Multiple Controls on Petroleum

Biodegradation and Impact on

Oil Quality
Lloyd M. Wenger, Cara L. Davis, and Gary H. Isaksen, ExxonMobil Upstream Research Co.

Summary
Biodegradation of oils in nature is important in reservoirs cooler
than approximately 80C. Oils from shallower, cooler reservoirs
tend to be progressively more biodegraded than those in deeper,
hotter reservoirs. Increasing levels of biodegradation generally
cause a decline in oil quality, diminishing the producibility and
value of the oil as API gravity and distillate yields decrease; in
addition, viscosity, sulfur, asphaltene, metals, vacuum residua, and
total acid numbers increase. For a specific hydrocarbon system
(similar source type and level of maturity), general trends exist for
oil-quality parameters vs. present-day reservoir temperatures of
<80C. However, other controls on biodegradation may also have
significant effects, making predrill prediction of oil quality difficult in some areas.
It has long been observed that fresh, oxygenated waters in
contact with reservoir oil can cause extensive aerobic biodegradation. More recently, it has been recognized that anaerobic sulfatereducing and fermenting bacteria also can degrade petroleum.
Highly saline formation waters may inhibit bacterial degradation
and effectively shield oils from oil-quality deterioration. The timing of hydrocarbon charge(s) and the post-charge temperature
history of the reservoir can have major effects on oil quality.
Reservoirs undergoing current charging with hydrocarbons may
overwhelm the ability of bacteria to degrade the oil, resulting in
better-than-anticipated oil quality. Fresh charge to reservoirs containing previously degraded oil will upgrade oil quality. Calibrated
methods of oil-quality risking, based on a detailed evaluation of
reservoir charge and temperature history and local controls on
biodegradation, need to be developed on a play and prospect basis.
Introduction
Biodegradation of hydrocarbons, and the resulting decline in oil
quality, is common in reservoirs cooler than approximately 80C.
Petroleum biodegrading organisms have a specific order of preference for compounds that they remove from oils and gases. Progressive degradation of crude oil tends to remove saturated hydrocarbons first, concentrating heavy polar and asphaltene components in the residual oil. This leads to decreasing oil quality by
lowering API gravity while increasing viscosity, sulfur, and metals
contents. In addition to lowering reservoir recovery efficiencies,
the economic value of the oil generally decreases with biodegradation owing to a decrease in refinery distillate yields and an
increase in vacuum residua yields. Furthermore, biodegradation
leads to the formation of naphthenic acid compounds, which increase the acidity of the oil (typically measured as Total Acid
Number, or TAN). Increased TAN may further reduce the value of
the oil and may contribute to production and downstream handling
problems such as corrosion and the formation of emulsions.
Reservoir gas caps and solution gases also undergo biodegradation in cool reservoirs. C2+ gas components, particularly propane (C3) and n-butane (n-C4), are preferentially removed from
natural gas, making biodegraded gases drier through the enrich-

Copyright 2002 Society of Petroleum Engineers

This paper (SPE 80168) was revised for publication from paper SPE 71450, first presented
at the 2001 SPE Annual Technical Conference and Exhibition, New Orleans, 30 September3 October. Original manuscript received for review 18 November 2001. Revised manuscript received 29 July 2002. Paper peer approved 22 August 2002.

October 2002 SPE Reservoir Evaluation & Engineering

ment of methane (C1). Most biodegrading organisms also generate

carbon dioxide (CO2) as a byproduct when they degrade hydrocarbons, increasing the CO2 content of solution gas or gas caps.
Elevated CO2 contents can impact development economics negatively by necessitating the use of special steels to resist corrosion.
Evaluating the decline in hydrocarbon quality associated with
biodegradation has become critical in recent years as offshore
drilling has progressed into deeper water depths. In many areas
(e.g., offshore west Africa, Brazil, mid-Norway, South Caspian,
eastern Canada), reservoir targets in deep-to-ultradeep water are
shallow, and geothermal gradients are low. These factors make oil
quality a major risk because decreased recovery efficiency and oil
value compound with higher deepwater operating costs to significantly impact economics, even on major discoveries.
Risking oil quality predrill in shallow compartments is a major
challenge. Reservoir temperature and the consequent level of biodegradation must be estimated. To do this, knowledge of the primary (generative), undegraded oil composition is essential. The
major controls on primary oil composition are characteristics of
the source rock: (1) organic-matter type, (2) depositional environment, and (3) level of maturity. These controls exert the dominant
influence on as-generated gravity, viscosity, gas/oil ratio (GOR),
sulfur, and residua contents. Geochemical analyses of natural oil
seepage on the sea bottom often provide direct evidence for evaluation of source-rock characteristics (sedimentary facies) and maturity. Thermal modeling of hydrocarbon generation timing and
mapping of source rocks from seismic also contribute to the understanding of the hydrocarbon system.
After emplacement in cool reservoirs, hydrocarbons are subject
to biodegradation, in addition to a number of other potential alteration processes, including water washing, phase separation, gravity
segregation, and de-asphalting. Some reservoirs have a complex
history with multiple episodes of charge and degradation. Fresh
charge to a reservoir may upgrade quality, while earlier episodes of
severe degradation (possibly when the reservoir was shallower and
cooler than at present) may downgrade quality. Thus, knowledge
of generation and charge timing and reservoir temperature history
can help improve predrill predictions of oil quality.
Oil and Gas Quality
Oil and gas quality reflects the compositional characteristics of
hydrocarbons that impact the economic viability of an exploration,
development, or production opportunity. Compositions may affect
the direct value of the product (e.g., crude valuation relative to a
benchmark oil) or the development or facility costs (e.g., additional wells required, emulsion processing, use of special steels),
or they may even cause the oil to be unrecoverable. Typical oilquality properties include API gravity, viscosity, sulfur, asphaltene, and metals (e.g., vanadium, nickel, and iron content), residua
(e.g., vacuum residua or Conradson carbon content), acidity
(TAN), wax content or pour point, and sensitivity to emulsion
formation upon production. Biodegradation impacts essentially all
oil-quality properties.
Gas quality reflects the content and distribution of hydrocarbon
gas constituents and the presence and content of nonhydrocarbon
gases, such as H2S and CO2. Within the hydrocarbon gases, heating value (e.g., BTUs) increases with methane content and declines
with wet gas (C2+) content on a per mass unit basis. Generally, the
increased value of individual natural gas liquids encourages the
375

80

70
Level of Gas
Biodegradation

60

None
Slight
Moderate

50

Heavy
Severe

40
200

400

600

800

1,000

Reservoir Temperature, oC

Reservoir Temperature,

90

100
90
80
70
60
50
40

GOR, scf/STB

separation of wet gas components during gas processing. Gas

biodegradation decreases GOR (Fig. 1) and wet gas percentages
(Fig. 2) and increases the percentage of CO2 (Fig. 3).
H2S in gas causes significant handling and processing expense
because of its high toxicity and corrosivity (sulfuric acid is formed
when H2S interacts with water). Small amounts of H2S (as low as
4 ppm) impact handling and economics and can result from reservoir souring initiated by the addition of sulfate to the reservoir
during waterflood operations and the consequent activities of sulfate-reducing bacteria.14 High H2S contents may be the result of
thermochemical sulfate reduction in gas-bearing, hightemperature, carbonate, and anhydrite reservoirs, or off-structure
in an overmature drainage area.
CO2 levels in natural gas have a variety of sources and controls:
High contents of CO2 (>15%) in natural gases may result
from high-temperature thermal decomposition of carbonate rocks
(limestone and dolomite).
Lower-level CO2 (<2.5%) in gases may originate from early
thermal maturation of organic matter in source rocks (although
much generated CO2 is subject to loss owing to high water solubility). These sources of CO2 can be differentiated by their carbon
isotopic compositions. Land-plant organic material generates more
CO2 than marine-algal organic matter.
Oxidation of oil and gas by hydrocarbon-degrading bacteria
in shallow, cool reservoirs may produce elevated CO2 contents
(Fig. 3). CO2 in gas causes corrosion in production facilities because of its acidity when dissolved in water and can require the use
of special steels when contents are >5%. High CO2 content also
increases the cost of surface gas processing.
Source and Maturity Controls on Hydrocarbon
Products and Composition
Organic-matter type, depositional environment, and the source
rocks level of thermal maturity determine primary (generative) oil
quality. Organic-matter type provides initial constraints on the
expected hydrocarbon products and their distribution. Landderived plant material tends to generate gas plus liquids, while
marine algal organic matter generally produces liquids. Liquids
from land-plant organic matter are often lighter and waxier and
contain less sulfur and polar and asphaltenic material compared to
marine-algal-derived oils. Not all land-plant organic matter has
equal generation potential; some types are more oil-prone (e.g., the
Niger Delta and southeast Asia are known for an abundance of
land-plant-derived oil along with gas). Source rocks dominated by
land-plant organic matter tend to show more lateral and vertical
variability in organic-matter type than those dominated by marine
algal organic matter.
The depositional environment in which source rocks are deposited is also very important in controlling primary oil composi376

7 %C2+ HCs 14

21

Fig. 2Reservoir temperature vs. %C2+ hydrocarbons by level

of solution gas biodegradation for solution gases from oil reservoirs in an area with marine organic-matter-type source.
Gases become drier with increasing levels of biodegradation.

Reservoir Temperature, oC

Fig. 1Reservoir temperature vs. gas/oil ratio (GOR) by level of

solution gas biodegradation for oil reservoirs in an area with a
marine organic-matter-type source. GOR generally declines
with increasing level of biodegradation; scf/STB0.1781076=
m3/m3.

Level of Gas
Biodegradation
None
Slight
Moderate
Heavy
Severe

90
80
70
60
50
400.0

Level of Gas
Biodegradation
None
Slight
Moderate
Heavy
Severe

2.0

4.0

6.0 8.0
%CO2

10.0

12.0

Fig. 3Reservoir temperature vs. %CO2 by level of solution gas

biodegradation for solution gases from oil reservoirs in an area
with marine organic-matter-type source. CO2 content generally
increases with increasing levels of biodegradation.

tion. Source rocks are most commonly deposited subaqueously in

anoxic-to-dysoxic bottomwater conditions that promote the preservation of organic matter. In marine depositional settings, sulfatereducing bacteria rework sedimentary organic matter under
anaerobic conditions, producing H2S as a byproduct. Clays usually
provide iron to the depositional environment, which reacts rapidly
with any available H2S to form iron sulfides (precursors of pyrite).
When iron is not available, H2S produced by sulfate-reducing
bacteria may accumulate to high levels and be incorporated into
organic-sulfur compounds. Therefore, in clastic-dominated (shale)
source-rock environments, sulfur is dominantly incorporated into
mineral phases. In carbonate and marly depositional environments
where clays are scarce, organic matter tends to be sulfur-rich.
Compared to clastic source rocks, carbonate and marly sources
with sulfur-rich organic matter begin oil generation at lower thermal maturity levels and yield heavy, high-sulfur oil with more
residua content and other detrimental components such as metals.
Shale source rocks from depositional environments rich in clay
and iron tend to generate lighter, sweeter oils.
The maturity level of a source rock is a measure of the dominantly thermal stress it has experienced. The level of maturity
needed for hydrocarbon generation depends on the organic-matter
type, composition, and depositional setting. For a given source
rock, early-generated oils tend to be heavier and have poorer oil
quality (e.g., lower API gravity and higher sulfur contents). At
progressively higher levels of maturity, generated liquids contain
fewer high-molecular-weight hydrocarbons and polar components.
Hence, oil quality and value typically increase at higher levels of
maturity within the oil-generative window (if maturity is too
October 2002 SPE Reservoir Evaluation & Engineering

high, gas may be produced instead of oil). For an equivalent level

of biodegradation, higher-maturity oil typically maintains better oil
quality than lower-maturity oil from the same source. Generalized
ranges of initial (as-generated) hydrocarbon properties for different source-rock types, at their respective mainstage- generation
maturity levels, are summarized in Table 1.
Biodegradation and Impact on Oil Quality
Bacterial degradation of oils in reservoirs has long been recognized.57 Many of the early examples that cited in-reservoir biodegradation and oil-quality decline were from shallow, onshore oil
fields in which meteoric water influx was suspected. This observation contributed to the dogma that biodegradation of oil was
carried out by aerobic bacteria only and required a supply of oxygen to the reservoir.810 Shallow onshore reservoirs with hydrodynamic drive from fresh meteoric influx are certainly prime candidates for heavy biodegradation. However, as drilling progressed
offshore into deep water, observations of biodegradation in shallow, cool reservoirs continued to be commonplace. In these areas,
it was difficult to explain where fresh, oxygenated water could be
coming from. This led to the conclusion that anaerobic bacteria,
such as the sulfate-reducing bacteria, must be capable of biodegrading petroleum. Recent studies from the bacteriologic literature1117 have verified that sulfate-reducing bacteria, iron oxidereducing bacteria, and bicarbonate-reducing (fermenting) bacteria
are capable of biodegrading oils in reservoirs in the absence of
dissolved oxygen. In addition to an oxygen source (free or combined), bacteria need water and certain nutrients to metabolize
hydrocarbons. Adequate pore size and surface area are also necessary. The connections between oil quality, microbes, and reservoir properties are summarized in Fig. 4.
Although traditional dogma also suggested that biodegradation
must occur at the oil/water contact, recent findings suggest that
biodegradation may occur elsewhere in the hydrocarbon column.
Irreducible (bound) water within the reservoir may provide an
adequate water supply, and bacteria have been observed inhabiting
the interface between water adsorbed to mineral grains and hydrocarbons in pore spaces. The high solubility of water in natural gas
at relatively low temperatures and pressures, especially if CO2 is
present, may further enhance biodegradation.
The reservoir temperature range is critical to bacterial degradation. Above temperatures of approximately 82C, petroleumdegrading bacterial activity is significantly inhibited. At temperatures just below this limit, bacteria are generally operating at lessened efficiency. Lower-temperature reservoirs (e.g., <50C) are
much more likely to undergo heavy-to-severe degradation. Formation-water salinity also may impact the efficiency of biodegrading
bacteria, necessitating consideration of the combined temperaturesalinity environment. High formation-water salinities appear to
lower the maximum temperature at which petroleum biodegradation can occur.11 Thus, it is possible that relatively shallow, cool
reservoirs in salt-diapir provinces with high formation-water salinity levels may protect oils from biodegradation. This is difficult
to document conclusively because formation-water salinity levels
are known to be highly variable around salt diapers,18 and ad-

October 2002 SPE Reservoir Evaluation & Engineering

Oil Quality

Specific Biodegradation

Controls on Oil Biodegradation

Reservoir Properties

Microorganisms

Growth Requirements
- Different microbes degrade
different oil components
- Reservoir properties restrict

- Availability of oxidant
( e.g., O2 , FeO, SO4 , HCO3 )
- Salinity

the variety of HC degrading

- Temperature

microbes

- Porosity/permeability/surface area

Fig. 4Connections between oil quality, microbes, and reservoir properties. (Figure provided by Steve Hinton, ExxonMobil
Corporate Strategic Research Co.)

equate water samples or log data to map isohaline contours rarely

exist. In addition, the recharging of reservoirs with fresh hydrocarbons along salt diapir faults may result in better-than-expected
oil quality. Collapsed salt stocks associated with salt diapirs, particularly when source-rock intervals are penetrated by the stock,
are thought to be among the most effective hydrocarbon migration
pathways to reservoirs.19,20 In areas with active hydrocarbon systems, it can be difficult to determine whether relatively undegraded
oils in cool reservoirs adjacent to salt are the result of reduced
biodegradation caused by high water salinity or the result of a very
recent hydrocarbon charge.
The impact of biodegradation on oil-quality parameters can be
significant. As biodegradation progresses, compounds are removed from oil according to the sequence shown in Table 2.
Although different bacterial types and reservoir environments do
have some effect on the order of compounds removed, the general
order-of-preference trends described are usually applicable. The
straight chain n-alkanes are typically attacked before branched
saturates (e.g., isoprenoids), cyclic saturates, and aromatic hydrocarbons. A series of whole oil gas chromatograms (GCs), which
illustrate the impact of increasing biodegradation levels on GC
appearance and bulk fluid properties, is illustrated in Fig. 5. All
these oils are from the same basin and have been generated from
the same source-rock facies at similar maturities. The multiringed
biomarker compounds tend to be resistant through moderate-toheavy biodegradation levels, and they provide an excellent means
of correlating biodegraded and unbiodegraded oils. Large differences in GC distributions and bulk properties of the oils shown in
Fig. 6 are tied directly to the level of biodegradation.
The unbiodegraded oil in Fig. 5 largely reflects the composition
of the original oil as generated from its marine shale source rock

377

TABLE 2REMOVAL OF SELECTED COMPOUND GROUPS AT

VARIOUS LEVELS OF BIODEGRADATION*

Level of Biodegradation
C 1-C 5 gases

very slight

slight

moderate

heavy

severe

methane
ethane
propane
iso -butane
n -butane

C 15-C 35 biomarkers

C 15-C 35 HCs

C 6-C 15 HCs

pentanes

n -alkanes
iso -alkanes
isoprenoids
BTEX aromatics
alkylcyclohexanes
n -alkanes, iso -alkanes
isoprenoids
napthalenes (C 10+)
phenanthrenes, DBTs
chrysenes
regular steranes
C30-C 35 hopanes
C27-C 29 hopanes
triaromatic steranes
monoaromatic steranes
gammacerane
oleanane
C21-C 22 steranes
tricyclic terpanes
diasteranes
diahopanes
25-norhopanes**
seco-hopanes**

*Table represents a generalized sequence of degradation. Different biodegradation pathways (aerobic vs. anaerobic) and different types
of bacteria will attack specific molecules and compound ranges. Degradation sequence is based on observation of reservoired oils
and seabottom seeps. BTEX refers to benzene, toluene, ethylbenzene, and xylene.
**Appearance, rather than removal of compounds (these compounds believed to be created during biodegradation).

at mainstage oil-window maturity levels (36 to 37 API with a

GOR of 800 scf/STB). The complete suite of n-alkanes is intact,
and n-alkanes are greater than adjacent isoprenoids (e.g., as monitored by pristane/n-C17 and phytane/n-C18 ratios). The unresolved
complex mixture (UCM) of branched and cyclic compounds under
the resolved peak envelope on the GC is small. With very slight
biodegradation, n-alkanes in the approximately C8C15 range are
attacked first, as illustrated in Fig. 5. By the next stage (slight
biodegradation), this carbon-number range is further depleted, and
isoprenoid-to-alkane ratios increase as the >C15+ n-alkanes are
attacked. Note in Fig. 5 that at the slight biodegradation stage,
pristane >n-C17 and phytane >n-C18, and the UCM is slightly
larger. For moderate levels of biodegradation, n-alkanes are significantly depleted, and the UCM hump is much larger. The isoprenoids survive, and the pristane/phytane ratio is still unaltered
and virtually the same as the less-degraded oils. By the heavy
biodegradation stage, virtually all n-alkanes and isoprenoids have
been removed and the UCM hump is large.
For all the oils in the biodegradation series shown in Fig. 5, the
multiring biomarkers remain unaltered, even at heavy levels of
biodegradation. These compounds are not typically detected in
GCs; rather, they are monitored by combination GC/mass spectroscopy for genetic source and maturity information. These components are relatively resistant to biodegradation and are very useful in extracting geochemical affinities from highly degraded
samples and providing a means for correlation of unbiodegraded
and biodegraded oils. Eventually, the biomarker components are
also subject to alteration as biodegradation goes beyond heavy into
the severe stage. Within the various biomarker groups, there is also
a general order of removal by bacteria (Table 2). If biodegradation
378

reaches extremely severe levels, a series of compounds (25-nordemethylated hopanes) is formed in response to bacterially mediated ring-opening processes. The co-occurrence of demethylated
hopanes with less-resistant components (e.g., n-alkanes) is strong
evidence for a multigeneration charge and degradation history,
where severe biodegradation of an initial charge is followed by
later recharge and, possibly, additional biodegradation.
The biodegradation stages described herein and presented in
Table 1 have been used to describe the alteration state of hydrocarbons in reservoirs and to describe the predicted biodegradation
level as it relates to oil quality in unpenetrated compartments.
Published biodegradation scales21 have limited applicability for
oil-quality assessments in the industry because they are focused on
heavy and severe biodegradation when complete removal of certain compound series (e.g., n-alkanes, isoprenoids) and the alteration of biomarker components occurs. However, the greatest impact on oil-quality parameters for conventional production occurs
at much lower levels of biodegradation. In deepwater offshore
plays, oil-quality reduction caused by biodegradation may render a
discovery uneconomic without proceeding to levels at which any
of the more resistant biomarker constituents have been altered.
An example of a complicated alteration history is shown in Fig.
6. Geochemical analyses were performed on oils from two reservoirs in the same well. The shallower reservoir contains the demethylated hopane series, indicating that severe biodegradation
has occurred. It also contains a full suite of n-alkanes and regular
hopanes, which are incompatible with the demethylated hopanes
unless multiple charges have occurred. The present reservoir temperature (85C) is too high to support ongoing biodegradation.
Therefore, the shallower oil was probably emplaced when the
October 2002 SPE Reservoir Evaluation & Engineering

Fig. 5Whole oil GCs illustrating the progression of increasing biodegradation and the decline in oil quality. All oils are from the
same basin, but from different depths and or wells, and have essentially identical source and maturity, as indicated by biomarker
distributions (not shown). Increasing pristane/n-C17 ratio illustrates the preference for n-alkanes over isoprenoids in biodegradation. N-alkanes over the approximately C8C15 range are attacked first. (Pr=pristane; Ph=phytane; MCH=methyl cyclohexane;
n-C6...=homologous n-alkane series.)

reservoir was shallower and cooler than it is today. Severe biodegradation was then followed by later recharge. Oil from the
deeper, hotter reservoir has a GC very similar to that for the
shallower reservoir, with a full, unaltered suite of n-alkanes. However, the deeper oil does not contain any demethylated hopanes
and shows no other evidence of biodegradation. As a consequence,
the deeper oil is 10 lighter in API gravity.
Progressive biodegradation almost invariably reduces oil quality. As the high-quality saturated hydrocarbons are removed, there
is residual enhancement of the low-quality, high-molecular-weight
multiring hydrocarbons and the nonhydrocarbon compounds, such
as asphaltenes. These compositional changes lead to lower gravity,
higher viscosity, and higher sulfur, nitrogen, and asphaltene contents. Metals, ash, and residua contents also are enhanced. These
changes result in lower value for the crude oil, diminished recovery efficiency, and possible additional production problems associated with handling and processing heavier oils. One oil-quality
parameter that does not always get worse with biodegradation is
wax content. High wax content and high pour-point oils are common in areas such as southeastern Asia. Because waxes are highmolecular-weight n-alkanes, they are attacked at slight-tomoderate biodegradation levels. Although this loss may contribute
to decreased API gravity, a slight API decrease is often offset
by lowered pour points and less wax deposition in tubulars
and facilities.
In addition to the concentration of low-quality oil components
during biodegradation, new compounds can be formed that negatively impact quality. Bacteria appear to manufacture acids, most
of which are naphthenic (i.e., cyclic) acids, during the biodegradation of petroleum.22 Because of solubility differences, lowmolecular-weight (C1-C5) acids occur predominantly in associated
October 2002 SPE Reservoir Evaluation & Engineering

formation waters,23 while higher-molecular-weight species (C6+)

are concentrated in the oil phase. The distribution of the various
naphthenic acid species in oils is poorly understood. Acid contents
are usually monitored as a TAN determined by potentiometric
titration as per the ASTM D-664 method. This method is wrought
with potential interferences and interpretive problems,24 but it
remains a standard method by which oils are assayed and valued.
TAN generally increases with increasing levels of biodegradation. The current activity of biodegrading organisms may be most
important in determining organic acid contents because acids
may dissipate rapidly owing to relatively high water solubility
and reactivity.
Elevated naphthenic acid contents (TAN >1 mgKOH/goil) are
detrimental to crude-oil value because acids cause refinery equipment corrosion at high temperatures.2527 This can result in an
additional valuation debit. Naphthenic acids and their salts (naphthenates) also may lead to the formation of emulsions upon production of biodegraded oils. Sometimes these emulsions can be
tight and difficult to break by conventional means. The additional
expense associated with breaking emulsions, especially on production platform sites in deep water, can further challenge field economics. Low-molecular-weight organic acids in water often impart
very foul odors and can cause wastewater disposal problems in
refineries processing some biodegraded oils.
Biodegradation and Impact on Gas Quality
Biodegradation of natural gases generally decreases the GOR (solution gas in oil legs) and wet gas content and increases the relative
proportion of methane (gas caps and solution gases), as illustrated
in Figs. 1 through 3. Biodegradation also may cause CO2 contents
to increase (a byproduct of bacterial oxidation). In addition to
379

Fig. 6Comparison of whole oil GCs and mass/charge (m/z) 177 biomarker scans for two reservoirs from Well A. The deeper
reservoir shows no evidence of biodegradation, while the shallower shows biomarker evidence of severe biodegradation, followed
by recharge with fresh oil. Current reservoir temperatures in both reservoirs are too high for active biodegradation. Geochemical
analyses constrain the filling and degradation history of reservoirs. [C28DM=C28-25-nor-demethylated hopane; C29DM=C29-25nor-demethylated hopane; C29H=C29 hopane; C29Ts=C29-22,29,30-norhopane; C29M=C29 normoretane; OL=oleanane; C30DM(1) &
(2)= C30-25-nor-demethylated hopanes; C31DM=C31-25-nor-demethylated hopanes; C31H=C31 hopanes; C32DM=C32-25-nordemethylated hopanes; C32H=C32 hopanes; C33H=C33 hopanes; C34H=C34 hopanes; C35H=C35 hopanes; peak labels on whole oil
GCs as per Fig. 5.]

380

-24
Sample 1
-25

Sample 3

Field C

Sample 5

13C ( vs. PDB)

compositional changes, bacterial degradation causes carbon isotopic changes in individual gas components. Geochemical analyses
of reservoir gases from around the world have shown that bacteria
preferentially attack propane during the initial stages of biodegradation.27,28 The decrease in concentrations of propane is accompanied by a fractionation of the stable carbon isotopic composition.
During biodegradation, the residual (parent) propane fraction becomes enriched in the heavier 13C isotope, whereas the CO2
byproduct (daughter) is isotopically enriched in 12C. Bacterialenzymatic processes and C-C bond energies control these compositional and isotopic changes.29 Less energy is required to break a
12
C-12C than a 12C-13C bond, and bacteria follow the path of
greatest reward (energy from oxidation) for the least amount of
work (bond energies). A comparison of gas analyses from a North
Sea field (see Table 2 and Fig. 7) with gases from two nearby
fields indicates that the reservoirs contain three distinct gas compositional groupings. All fields received the same hydrocarbon charge.
Relatively heavy isotopic compositions for wet gas (C2+) components in Field C gases suggest significant biodegradation. Gases
from Fields B and A show less intense alteration (Fig. 7). The
relative intensity of biodegradation becomes apparent when the
isotopic difference between propane and n-butane is plotted
against the isotopic composition of propane (Fig. 8). This trend
results from the fact that propane is degraded preferentially to
n-butane. For samples from Field B, biodegradation is greatest for
Sample 1 and least for Sample 12. Molecular compositions also
support the degradation trend indicated by isotopic compositions.

-26
Sample 10
-27

Field B

Sample 13
Sample 17

-28

-29
Field A
-30

-31
Ethane

Propane

-Butane

i -Butane

Fig. 7Average wet gas isotope ratios for select North Sea
fields. Stable carbon isotopic ratios are plotted against the wetgas components.

In biodegraded samples, propane is depleted relative to n-butane,

and n-butane is depleted relative to i-butane.
Other In-Reservoir Alteration Processes
In addition to biodegradation, other in-reservoir alteration processes can impact hydrocarbon quality. These include water washing, phase separation, gravity segregation, gas de-asphalting, and
in-reservoir oil cracking. These processes are reviewed as follows
and summarized in Fig. 9.
October 2002 SPE Reservoir Evaluation & Engineering

2
Well 1-4
18

Well 5-8

13C propane - 13C n-butane

1.5

0.5

In

n
si
ea
cr

io
B

d
ra
eg

i
at

Well 9-12

on

Well 13-16
17

Well 17-18

14
9

-0.5

15
13

-1

16

3
10

11

-1.5
-29

-28

-27

-26

-25

-24

13C propane ( vs. PDB)

Fig. 8Biodegradation of wet gases in select North Sea fields.

The difference in isotopic ratios between propane and n-butane
is plotted against the stable carbon isotopic ratio of propane to
show the increase in biodegradation of wet gases toward the
upper right in the plot. Sample labels refer to the sample numbers in Table 3.
Reservoir

(PVT effects)
Conditions

Reservoir Alteration
Thermochemical
SO4 Reduction

BIODEGRADATION
temperature

GAS DE-ASPHALTING

GRAVITY

Bacterial
Activity

nutrients

SEGREGATION

oxidant

PHASE-SEPARATION
CRACKING

salinity
WATER WASHING

History of charge,
reservoir

Migration

conditions

Alteration
Generative HC properties
Maturity

Increasing

Source Facies

Gravity Segregation. The stratification of an oil column by density is referred to as gravity segregation. This process typically
requires high permeability and most often occurs in steeply dipping reservoirs where heavy-end components from the oil settle to
the lower portion of the reservoir. There may be a time requirement for the development of a segregated column.

12

soluble (e.g., aromatic hydrocarbon) components of similar molecular weights.

HC
Yield
C

15+

OIL & GAS QUALITY:

C -C
6

C -C
1

Value and producibility

14

Fig. 9Summary of factors affecting oil and gas quality. Source

facies and level of maturity control generative hydrocarbon
(HC) composition. After potential fractionation along the migration pathway, a range of possible processes can occur in the
reservoir, including biodegradation at temperatures lower than
approximately 82C. The timing of HC charge event(s) and the
temperature history of the reservoir after filling also ultimately
contribute to the quality of oil and gas in the reservoir.

Water Washing. Alteration of oil by water washing occurs when

the most water-soluble components (e.g., light aromatic hydrocarbons) are removed from the oil by contact with formation waters.
The limited solubility of hydrocarbons in water increases at higher
temperatures and pressures and declines with increasing salinity.30,31 Water washing often occurs simultaneously with biodegradation in reservoirs < 80C. The two processes are sometimes
difficult to distinguish.
Phase Separation. When both gas and oil phases are present in a
reservoir, faulting or other seal-related processes may allow gas to
escape preferentially. This gas may migrate to a shallower reservoir where lower pressure and temperature conditions cause exsolution of a lighter liquid phase. The residual oil remaining in the
deeper reservoir will be light-end depleted and generally of poorer
quality than it was before gas loss32,33 occurred. Phase separation
is generally recognized by the relative enrichment or depletion of
more gas-soluble (e.g., saturated hydrocarbons) vs. less gasOctober 2002 SPE Reservoir Evaluation & Engineering

Gas De-Asphalting. De-asphalting of oils in the refinery is often

accomplished by bubbling natural gas through the oil. This destabilizes heavy asphaltene molecules, causing their precipitation.
This same process can occur in reservoirs if gas is directed into an
oil reservoir through diapir-related reservoir tilting or other geologic processes. Tar mats commonly result from in-reservoir gas
de-asphalting.
In-Reservoir Cracking. The thermal cracking of oils in reservoirs
occurs when the reservoirs are exposed to high temperatures
(>150C), usually because of deep burial. As heavier oil components thermally crack into lighter molecules, a lighter hydrocarbon
product results. Should burial to higher temperatures continue,
further cracking might result, ultimately yielding gas and solid
bitumen residue (pyro-bitumen).
Applications of Biodegradation and Oil Quality
to Prospect Evaluation and Risking
Exploration Risking and Block Ranking. Oil-quality risking is
an important assessment parameter when making exploration decisions regarding the viability of plays or prospects. Calibrations of
expected reservoir temperature and biodegradation level to oilquality parameters provide the groundwork for predrill predictions.
Local calibration of parameters, or selection of appropriate analogs, is critical because degradation trends are dependent on effective hydrocarbon system(s) and are tied to source type, source
depositional environment, maturity, and filling history.34 Selection
of the appropriate biodegradation trend calibration is based on the
geochemistry of nearby discoveries or shows, if available. In many
deepwater frontier areas, surface hydrocarbon seeps provide initial
information on source type and maturity level before any drilling.35 In the absence of geochemical data on actual hydrocarbon
samples, the characteristics of the effective source can be estimated from depositional models and thermal yield calculations.36
Field Development. Geochemical analyses and interpretations,
when integrated with pressure trends and a geologic and geophysical framework, provide important input to development and production planning. Exploitation geochemical approaches are especially pertinent to help determine continuity or segmentation of
reservoir compartments when pressure or geologic data are ambiguous. Understanding reservoir continuity is critical to optimizing field-development planning. Identification of reservoir segmentation is also important to the efficient placement of injector/
producer pairs when pressure maintenance by water injection is
planned. Differences in biodegradation level can sometimes indicate segmented compartments. Geochemical analyses also can
detect gradients in hydrocarbon properties within continuous
reservoirs (e.g., caused by gravity segregation). Recognition of
such gradients is important for reservoir models and field planning.
In heavy-oil fields, geochemical analyses of sidewall cores can
help to identify oil-quality variations and sweet spots for targeted production.
Corrosion/Facilities Design. As exploration proceeds into deeper
water offshore, biodegraded oils appear to be more commonly
encountered in many basins as cool, shallow reservoirs are penetrated. An increasing number of elevated TAN oils will therefore
be developed and produced in the future. In addition to lower crude
values resulting from high-temperature corrosion problems in refineries, biodegraded oils tend to have associated problems such as
tight emulsion formation. The need to handle and remediate pro381

duced fluids on deepwater production sites will continue to impact

and challenge economic scenarios. An increased understanding of
biodegradation processes, including the origin and molecularweight-range distributions of organic acids and related compounds
in oils and waters, can aid in early recognition and reconciliation
of potential problems while in the planning stages. This permits
better early valuation of new crude-oil grades and early recognition of processing and handling requirements impacting both upstream and downstream business decisions.
Conclusions
Oil and gas quality determines the direct value of a hydrocarbon
product and the economics of its development. Hydrocarbon quality is determined by source-rock composition and thermal maturity
and by the degree of alteration. Biodegradation is the most important process altering reservoir hydrocarbons in many areas, but
water washing, phase separation, gravity segregation, gas deasphalting, and thermal cracking also can impact hydrocarbon
quality. Biodegradation, active at reservoir temperatures <80C,
can significantly reduce hydrocarbon quality, particularly in the
shallow, cool reservoirs that have dominated recent deepwater
exploration. As biodegrading organisms attack higher-quality hydrocarbon components, they residually concentrate poor-quality
components, including sulfur, asphaltenes, and residua. Because
bacteria attack different hydrocarbon compounds based on an order of preference, the biodegradation stage can be determined
based on the alteration of specific compound classes and structures.
The classification of biodegradation stages presented herein is
important for describing and predicting oil and gas quality. Some
compounds are produced during biodegradation, notably naphthenic acids and demethylated hopanes. Naphthenic acids contribute to oil-quality debits and may cause additional processing and
downstream handling problems. Bacterial activity is strongly controlled by temperature, but it also may be impacted by formationwater salinity, availability of free or combined oxygen, reservoir
characteristics, and the timing of charge(s).
Gas biodegradation results in the decline and loss of wet components and, often, the production of undesirable gases such as
CO2. The stage of gas biodegradation is not necessarily linked to
that of the associated oil.
382

Geochemical analyses are relatively quick and inexpensive and

provide critical information regarding oil and gas quality. If calibration data are available, predictive models of oil and gas degradation often can be constructed that improve predrill estimates of
hydrocarbon quality during the exploration and development
phases. After production commences, routine collection and analysis of fluid samples at little cost can allow changes in production
characteristics to be determined and efficiently exploited. Applications include recognition of the production-stimulated breakdown of natural reservoir baffles, rapid and inexpensive diagnosis
of tubing or casing damage, and production allocation from commingled reservoirs. It is therefore critical to collect and analyze
representative samples through all phases of a fields history.
Wireline or drillstem test samples from early exploration often
provide the only characterization of individual reservoir zones before commingling. Even the analysis of sidewall cores in reservoir
zones can provide important information. Later, routine (e.g.,
monthly) sampling of the production stream permits compositional
changes to be monitored and evaluated.
Acknowledgments
The authors thank ExxonMobil Upstream Research Co. for permission to publish this work. Productive discussions with Steve
Hinton and Winston Robbins at ExxonMobil Corporate Strategic
Research Co. are gratefully acknowledged. Constructive review of
the manuscript by Paul Mankiewicz (EMURC; during the great
Houston Flood of 2001) and additional discussions and insights
were most helpful. W. Allen Young provided useful comments.
Jan Herbst assisted in figure and manuscript preparation. The SPE
Editorial Review Committee is acknowledged for their efforts and
editorial suggestions that improved this paper.
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SI Metric Conversion Factors

API
41.5/(131.5+API)
bbl 1.589 873
E01
ft 3.048*
E01
F
(F32)/1.8

g/cm3
m3
m
C

*Conversion factor is exact.

Lloyd M. Wenger is a petroleum geochemist with ExxonMobil

Upstream Research Co. His work focus has been on the application of geochemical technologies to exploration, development, and production problems and linkage to downstream
organizations for early recognition of value and handling/
processing issues. After many years of working in the Gulf Coast
and the Gulf of Mexico, he has worked primarily in west Africa,
including Nigeria and Congo, and he is currently involved in
development and exploration activities in deepwater Angola.
Wenger holds a PhD degree in organic geochemistry from
Rice U. Cara L. Davis has been with ExxonMobil Upstream Research for 5 years, focusing on oil quality and reservoir geochemistry research and applications. She holds a PhD degree
in geology (specializing in organic geochemistry) from Indiana
U. Gary H. Isaksen is Research Supervisor for Petroleum Geochemistry with ExxonMobil Upstream Research Co. Since joining Exxon in 1985, the major themes of his work have been
integration of geology and petroleum geochemistry, molecular geochemistry, play-element risking, and applications of
geochemistry to field development and production. From
1993 to 1995, he worked frontier and established plays within
U.K. and Norwegian acreage, and from 1997 to 1999, he
worked regional- and prospect-scale assessments within Azerbaijan, Turkmenistan, Uzbekistan, and Russia. His current geoscience focus is on applied research to solve exploration, development, and production problems. Isaksen holds a PhD degree in petroleum geochemistry and petroleum geology from
the U. of Bergen, Norway.

383