Magoon. L. B, and W. G. Dow, eds.

, 1994, The petroleum

system-from source to trap: AAPG Memoir 60.

Chapter 14

Preservation, Degradation, and

Destruction of Trapped Oil
Philippe Blanc
Jacques Connan
Elf Aquitaine
Pall Ccdex, France

Abstract
Petroleum is a fragile fluid, a part of which is likely to be destroyed or lost to the atmosphere.
The moment crude oil separates from bitumen in the source rock, it begins to undergo composi-
tional changes that continue throughout migration and accumulation. The processes and factors
influencing oil composition in an accumulation take effect before, during, and after entrapment.
The primary factors influencing oil composition before entrapment are source rock characteristics,
primary migration, and secondary migration. The main factors influencing oil composition during
entrapment are pressure and temperature, as they establish the conditions under which secondary
alteration processes take place. After entrapment, secondary alteration processes influencing oil
composition are the effect of thermal maturation, physical and biological degradation, gravity
segregation, dysmigration (separation-migration), and deasphalting. These alteration processes can
increase the API gravity and gas-oil ratio of the oil, but generally decrease the API gravity.
Knowledge of the conditions and mechanisms of degradation are needed to understand the
nature and distribution of oil shows and to carry out oil-oil and oil-source rock correlations.
Considerable progress hasbeenmade in understanding secondary alteration processes, but more is
expected as the more poorly understood macromolecular and polar fractions are investigated.
Presently, molecular chemistry is a useful tool that can recognize incipient biodegradation. detect
oil gravity segregation, and discriminate a pyrobitumen from a precipitated asphaltene, whereas
bulk analyses are currently inaccurate.

preseroed petroleum. TIle longer a petroleum accumulation

INTRODUCTION
Petroleum is a fragile mixture of oil and gas that is
difficult to preserve. It is easily degradable by destruction
or loss to the atmosphere of an unknown amount of it.
The critical moment oil separates from bitumen in the
source rock, it undergoes compositional changes during
migration and accumulation. Except for changes in the
oil and gas mix that occurs in response to pressure and
temperature variations during petroleum migration,
most degradation and destructive processes occur in the
reservoir rock within the trap. Generally, oil and gas that
first comes to the trap is defined as normal. By this we
mean a petroleum accumulation whose composition is
commonly associated with a particular kerogen type and
whose chemical composition at a molecular level shows
little sign of alteration. The API gravity for such oil accu-
mulations can range from 25 to 40° API, while the gas-oil
ratio (GOR) is generally 100-200 m 3jm3 (500-1000
ft 3 jbbl). This oil is generally considered to be the
exists in nature, the more likely the original chemical
composition should be altered or degraded by physico-
chemical or biological processes. These processes include
increase or decrease in burial depth (temperature
change), flushing by meteoric water, and bacterial
activity. The complete destruction of a petroleum accu-
mulation is usually caused by erosion.
Petroleum is a complex mixture of liquid and gaseous
fluids of mainly organic compounds whose proportions
may depend on the PVT conditions in the trap. These
fluids are usually described by bulk properties, such as
API gravity, percent sulfur, GOR, and viscosity.
Although these bulk properties are of limited interpre-
tive value in shallower reservoirs, they do provide guide-
lines for fluids in deeper reservoirs. For instance, the API
gravity of a series of oils tends to increase with burial
depth. However, the composition of petroleum depends
upon such complex phenomena that bulk parameters
(physical and chemical) are unable to describe

237
238 Blanc and Connan
adequately the subtle shift in molecular composition that
occurs when an oil passes through various levels of
degradation.
Generally, oil in reservoir rocks and bitumen from
source rocks have many similarities in their composition.
Both are composed of hydrocarbons (including
naphtheno-aromatics and organo-sulfur species) and
polar compounds (rich in nitrogen, sulfur, and oxygen
atoms), the latter being divided into asphaltenes (macro-
molecular fraction insoluble in light alkanes) and resins
(more soluble but very polar). The main differences
between accumulated oil and bitumen are created
during primary migration (expulsion) and secondary
migration. For instance, polar compounds are depleted
in accumulated oil because these components are
strongly sorbed within the source rock matrix and within
the kerogen. Such a phenomenon is well documented
from natural cases as well as from experimental studies
(Connan et al., 1991;Lewan, Chapter 11, this volume).
The molecular composition of oil is much less affected
during migration than are the bulk parameters, even
though previous studies have shown that different
molecules could exhibit differences in "retention times"
during migration within a petroleum system (Seifert and
Moldowan, 1981; Zhao-An and Philp, 1987). In general,
the original biological marker fingerprint of a source rock
is preserved sufficiently in migrated oils to allow its use
as a tool to assess oil-source rock correlations (Curiale,
Chapter 15, this volume), unless (1) the oil is a mixture
from more than one source rock, (2) the migrating oil
becomes contaminated by extracting biological markers
from thermally immature organic matter before accumu-
lating, or (3) the oil undergoes secondary alteration, such
as biodegradation.
Hence, depending on the analytical approach, the
preservation or degradation of petroleum can be demon-
strated using different parameters, either physical or
chemical, bulk or molecular. Some of these parameters
are modified during petroleum degradation. This
chapter provides a review of the major processes likely to
influence oil composition after it is trapped. Diagnostic
tools developed to detect this degradation are empha-
sized.
OIL PRESERVATION OR
DEGRADATION
Assuming that a given accumulated oil will be
"preserved" indefinitely makes little sense, for petroleum
is a mixture of compounds that is not in a state of equilib-
rium. It is likely that, over geologic time, this mixture will
undergo significant physical and chemical changes. The
longer the time, the more likely the changes. Here again,
assessment of preservation depends upon the criteria
adopted. From an economic point of view, petroleum
quality deteriorates if it is affected greatly by alteration
processes: preseroed petroleum is an appropriate term for a
fluid that is of economic interest when a prospect evalua-
tion is carried out. However, investigations of the
petroleum system are done without regard to economics,
that is, an accumulated oil is worth studying regardless
of its economic worth because of the information it may
contain. Therefore, the preserved oil is synonymous with
the normal oil, which in itself is difficult to define. The
normal oil shows no signs of being degraded or altered.
Normal oils are different depending on the composition
of their source rock. The GOR also varies for the same
reason. From a molecular point of view, this oil will
never be completely preserved or remain normal since
minor modifications are always occurring. At a
molecular level, cases are encountered in which some of
the biological markers are degraded whereas others are
preserved. The challenge to the investigator is to
determine the nature and extent of this oil degradation
so as to carry out better oil-source rock correlations and
more accurately reconstruct the accumulation history of
the petroleum system.
The main factors influencing oil composition before,
during, and after being trapped in the reservoir rock are
outlined in Figure 14.1 (Blanc and Connan, 1993). The
primary factors influencing oil composition before
trapping are source rock characteristics and primary and
secondary migration conditions. Oil composition is influ-
enced to some extent by the nature of the source
(organic) material and by the paleoenvironmental condi-
tions in which it was deposited. Both factors lead to
different types of kerogen that behave differently during
catagenesis. In addition, several other agents (geologic,
physical, and chemical) are at work to affect oil composi-
tion significantly during primary and secondary
migration. These three primary factors affect oil composi-
tion before it enters the trap.
The main factors influencing oil composition in the
reservoir rock are pressure and temperature. Both
pressure and temperature, which increase or decrease
with an increase or decrease in burial depth, affect the
GOR at the time of accumulation. Otherwise, the PVT
conditions in the reservoir establish the conditions under
which secondary alteration processes take place.
Secondary alterations influencing oil composition
after it accumulates in the trap are discussed relative to
five different processes (Figure 14.1). These processes are
thermal maturation, physical and biological degradation,
gravity segregation, dysmigration, and deasphalting.
They are discussed relative to the main agent causing
them as well as the products, API gravity, and relative
change in depth of the fluids. Their alteration effects,
though clearly identified, are sometimes difficult to
recognize unequivocally because they can lead to similar
kinds of degradation products.
Thermal Maturation
Thermal maturation of oil, or oilcracking, is a process
that sometimes occurs in the trap because temperature
increases when the trapped oil is buried deeper. Hence,
oil cracking reactions within the reservoir rock favor the
formation of light hydrocarbons, the depletion of poly-
cyclic biomarkers, an increase in GOR, a decrease in
specific gravity (increase in API gravity), and a decrease
in sulfur content. An oil expelled from a source rock that
 14. Preservation, Degradation, and Destruction of Trapped Oil
PRIMARY PROCESSES SECONDARY ALTERATION PROCESSES
INflUENCING OIL COMPOSITION INFLUENCING OIL COMPOSITION
BEFORE TRAPPING AFTER TRAPPING
SOURCE ROCK
CHARACTERISTICS
------------- ,--';;';"'''':;'';''''';'':';''''';''--.1
ellllun 01_ - - .
l. ~1ypt(~J.l-SJII
e ~ron...1IIcondltlonl
ellllulttroIlOUrce racIl
~~~~--~-----------------
PRIMARY MIGRAlION
• TlmIng 01 gBIlII'I1Ion IIICl Ujluislon
'-::-~~:.::.L.._"dysmlgratlo
SECONDARY MIGRATION
L;;.;..=-_ _---.,.. deasphaltin~htoll
Figure 14.1. Schematic representation of the main factors and processes influencing oil composition. Arrows inclined
upward indicate an increase; arrows inclined downward, a decrease.
is experiencing increasing levels of thermal maturity also
shows similar compositional changes. Consequently, it
often becomes difficult to separate the thermally cracked
oil in the reservoir rock from the high API gravity oil
caused by expulsion from a mature source rock. However,
the thermal evolution of oil in a reservoir rock induces a
disproportionation reaction that leads to the formation of
gaseous and light hydrocarbons on one side and a black
solid residue on the other side. This solid residue, often
called pyrobitumen, is therefore a diagnostic indicator
enabling the recognition of thermal cracking of the
original oil. A well-known example illustrating that
feature occurs in Rainbow reefs, Canada, where gas and
high API gravity oil are associated with pyrobitumen
(Evanset al., 1971; Baileyet al., 1974; Rogers et al. 1974).
Pyrobitumens are highly dehydrogenated structures
that show a low hydrogen index (HI is -80 mg HC/ g
TOC) and a very high Tmax (>460 0C) with a reflectivitythat
ranges between 1.5 and 2.5% Ro (}. Connan, personal
communication, 1991). Their dehydrogenated character,
coupled with their insolubility in CHClJ, allow their easy
differentiation from asphaltene-like material that may
have been precipitated in the reservoir rock through a
different process (e.g., gas injection resulting in natural
deasphalting).
The upper temperature limits for oil occurrence before
239
maturation ---<Ilghl 0. . . . gas
pyrobltumen
water washing conventional
biodegradation'" hea':rol
oxidation eXInt-heavy 011
evaporatio~ to
solidbllumen
gravity --"""light 011
segregation 'heavy 011
.. ~htOII
avy 011
<II "'sotld residue
it is thermally cracked have been reviewed by Horsfield et
al. (1991): a mean value of 150°C is often given, but
regional studies have produced values ranging from
about 93-104 °C in western Canada, 138°C in Powder
basin, 150°C in Niger delta and Norway, 158°C in Italy,
and up to 175-204°C in California. Closed-system
pyrolysis and kinetic modeling by Horsfield et al. (1991)
showed that the onset of gas generation from an oil
acquired from the Norwegian North Sea Central Graben
might occur between 160° and 190°C. These conclusions
agree with the observation that liquid hydrocarbons can
occur in fields where reservoir rocks are hot (165°C).
However, the existence of liquid fluids in deep hot rocks
can also be accounted for by a retardation effect of high
pressure on the evolution of organic matter or overpres-
suring within a reservoir (Price, 1982;Coffe and Villey,
1984; Domine, 1991; Connan et al., 1991; Blanc and
Connan, 1992a).
Although well accepted on the basis of various obser-
vations in oil systems, it should be mentioned that the
process of thermal decomposition of petroleum ultimately
yielding methane and pyrobitumen has recently been
disputed on the basis of both kinetic (Mango, 1991) and
thermodynamic (Helgeson et al., 1991) considerations.
240 Blanc and Connan
Water Washing-Biodegradation and
Oxidation-Evaporation
Biodegradation is the microbial oxidation of crude oil,
and it usually takes place at a shallow depth where the
oil is in contact with flowing water, whereas water
washing applies to the removal of the more water-soluble
compounds. Although these phenomena are unrelated,
they frequently occur simultaneously because both
processes require contact with flowing meteoric water.
However, petroleum geochemistry techniques are
currently unable to selectively recognize the diagnostic
effects of each type of alteration whenever they are
extensive or even modest.
The process of water washing alone is poorly dOQ1-
mented since bacterial degradation generally obscures its
effects. Based on solubilities of hydrocarbons, simulation
experiments, and field examples, water washing has
been shown to be particularly effective in the low boiling
range of hydrocarbons, thus causing a decrease in API
gravity. Aromatics (especially benzene and toluene) are
the most soluble compounds, followed by light alkanes
and then naphthenes (Connan, 1984; Palmer, 1984;
Lafargue and Barker, 1988). However, one should
remember that benzene, toluene, and xylene concentra-
tions are also source rock dependent. Molecular changes
due to water washing without biodegradation have been
tentatively proposed. They are 0) a decrease in the
amount of aromatics and n-alkanes while naphthenes are
unaltered, (2) a partial removal of C15+ aromatics while
C 15+ alkanes are unaffected, and (3) a decrease in sulfur-
bearing aromatics (especially dibenzothiophene) while
the C 15-C20 saturate fraction remains unchanged
(Lafargue and Barker, 1988). Recently, phenols have been
proposed as sensitive indicators for water washing
(Ioppolo et al., 1991).
A review of the conditions under which biodegrada-
tion occurs and the important changes in the physical
and chemical properties of crude oil has been given by
Connan (984). Generally, biodegradation affects both
physical and chemical parameters. In particular,
biodegradation induces a decrease in the GOR, light
hydrocarbon content, and API gravity, whereas it
increases the viscosity, optical activity, and heteroatomic
(especially sulfur) content of the oil. These features are
due to the consumption of specific molecules by aerobic
bacteria, which results in the formation of oxidized
compounds (the latter likely to be attacked subsequently
by anaerobic strains). Because of the depletion in alkanes
and aromatics, there is a relative increase in concentra-
tion of polar compounds, which is why bulk chemical
composition of the oil fraction is affected by biodegrada-
tion.
The effects of biodegradation are also recorded at a
molecular level. Both field observations and laboratory
experiments have contributed information about the
sequence in which alkanes and aromatics have been
removed. Among saturated hydrocarbons, for instance,
normal alkanes are consumed by bacteria first, followed
by isoprenoids, regular steranes, diasteranes, hopanes,
and neohopanes, in that order. Moreover, bacterial
consumption of hydrocarbons also depends on the
oxic-anoxic conditions of the active water adjacent to the
oil and on the nutrients in the water. When nutrients
(nitrogen and phosphorus) are depleted, biodegradation
preferentially starts with aromatics, and alkanes are
unchanged. Under more favorable conditions (i.e., a
medium rich in oxygen and nutrients), both alkanes and
aromatics are attacked simultaneously (Fedorak et al.,
1983). In addition, it has been demonstrated conclusively
that anaerobic biodegradation of alkanes is possible with
a strain of sulfur-reducing bacteria (Bailey et al., 1973;
ZoBell, 1973; Connan and Orgeval, 1976; Aeckersberg et
al., 1991). However, this form of biodegradation has
limited effects on oil properties as a whole. The most
effective biodegradation proceeds through aerobic
pathways.
A more extreme form of degradation occurs through
evaporation (inspissation) and oxidation of oil at the
surface (Figure 14.1). Usually the oil degrades from an
extra-heavy oil to solid bitumen (Connan, 1988). If
oxidation and erosion continues, all remnants of the oil
field are removed or destroyed.
Gravity Segregation
Although API gravity of oils should increase step by
step with greater burial depth, a reverse situation has
been observed in some reservoirs (Evans et al., 1971;
Price, 1980; Ungerer et al., 1984) which cannot be attrib-
uted to thermal maturity differences of the oil or source
rock. In fact, this reverse phenomenon is poorly under-
stood, and two explanations can be proposed: (l) either a
gravity segregation is occurring, with oil becoming
heavier with increasing depth by a simple gravity
process (larger molecules settling toward the bottom of
the oil column), or (2) an "inverted gravity" phenom-
enon is occurring that involves lower pressure and a
higher quantity of gas at the top of the reservoir than at
the bottom. Silverman (965) had previously described a
similar phenomenon called a retrograde condensation
process (see also Tissot, 1988), in which a liquid phase
separates from a single phase system of gas when the
pressure is reduced.
This decrease in API gravity with depth in a continous
oil column should be ascribed to gravity segregation if
other possible causes can be definitively ruled out. For
instance, the more deeply buried oil fields should be
checked for incipient biodegradation to show that a
definite interaction with bacteria-containing waters does
not increase with depth of burial. If all molecular proper-
ties are similar in both the conventional oils and the
heavy oils, then the downward compositional changes
that generate heavier and heavier oils should be
explained by gravity segregation within the oil column.
Gravity segregation explains the increase in specific
gravity (decrease in API gravity) in the Vic Bilh oil field
in the Aquitaine basin (Figure 14.2). A vertical sequence
of oil samples was obtained from two wells drilled
through upper Kimmeridgian-Portlandian (Upper
Jurassic) and Barremian (Lower Cretaceous) reservoir
rocks. Six oil samples were recovered from weill: three
 14. Preservation, Degradation, and Destruction of Trapped Oil
ALKANES
100
+ P;2431.2481m
ASPlW.TElES
(b)
VOLATILE FRACTION (%CRUCE)
10 20 30
• W,111 • W,1I2
5 : Drill 111mII" number P: Production .."
• }8ARREMIAN C }upper KNMERIDOIAN to PORTLANDIAN
• Lo_ CRETACEOUS 0 Upper JURASSIC
Figure 14.2. Occurrence of a possible gravity segregation
phenomenon in two wells of the Vic Bilh oil field (south-
western France) on the basis of the evolution of bulk para-
meters with depth: (a) oil composition and (b) API gravity
and volatile content. Biological marker data are needed to
provide an adequate explanation for this change in bulk
parameters (see Blanc and Connan, 19928).
drill-stern test samples from the Barremian (solid
squares) and two production samples and one drill-stern
test sample from the Upper Jurassic (open squares).
Although the relative proportion of alkanes and
aromatics remained constant, the API gravity decreased
with depth, coinddent with a corresponding increase in
polar compounds (resins and asphaltenes) for these six
oil samples (Figure 14.2A). In addition, the volatile
fraction of the crude oil also decreased with a decrease in
API gravity (Figure 14.2B). On the basis of the molecular
chemistry of these oils, it is concluded that they were
expelled from the same source rock at the same level of
thermal maturity. Therefore, this progressive enrichment
in polar compounds associated with a decrease in API
gravity with depth leads to the conclusion that this
phenomenon is most likely related to gravity segregation
(see Blancand Connan, 1993).
241
Dysmigration
Some compositional changes within accumulated oil
can be related to the efficiency of the seal rock. A seal
rock over an accumulation that provides a perfect seal
will prevent any compositional change in the trapped oil
due to leakage. However, most hydrocarbon traps leak
to some extent. This leakage is linked to the geologic
conditions that formed the trap. Sometimes these condi-
tions are related to tectonic events that cause movement
along a major fault that traps hydrocarbons. In this case,
a dysmigration phenomenon may occur where significant
losses of the lightest hydrocarbons from oil can take
place in a two-step process (described by Silverman,
1965, as a "separation-migration" process). First, the
pressure release due to faulting converts the single phase
fluid system to a two-phase system where a gas cap
forms above the oil. Second, this gas is lost through the
leak along with light oil and migrates to shallower traps
where temperature or pressure drops can induce the
previously discussed retrograde condensation. A new
pool can be formed that contains a fluid with a high API
gravity. This is in contrast to the low API gravity oil left
behind in the original pool which, based on its molecular
composition, will have a level of thermal maturity that is
similar to the high API gravity oil. Therefore, significant
differences in chemical composition and distinctive
physical characteristics of the two respective oil accumu-
lations will be recorded.
An example of dysmigration has been found in the
Lagrave area in the Aquitaine basin. Here, an oil field
that has an Upper Cretaceous reservoir rock contains a
fairly light crude oil (45' API), whereas the heavy
residual oil corresponding to the original oil accumula-
tion has been found much deeper in a Barremian (Lower
Cretaceous) reservoir rock of a nearby field. These
upward-migrating hydrocarbon fluids accumulated in a
shallower trap; the result is a shallow accumulation of
high quality oil.
When no trap exists at a shallower depth above a
deeper accumulation that leaks, oil shows are found
within the sedimentary rock column above the deeper
accumulation. In the Emeraude area offshore of the
Congo in Africa, there is a good example of intense
leakage through the seal rock of deeper accumulations.
Oil shows have been detected in the sedimentary rock far
above the oil accumulation. Studies reveal that the
degree of biodegradation of these oil shows increases as
the shows approach the sea floor. Large amounts of gas
bubbles are recorded on the sea floor just above the
Emeraude oil field (Connan and Coustau, 1987).
Deasphalting
Oils and condensates in traps are usually associated
with gas. This gas can originate from the thermal
maturity of a source rock as well as from secondary alter-
ation processes affecting oil already in the reservoir rock.
Gas content depends on numerous parameters, such as
kerogen type, hydrocarbon availability (oil or gas) at the
time of pool formation, reservoir pressure, reservoir
242 Blanc and Connan
temperature, trap efficiency, and secondary alteration
processes.
The postaccumulation introduction of gas into an oil
field can lead to chemical changes because the influx of
gaseous hydrocarbons decreases the average molecular
weight of the pooled mixture. Hence, what the organic
chemist does in the laboratory when precipitating
asphaltenes from an oil by adjunction of n-heptane, for
instance, is also naturally undertaken in the oil field
when gas moves up through the oil column. This natural
deasphalting can be triggered by external gas injection,as
a result of secondary migration, or by oil cracking within
the reservoir rock (Evans, et a1., 1971; Bailey et a1., 1974;
Rogers et al., 1974). This process therefore leads to the
formation of a light oil on one hand and a solid residue
containing asphaltenes on the other (Speight, 1984;
Speight et al., 1985). This process of deasphalting is
thought by Dahl and Speers (1986) to explain the occur-
rence of a tar mat in the Oseberg oil field in the
Norwegian North Sea.
RECOGNIZING
PALEODEGRADATION
The preservation, degradation, and destruction of
petroleum is usually viewed from present-day.
However, the petroleum system study requires the
investigator to describe oil and gas accumulations at the
time they formed. Whenever a degraded oil is encoun-
tered at the surface or in the subsurface, one must ask at
what time this degradation process commenced and
what type of paleodegradation occurred. Figure 14.1
emphasizes that most degradation processes lead to the
formation of heavy or extra-heavy oils up to solid
bitumens. Therefore, these various processes are difficult
to disentangle, especially because they are interrelated
and continuous and take place successively. Most of the
time, examination of bulk parameters of the degraded oil
only leads to conflicting interpretations. An increase in
the API gravity, for instance, is usually thought to
correlate positively with an increase in depth since
pooled fluids become lighter, that is, the average hydro-
carbon molecule becomes smaller with increasing
thermal maturity. However, other phenomena are likely
to interfere, especially at shallow depths. For example,
when oil migrates updip a long distance from the source
rock, it may become heavier because lighter hydrocar-
bons can be lost before the oil accumulates. In addition,
secondary alteration processes can act on the oil within
the reservoir rock to lower its API gravity. This influence
of various phenomena on the API gravity of oils is illus-
trated in Figure 14.3. This figure shows the evolution of
API gravity of oils from the North Sea as a function of
depth. Although a general trend is observed (oils
increase in API gravity when the reservoir rock depth
increases), the correlation is not perfect due to the
existence of other processes than simply a lightening of
oils under increasing temperature.
To better understand the degradation of oil, a multi-
disciplinary approach should be undertaken (Blanc et al.,
1982; Connan and Coustau, 1987). This approach
includes tools such as molecular and isotopic geochem-
istry, both of which provide complementary information
that shows more potential for investigating degradation
than do the bulk properties of oil. For instance, it would
be impossible to evaluate a biodegraded oil occurrence
exclusively by considering bulk properties because a
heavy oil, for example, can result from various factors or
phenomena, including kerogen type, level of thermal
maturity, water washing, gravity segregation, and
dysmigration. In contrast, since biological markers are
sensitive to bacterial consumption, they are likely to give
key indications, not only on the occurrence of the
biodegradation itself but also on the extent of the alter-
ation processes.Hence, classifications of biodegraded oils
are proposed in relation to their level of biodegradation:
incipient, minor, moderate, extensive, and severe or extreme
(Seifert and Moldowan, 1979; Goodwin et al., 1983;
Volkman et al., 1983; Connan, 1984; Peters and
Moldowan, 1991; Cassani and Eglinton, 1991).
The criteria used to determine this level of biodegra-
dation is based on the presence or absence of compound
classes.Moreover, while severe biodegradation is usually
relatively easy to recognize because aromatics and
alkanes are strongly altered, incipient biodegradation
may be questionable. Incipient biodegradation can be
defined as degradation of n-alkyl chain--eontaining struc-
tures (n-alkanes, iso- and anteiso-alkanes, alkylbenzenes,
and methylalkylbenzenes). In such a case, this degrada-
tion is likely to be mistaken for a token of immaturity
since some n-alkanes can still remain. The identification
of incipient biodegradation will depend on the ability of
the geochemist to find suitable diagnostic information for
appraisal. This significant information, which is hidden
in the gas chromatograms of the saturated and aromatic
hydrocarbon fractions, may be obvious in the isolated
monoaromatic fraction.
Such an approach has been adopted to identify
incipient biodegradation in the Pecorade oil field from
the Aquitaine basin (southwestern France). The heavy
(low API gravity) oil recovered from the Albian reservoir
rock in the Pecorade field is a normal oil with respect to
alkanes and aromatics, as the n-alkanes are still present
and the aromatics still contain naphthalenes and benzo-
and dibenzothiophenes (Figure 14.4A). Comparison of
the monoaromatic fraction from the normal (medium
API gravity) oil and the heavy oil recovered from the
Pecorade well enables us to reach a definitive conclusion
about the extent of the degradation (Figure 14.4B). Alkyl-
benzenes, well represented in the normal oils from the
Pecorade field, have been completely removed from the
heavy oil. The lack of alkylbenzenes that are readily
degradable structures in this oil provides proof that this
heavy oil is a residual fluid that resulted from attack by
bacteria (Blanc and Connan, 1993).
Specific biological markers are also resistant to
bacterial activity and are therefore of great help in
assessing the level of biodegradation. Examples are
gammacerane, 18a(H),21 ~(H)-30-norneohopane or
17a(H),21~(H)-25-norhopane (Blanc and Connan, 1992b).
The use of gammacerane in this manner has been docu-
 14. Preseroation, Degradation, and Destruction of Trapped Oil 243

20 25 30 35 40 45 50
·1000 °API
Important migration and

-1500
J . --- ,-
poorpreservation of oils.
(degraded oil)

• •
Important migration and

·2000
- • - •
• • ....
•• goodpreservation
• ~ ·
of oifs
(HC slightly degraded)

·2500 •
• I• ••• •
0

• • <11 0 •• • •
-
• goodpreserva
-3000
• •• • •
• Limited mig"etion with
0
tion of oils
(HCslightly or not degraded)
00
topoi I •
window
-3500
I •• •
• I •• •
•• • •
•
LEGEND • •
No migration or migration
within theoil windo w
• TERTIARY
o CRETACEOUS •
• JURASSIC
04500 [J TRIASSIC
DEPTHISEA LEVEL limit < °API
• PERMIAN within the oil window
TOP RESERVOIR (m)

Figure 14.3. The change in API gravity of oils with reservoir depth for samples from the North Sea. (After F. Issard, personal
communication, 1991.)

mented in the case of Syrian oil seepages. In this series of
surface samples, different levels of biodegradation can be
assessed using the gammacerane-hopane ratio because
gammacerane is more resistant than hopane to biodegra-
dation (Blancand Connan, 1992b). This ratio is calculated
easily on the mlz 191 mass fragmentogram. This example
is illustrated in Figure 14.5, which shows the following
sequence of biodegradation: sample 170 > sample 169 >
sample 168. This result is confirmed by the prominence
of diasteranes (rearranged steranes) among the steranes
in sample 170 im]: 217 mass fragmentogram on Figure
14.5). Diasteranes are in fact believed to be more bacteri-
ally resistant than the regular steranes (e.g., Seifert et al.,
1984).
Particular attention should be paid to 25-norhopanes
(usually called demethylated hopanes and easily
observed on the m]z 177 mass fragmentogram) because
they are particularly useful in biodegradation studies.
First detected by Reed (1977) in a weathered, oil-impreg-
nated sandstone from Utah, their presence in an oil has
been subsequently regarded as indicative of extensive
biodegradation (e.g., Seifert and Moldowan, 1979).
Although some controversy still exists concerning their
origin, geochemists now consider them as key indicators
of paleobiodegradation in instances where the oil does
not otherwise appear biodegraded (Philp, 1983;Volkman
et al., 1983; Blanc and Connan, 1991, 1992b). Therefore,
25-norhopanes provide the geochemist with a possible
tool for an oil-source rock correlation even in the case of
(paleo)biodegraded oils. Paleobiodegradation indicators
are not restricted to 25-norhopanes, and other biological
marker compounds should be considered. For instance,
secohopanes and hexahydrobenzohopanes can be used
as paleobiodegradation indicators in evaporitic carbon-
ates (Chosson et al., 1992).
Oil-oil correlations among oils that show levels of
biodegradation from incipient to severe can also be
evaluated by probing the macromolecular entities
(geopolymers) such as the asphaltenes and resins to find
the unaltered biological markers. Indeed, these geopoly-
mers can offer an efficient protection for covalently
bound molecular structures from secondary alterations
such as biodegradation. These unaltered biological
markers are most likely released by pyrolytic degrada-
tion (Cassani and Eglinton, 1986; Jones et al., 1987;
Connan, 1993) or chemical degradation (Chappe et al.,
1980;Blanc and Albrecht, 1990;Trifilieffet al., 1992).
A more systematic investigation of the molecular
content of geopolymers and solid bitumens (Curiale,
1986) seems to possess considerable geochemical
potential for the future. These types of analyses will
provide information making it possible to differentiate,
for example, pyrobiturnen resulting from intense thermal
cracking of oil and precipitated asphaltene formed
through natural deasphalting by gas migration. Selective
chemical degradations appear to be the key techniques to
document this problem (see Rullkotter and Michaelis,
1990,for a review).
244 Blanc and Connan

C 15+ALKANES C1s+AROMATICS
....
(a) ~ ~ III
I-MDBl

I1500-1560m I
~u o FPO
i: C: ~~/
y~
CrS iii
~~ ~

r
" 1+ BICYCLANES I
~;n~
l'l ~ t
11~
c.> N

't.
8-1O"AP,1 I I ' ! I
E!: FlO

50 100

~
........ l-MDBT
0 ~~ /

I2477-2485m I
,",

" 0
~
~,
FPO
"

::: ~
to 50

N ~

't. o• N
t.>
~

C C ~
C't

cf
0

FlO

50 100

't.
0
~

I2671-2790m I FPO

7' 2o-2~AP"'" "

to 50 100

. I,~b~' J
N
N ~
U N ~

" t:te c<t:f N

0
co
N go

0 50 100

Figure 14.4. Gas chromatograms of (a) C15+ alkanes and C 15+ aromatics and (b) C 15+ mono-, dl-, and polyaromatics of heavy
and conventional oils from the Pecorade 26 well (Aquitaine basin, southwestern France). C15+ aromatics have been analyzed
using a dual detector (FlO for carbon, FPO for sulfur). In part (b), incipient biodegradation has been diagnosed from the lack
of alkylbenzenes in monoaromatics of the heavy oil.

As already mentioned, such techniques have been

successfully applied to identify coal, kerogen, or asp hal-
tene moieties. The released molecular entities could
provide information complementary to that provided by
the "free" molecular components. Unlike the free compo-
nents, the "bound" components are likely to avoid (or
undergo to a less extent) secondary alteration, migration,
and thermal maturation processes. These bound biolog-
ical markers or structural subunits of the macromolecular
entities (Blancand Albrecht, 1991) could therefore be used
for oil correlation or thermal maturation studies. They
may also be more discriminant than "mobile"
compounds in characterizing and differentiating partic-
ular geopolymers at a molecular level (Blancet al., 1991).
Finally, this type of analysis could prove useful in
understanding how oxygen is incorporated into
degraded oil samples on the surface. The preferential
quenching of particular classes of molecules could even
be highlighted, as has been observed recently for higher
plant triterpenes in high-sulfur crudes (Adam et al., 1991).
It is therefore likely that geochemical interpretations
based only on the free and apolar biological markers are
incomplete or erroneous (Kohnen et al., 1991).
CONCLUSIONS
Among the factors influencing petroleum composi-
tion, secondary alteration processes that occur after oil
entrapment are most important, as they can lead to
considerable changes in both the composition and
quality of the oil. Knowledge of conditions and mecha-
nisms of degradation processes are needed for petroleum
exploration, not only for economic reasons but also
because multidisciplinary approaches must be
developed to improve already established techniques
and to create new techniques. The investigation of the
detailed molecular pattern of organic natural substances
(gaseous, liquid, and solid) has great potential. Research
to date indicates that information relevant to oil explo-
ration and exploitation is hidden in oil fractions presently
not routinely studied. These fractions generally consist of
polar compounds and macromolecular entities.
Presently, molecular chemistry is a useful tool that is able
to recognize incipient biodegradation, to detect oil
gravity segregation, and likely to discriminate a pyrobi-
tumen from a precipitated asphaltene, whereas bulk
analyses are currently inaccurate.
 14. Preservation, Degradation, and Destructionof Trapped Oil
(b)
HEAVY OIL 1500-1560 m
1
1:1
Ill' ,"
It .J
I <oIL ..I, Ll1.1
o 50 100 MINUTES 150
+ MONOAROMATICS
o 100
• •
MINUTES 150
+__----'POL YAROMATICS,
Figure 14.4 (continUed)
Acknowledgments We are indebted to 1. B. Magoon, J. A.
Curiale, J. T. Smith, and P. van de Kamp, who greatly
improved ourmanuscript.
References Cited
Adam, P., J. M. Trendel, P. Albrecht, and J. Connan, 1991,
Novel thiophene derived from higher plant triterpenes in
sediments: Tetrahedron Letters, v. 32, p. 4179-4182.
Aeckersberg, F., F. Bak, and F. Wid del, 1991, Anaerobic
oxidation of saturated hydrocarbons to C0:2 by a new type
of sulfate-reducing bacterium: Archives of Microbiology,
v. 156, p. 5-14.
Bailey, N. J. L., A. M. Jobson, and M. A. Rogers, 1973, Bact~rial
degradation of crude oil: comparison of field and expen-
mental data: Chemical Geology, v. 11, p. 203--221
Bailey, N. J. L., C. R. Evans, and C. W. D. Milner, 197~,
Applying petroleum geochemistry to search for 011: .
examples from Western Canada basm: AAPG Bulletin, v.
58, p. 2284-2294.
Blanc, Ph., and P. Albrecht, 1990,Molecular parameters in
bitumen and macromolecular matrix of coals: their evalua-
tion as rank parameters, in H. Charcosset, ed., Advanced
methodologies in coal characterization, Coal Science &
Technology, v. 15:Amsterdam, Elsevier, p. 53-82.
Blanc, Ph., and P. Albrecht, 1991, Parameters of "macromatu-
rity" (PMM): novel rank and type related indices from
chemical degradation of macromolecular network of coals:
Organic Geochemistry, v. 17, p. 913--918.
245
PRODUCTION OIL 2671-2790 m
0 100 MINUTES 150
_ +
~----------------,
MINUTES 150
0 MINUTES1
•
-.I
Blanc, Ph., and J. Connan, 1991,Paleobiodegradation and
paleoenvironmental assessments using demethylated
hopanes, in D. A. C. Manning, ed., Organic geochemistry,.
Advances and applications in energy and the natural envi-
ronment: Manchester and New York, Manchester Univer-
sity Press, p. 346-348.
Blanc, Ph., and J. Connan, 1992a, Generation and expulsion of
hydrocarbons from a Paris basin Toarcian source rock: an
experimental study by confined-system pyrolysis: Energy
and Fuels, v. 6, p. 666-677.
Blanc, Ph., and J. Connan, 1992b, Origin and occurrence of 25-
norhopanes: a statistical study: Organic Geochemistry, v.
18, p. 813--828.
Blanc, Ph., and J. Connan, 1993, Crude oils in reservoirs: the
factors influencing their composition, in M. L. Bordenave,
ed., Applied petroleum geochemistry: Paris, Technip, p.
151-174.
Blanc, R., H. Coustau, J. Connan, W. J. Ebanks, and C. Roux,
1982,A multidisciplinary approach to the characterization
of heavy oil deposits from the tri-state area (U.s.A.):
Proceedings of the Second International Conference on
Heavy Crudes and Tar Sands, Caracas, Venezuela,
February 7-17, p. 633--657.
Blanc, Ph., J. Valisolalao, P. Albrecht, J. P. Kohut, J. F. Muller,
and J. M. Duchene, 1991, Comparative geochemical study
of the three maceral groups from a high volatile bitumi-
nous coal: Energy and Fuels, v. 5, p. 875-884.
Cassani, F., and G. Eglinton, 1986,Organic geochemistry of
Venezuelan extra-heavy crude oils, 1. Pyrolysis of
asphaltenes: a technique for the correlation and maturity
evaluation of crude oils: Chemical Geology, v. 55, p.
157-183.
 246 Blanc and Connan
Terpanes
168 HAWIVVET ABOU JIR
169 HAWIYVET ABOU JIR
170 EL SleHRI
Figure 14.5. Mass fragmentograms showing theterpane (miz191)andsterane (miz217) distributions foroilfrom three
Syrian seeps. A molecular ratio using gammacerane shows thelevel of biodegradation.
Cassani, F., and G. Eglinton, 1991, Organic geochemistry of
Venezuelan extra-heavy crude oils, 2. Molecular assesment
of biodegradation: Chemical Geology, v. 91, p. 315--333.
Chappe, B.,W. Michaelis, and P. Albrecht, 1980, Molecular
fossils of Archaebacteria as selective degradation products
of kerogen, in A G. Douglas and J. R. Maxwell, eds.,
Advances in Organic Geochemistry 1979:Oxford,
Pergamon Press, p. 265--273.
Chosson, P., J. Connan, D. Dessert, and C. Lanau, 1992, In
vitro degradation of steranes and terpanes: a clue to under-
standing geological situations, in J. M. Moldowan, P.
Albrecht, and R. P. Philp, eds., Biological Markers in
Sediments and Petroleum: Englewood Cliffs, NJ, Prentice-
Hall, p. 320-349.
Connan, J., 1984, Biodegradation of crude oils in reservoirs, in
J. Brooks and D. H. Welte, eds., Advances in Petroleum
Geochemistry: London, Academic Press, v. 1, p. 299-335.
Connan, J., 1988,Quelques secrets des bitumes archeologiques
de Mesopotarnie reveles par les analyses de geochimie
organique petroliere: Bulletin des Centres de Recherches
Exploration-Production Elf-Aquitaine, v. 12, p. 759-787.
Steranes
26.3
Connan, J., 1993, Origin of severely biodegraded oils; a new
approach using biomarker pattern of asphaltene
pyrolysates, in M. L. Bordenave, ed., Applied Petroleum
Geochemistry: Paris, Technip, p. 457-463.
Connan, J., and H. Coustau, 1987, Influence of the geological
and geochemical characteristics of heavy oils on their
recovery, in R. F. Meyer, ed., Exploration for heavy crude
oil and natural bitumen: AAPG Studies in Geology, v. 25,
p.261-279.
Connan J., and J. J. Orgeval, 1976, Relationship between
hydrocarbons and mineralizations: the Saint-Privat barite
deposit (Lodeve basin, France): Bulletin du Centre de
Rechercres de Pau-SNPA, v. 10, p. 359-374.
Connan, J., F. Montel, Ph. Blanc, B. Sahuquet, and R.
[ouhannel, 1991,Experimental study of expulsion of
hydrocarbons from shaly source rocks: importance of
pressure on expulsion efficiencies, (abs.): European Associ-
ation of Organic Geochemists, 15th International Meeting
on Organic Geochemistry, Manchester, England,
September 16-20, p. 14-15.
Curiale, J. A, 1986,Origin of solid bitumens, with emphasis
on biological marker results, in D. Leythaeuser and J.
 14. Preseroation, Degradation, and Destruction of Trapped Oil
Rullkotter, eds., Advances in Organic Geochemistry 1985:
Oxford, Pergamon, p. 559-580.
Dahl, B., and G. C Speers, 1986, Geochemical characterization
of a tar mat in the Oseberg field, Norwegian sector, North
Sea, in D. Leythaeuser and J. Rullkotter, eds., Advances in
Organic Geochemistry 1985: Oxford, Pergamon, p.
547-558.
Domine, F., 1991, High pressure pyrolysis of n-hexane, 2,4-
dimethylpentane, and l-phenvlbutane: is pressure an
important geochemical parameter?: Organic Geochem-
istry, v. 17, p. 619-634.
Evans, C R, M. A Rogers, and N. J. L. Bailey, 1971, Evolution
and alteration of petroleum in Western Canada: Chemical
Geology, v. 8, p. 147-170.
Fedorak, P. M., J. M. Foght, and D. W. S. Westlake, 1983,
Comparative studies on microbial degradation of
aromatics and saturates in crude oil, in J. E Zajic, D. G.,
Cooper, T. R. Jack, and N. Kosaric,eds., Microbial
enhanced oil recovery: Tulsa, PennWell Books, p. 162-172.
Coffe, B., and M. Villey, 1984, Texture d'un materiel carbone
implique dans un metamorphisme haute pression-basse
temperature (Alpes francaises): les hautes pressions influ-
encent-elles la carbonification?: Bulletin de Mineralogic, v.
107, p. 81-91.
Goodwin, N. S., P. J. D. Park, and A P. Rawlinson, 1983,
Crude oil biodegradation under simulated and natural
conditions, in M. Bjorey,ed., Advances in Organic
Geochemistry 1981: Chichester, John Wiley, p. 650-658.
Helgeson, H. C, A. M. Knox, and E. L. Shock, 1991,
Petroleum, oil field brines, and authigenic mineral assem-
blages: are they in metastable equilibrium in hydrocarbon
reservoirs? (abs.): European Association of Organic
Geochemists, 15th International Meeting on Organic
Geochemistry, Manchester, England, September 16-20, p.
39-40.
Horsfield, 8., H. J. Schenk, N. Mills, and D. H. Welte, 1991,
Closed-system programmed-temperature pyrolysis for
simulating the conversion of oil to gas in a deep petroleum
reservoir: compositional and kinetic findings (abs.):
European Association of Organic Geochemists, 15th Inter-
national Meeting on Organic Geochemistry, Manchester,
England, September 16-20, p. 56.
Ioppolo, M., R. Alexander, and R. 1. Kagi, 1991, Phenols in
crude oils (abs.): European Association of Organic
Geochemists, 15th International Meeting on Organic
Geochemistry, Manchester, England, September, 16-20, p.
56.
Jones, D. M., A. G. Douglas, and J. Connan, 1987, Hydro-
carbon distribution in crude oil asphaltene pyrolysates, 1.
Aliphatic compounds: Energy and Fuels, v. 1, p. 468-476.
Kohnen, M. E L.,J. S. Sinninghe Damste, and J. W. de Leeuw,
1991, Biases from natural sulphurization in paleoenviron-
mental reconstruction based on hydrocarbon biomarker
distributions: Nature, v. 349, p. 775-778.
Lafargue, E, and C Barker, 1988, Effect of water washing on
crude oil compositions: AAPG Bulletin, v. 72, p. 263-276.
Mango, F. D., 1991, The stability of hydrocarbons under the
time-temperature conditions of petroleum genesis: Nature,
v. 352, p. 146-148.
Palmer, S. E., 1984, Effect of water washing on C 15+ hydro-
carbon fraction of crude oils from northwest Palawan,
Philippines: AAPG Bulletin, v. 68, p. 137-149.
Peters, K E., and J. M. Moldowan, 1991, Effects of source,
thermal maturity, and biodegradation on the distribution
and isomerization of homohopanes in petroleum: Organic
Geochemistry, v. 17, p. 57--61.
247
Philp, R P., 1983, Correlation of crude oils from the San Jorge
basin, Argentina: Geochimica et Cosmoschimica Acta, v.
47, p. 267-275.
Price, L. C, 1980, Crude oil degradation as an explanation of
the depth rule: Chemical Geology, v. 28, p. 1-30.
Price, L. C, 1982, Organic geochemistry of core samples from
an ultra-deep hot well (300'C, 7 km): Chemical Geology, v.
37, p. 215-228.
Reed, W. E, 1977, Molecular compositions of weathered
petroleum and comparison with its possible source:
Geochimica et Cosmochimica Acta, v. 41, p. 237-247.
Rogers, M. A, J. D. McAlary, and N. J. L. Bailey, 1974, Signifi-
cance of reservoir bituments to thermal-maturation
studies, Western Canada basin: AAPG Bulletin, v. 58, p.
1806-1824.
Rullkotter, J., and W. Michaelis, 1990, The structure of
kerogen and related materials: a review of recent progress
and future trends, in B. Durand and F. Behar, eds.,
Advances in Organic Geochemistry 1987: Oxford,
Pergamon Press, p. 829-852.
Seifert, W. K, and J. M. Moldowan, 1979, The effect of
biodegradation on steranes and terpanes in crude oils:
Geochimica et Cosmochimica Acta, v. 43, p. 111-126.
Seifert, W. K, and J. M. Moldowan, 1981, Paleoreconstruction
by biological markers: Geochimica et Cosmochimica Acta,
v. 45, p. 783-794.
Seifert, W. K, J. M. Moldowan, and G. J. Demaison, 1984,
Source correlation of biodegraded oils: Organic Geochem-
istry, v. 6, p. 633-643.
Silverman, S. R, 1965, Migration and segregation of oil and
gas, in A. Young and J. E Galley, eds., Fluids in subsurface
environments: AAPG Memoir #4, p. 53--65.
Speight, J. G., 1984, The chemical nature of petroleum
asphaltenes, in B. Tissot, ed., Characterization of heavy
crude oils and petroleum residues: Paris, Technip, p.
32--61.
Speight, J. G., D. L. Wernick, K A Gould, R. E. Overfield, B.
M. L. Rao, and D. W. Savage, 1985, Molecular weight and
association of asphaltenes: a critical review: Revue de l'In-
stitut Francais du Petrole, v. 40, p. 51--61.
Tissot, B. P., 1988, La migration des hydrocarbures dans les
bassins sedimentaires: aspects geologiques et geochim-
iques: Revue de l'Institut Francais du Petrole, v. 43, p.
143-153.
Trifilieff, S., 0. Sieskind, and P. Albrecht, 1992, Biological
markers in petroleum asphaltenes: possible mode of incor-
poration, in J. M. Moldowan, P. Albrecht, and R P. Philp,
eds., Biological Markers in Sediments and Petroleum:
Englewood Cliffs, Prentice-Hall, p. 350-369.
Ungerer, P., F. Bessis, P. Y. Chenet, B. Durand, E. Nogaret, A.
Chiarelli, J. L. Oudin, and J. F. Perrin, 1984, Geological and
geochemical models in oil exploration: principles and
practical examples, in G. Demaison and R J. Murris, eds.,
Petroleum geochemistry and basin evaluation: AAPG
Memoir 35, p. 53-77.
Volkman.]. K, R Alexander, R 1. Kagi, and G. W.
Woodhouse, 1983, Demethylated hopanes in crude oils
and their applications in petroleum geochemistry:
Geochimica et Cosmochimica Acta, v. 47, P: 785-794.
Zhao-An, F., and R. P. Philp, 1987, Laboratory biomarker frac-
tionations and implications for migration studies: Organic
Geochemistry, v. 11, p. 169-175.
ZoBell, C E., 1973, Microbial degradation of oil: present status,
problems and perspectives, in D. G. Ahearn and S. P.
Meyers, eds., The microbial degradation of oil pollutants:
Baton Rouge, LA, Center for Wetland Resources, p. 3-16.