release potential will be assigned using either
approach. Ironically, the source rocks which - for sound economic reasons - are
most frequently studied are actually the least useful in testing petroleum release
concepts!
By substituting reasonable values for typical Organofacies A, B, or C in
Equation 12 (e.g. cOE = 0.7; P0 =0.03; rhos = 2.4 X106 g m-3; hs = 50m; rhom =
2.5*106 g m-3), and taking sO = 0.0005 (i.e. roughly the midpoint of the range
0.1 < sO < 1 mg g-1) it becomes apparent that substantial vertical migration is
possible: in this case, when fully mature, 2 km. Thus, such source beds, even
when buried deeply by thick sedimentary piles such as the Tertiary Gulf of
Mexico delta system, can charge prolific fairways at much shallower depths.

56

Vertical migration distances would be much more limited - of the order 200m in
this case - if si were an order of magnitude larger i.e. 0.005 (5 mg g-1).
However, differing behaviours are predicted for source rocks plotting
elsewhere on the matrix. Field 3 contains a family of source rocks whose
petroleum potential has been widely debated: the humic coals (Durand and
Paratte, 1983). We have emphasised that the key to understanding oil expulsion
capability of coals lies in organic quality rather than richness (Figures 24b and
25). It is our experience in humic coal-bearing basins (Figures 19f and g) that
coal-sourced petroleum systems are relatively oily when significant proportions of
the coal population has HI0 >> 200 mgHC gC-1 (e.g. Mahakam Delta, Kalimantan:
GOR of reserves ca. 104 scf bbl-1); exceedingly gas-rich petroleum systems
result when significant proportions of the coal population has HI0 << 200 mgHC
gC-1 (e.g. Southern North Sea Basin: GOR 105-106 scf bbl-1). Our projections
are generally consistent with global observations of oil and gas reserves tied to
coal source rocks (Macgregor, 1994). For 2 km vertical migration to occur from a
fully mature low-ash coal source rock (cOE = 0.3; P0 =0.22; rhos = 1.35 X106) the
bed thickness hs(j) would need to be 30m.
Field 4 comprises source rocks with, at best, modest richness and quality
(e.g. Upper Jurassic and Lower Cretaceous marine mudrocks on the northwest
Australian continental margin; some zones of the Upper Jurassic Heather
Formation of the UK North Sea Basin). While "pore saturation" models would
largely relegate such rocks to potential gas sources, our model permits - so long
as HI0 exceeds ca. 200 mgHC gC-1 - some fraction of P0 to be expelled as oil
before the gas expulsion window is entered.
However, vertical migration will be increasingly limited as the product (ciE(j)
* P0(j)) approaches si, eventually constrained within the source bed itself as
hm(j) / hs(j) approaches unity, when:
ciE(j) * P0(j) = si

(13)

As P0 drops significantly below 5 mg g-1, any oil concentrations successfully

expelled from kerogen will become increasingly sensitive to the internal primary
migration losses which can largely be ignored in predicting the behaviour of
richer source rocks. Also, significant thicknesses will be required for volumetric
significance after external migration losses are overcome. Substituting again in
Equation 12 reasonable values for a source rock of modest quality and potential
(cOE(j) = 0.3; P0(j) =0.004; rhos(j) = 2.4*106), 2 km of vertical migration could
only occur if 900m of that thickness were source rock itself!
In such situations, exemplified by the Australian NW Shelf, the stratigraphic
architecture begins to exert strong control on whether petroleum accumulation is
possible: presence of carrier / reservoir beds within or next to the source bed
becomes a deciding factor; so does the presence of occasional high quality, high

57

potential source beds in a sequence where the role of the remaining source
rocks is mainly to "prime" the migration pathway out of the gross interval. While
such source rocks are rarely responsible for prolific petroleum systems,
reluctance to recognise their capability to charge modest oil fairways can lead to
a great deal of wasted geochemical effort whereby increasingly obscure undrilled
locations in the basin are proposed as the location of the 'actual' source interval.
Because of the general observation that lean source rocks with very low
potential (P0 << 5 mg g-1) typically also have low organic quality (HI0 << 200
mgHC gC-1), both approaches agree on the lack of oil potential associated with
source rocks in Field 5, whose resource potential would widely be accepted as
minor, gas-prone, irresspective of stratigraphic architecture.

CONCLUSIONS
Petroleum moves from kerogen to secondary migration avenues in two steps:
expulsion is the release of petroleum from kerogen, where it is generated;
primary migration is the movement of petroleum through the inorganic pore /
fracture (void) networks of fine grained rocks.
Expulsion is controlled by kerogen's ability to sorbe (adsorb / absorb)
petroleum, hence ultimately by the relative proportions of generative
(Reactive)vs. retentive (Inert) kerogen. These proportions are reflected in the
initial Hydrogen Index (HI0). HI0 > ca. 200 mgHC gC-1 distinguishes OM with
the potential to expel oil from OM which retains all generated oil by sorption.
Source rocks with higher HI0 expel oil earlier and more efficiency.
HI0 also controls intra-source cracking. Low HI0 OM generates aromatic
oils which crack more rapidly than the saturate-rich oils generated by high HI0
OM. Thus, lower HI0 source rocks are affected by increasingly inefficient and
late expulsion of oil, which is increasingly quickly cracked to gas.
Equally important is the kinetic Organofacies, which governs the thermal
stress required for kerogen to generate petroleum. We recognise five global
kinetic Organofacies A, B, C, D/E and F which generate oil at thermal stress
levels increasing in the same order. Many source rocks with low HI also belong
to Organofacies D/E, and especially F, and so suffer even further from
concurrent generation and cracking of oil in a low expulsion efficiency
environment.
Variations in Organofacies kinetics, and in the HI0 typical of each
Organofacies, lead to consistent variation in expulsion threshold temperatures
(oC): (A) 100; (B) 110; (C) 120; (D/E) 135; (F) cannot expel oil; at a reference
heating rate of 2 oC Ma-1. Each order of magnitude increase (decrease) in
heating rate elevates (depresses) these thresholds by 15 oC.
Ultimate cumulative gas yields (as a mass fraction of total expelled
petroleum) from each typical Organofacies also vary: (A) 0.25; (B) 0.30; (C) 0.25;
(D/E) 0.65; (F) 1.0.

58

Once petroleum enters the source rock's inorganic void network, primary
migration begins. Its effectiveness is determined by a source rock's initial
petroleum potential (P0). However, primary migration is efficient, with minimal
saturation losses. Past estimates of losses in the 5 mg g-1 region in source
rocks have confused organic- and inorganic void-derived quantities. Primary oil
migration losses sO are of the order 1 mg g-1 or less. The effectiveness of
primary oil migration from source rocks (provided HI0 > ca. 200 mgHC gC-1) is
therefore constrained by the product [cOE*P0) and the stratigraphic architecture:
vertical migration from thick, rich, high quality source beds may be several km;
but as the value of this product decreases to approach the value of sO, the
shorter will be the permitted distance between source bed and secondary
migration avenue and the more important will be an understanding of
stratigraphic architecture of the basin.
ORGAS provides very similar predictions to 'pore saturation' models for
release efficiency from rich, high quality source beds, but offers greater
predictive capability for understanding the behaviour of source rocks with lowmodest potentials, and of coals. Humic coals in particular have been the subject
of great debate, with opposing views expressed throughout the last decade
concerning their oil resource potential. Our model suggests that all views are
correct, up to a point. Humic coals belong to Organofacies D/E/F and have HI0
values which span the critical 200 mgHC gC-1 value. Those with Organofacies
D/E kinetics and HI0 > 200 mg g -1 are able to expel some of their potential as
HC

oil; the rest are not!

Acknowledgments
We thank the management of BP Exploration for permission to publish; Drs. D.
Mann and A. Barwise of BP Research who re-wrote the original Vax-based
ORGAS code for the Apple MacintoshTM; Dr. R. Miller for the KCF data on
Figure 7a; R. Drozd for the Monterey data on Figure 22; Dr. C. Cornford and D.
Macgregor for reviews of the first draft; Misran and the Jakarta drawing office;
Ade and Agus for technical assistance; and Drs. C. Travis and Z. Yu for
comments on a revised manuscript. ASP thanks ICP, KJP and RCP for their
support and patience.

APPENDIX A
PRACTICAL DIFFICULTIES IN MODEL CALIBRATION
As a measure of total oil concentration in a rock, the S1 yield will be an underestimate since the lighter ends of the C6+ spectrum are prone to loss during
drilling, recovery and handling, while the heavy non-hydrocarbons are not
volatilised (Forbes et al., 1991). Thus, data must be corrected before use in
calculations (Cooles et al., 1986; Price, 1989; Forbes et al., 1991; Pepper, 1991).

59

Cooles et al. (1986) used an average correction factor Z, estimating that about
35% of the total oil concentration was lost during work-up of a conventional C15+
organic extract; they treated S1 yields in the same way.
However, an average correction factor may be inappropriate if the
molecular weight range of the residual petroleum decreases with increasing
maturity, when underestimation of total C6+ oil present in the source rock will
lead to overestimation of 'observed' expulsion efficiency. Coals are particularly
susceptible to this effect: Durand et al. (1987) showed that the proportion of
volatile products in pyrolysis effluent compositions of Mahakam Delta coals
increases dramatically with maturity.
Even worse, gas quantities predicted by ORGAS will remain largely
untestable in the absence of reliable methods of measuring or estimating virgin
gas concentrations in geochemical samples. Uncorrected gas and low molecular
weight C6+ petroleum losses may be the cause of high apparent (oil) release
efficiencies reported for coals from the Mahakam and Gippsland (Macgregor and
Mackenzie, 1986) and Australian Cooper-Eromanga and Clarence-Moreton
basins (Powell and Boreham, 1994).
Petroleum Release Efficiency (PRE), can be calculated using an estimated
gas correction. Pepper (1991) used corrections derived from closed vessel
pyrolysis of comparable source rock samples. The effects on PRE were
relatively minor for high quality source rocks, but quite dramatic for coals.
Thus, although PGI will be unaffected:
PGI =1- [{CKO + CKG} / {CO0 + CKO0 + CKG0}]

(A1)

PRE will be affected:

PRE = 1- [{CO + CG} / [{CKO0 + CO0 + CKG0}
- {CKO + CKG}]]
(A2)
Overall, there are fewer uncertainties in calibration using quantities which avoid
gas quantities, viz. Oil Release Efficiency (ORE) and Oil Generation Index (OGI):
OGI = 1- [CKO / {CO0 + CKO0}]
ORE = 1- [CO / [{CKO0 + CO0} - CKO]]

(A3)
(A4)

Even OEE determined from back-calculation of field sample data will always be
an apparent maximum (OEEapparent) since, the residual quantity CO is affected
by removal of oil by thermal cracking as well as by expulsion!
For completeness, the gas quantities are:
GGI = 1- [CKG / CKG0]

60

(A5)

GRE = 1- [CG / [{CKG0 + CGO} - CKG]]

(A6)

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