SPE 71450
Multiple Controls on Petroleum Biodegradation and Impact on Oil Quality
Lloyd M. Wenger, Cara L. Davis and Gary H. Isaksen / ExxonMobil Upstream Research Company
Copyright 2001, Society of Petroleum Engineers Inc.
This paper was prepared for presentation at the 2001 SPE Annual Technical Conference and
Exhibition held in New Orleans, Louisiana, 30 September–3 October 2001.
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Abstract
Biodegradation of oils in nature is important in reservoirs
cooler than approximately 80o C. 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; and viscosity, sulfur,
asphaltene, metals, vacuum residua, and total acid number
increase. For a specific hydrocarbon system (similar source
type and level of maturity), general trends exist for oil quality
parameters versus present-day reservoir temperature < 80o C.
However, additional controls on biodegradation may have
significant effects, making pre-drill prediction of oil quality
difficult.
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 sulfate-reducing and fermenting bacteria can also
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. Currently charging
reservoirs 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
80o C. 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 due to
a decrease in refinery distillate yields and 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 enrichment of methane (C1). Most
biodegrading organisms also generate carbon dioxide (CO2) as
a by-product when they degrade hydrocarbons, increasing the
CO2 content of solution gas or gas caps. Elevated CO2 contents
can negatively impact development economics 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 low.
These factors make oil quality a major risk as decreased
recovery efficiency and oil value compound with higher
deepwater operating costs to significantly impact economics,
even on major discoveries.
Risking oil quality pre-drill in shallow compartments is a
major challenge. Reservoir temperature and the consequent
level of biodegradation must be estimated. To do so,
knowledge of the primary (generative), undegraded oil
composition is essential. The major controls on primary oil
2 L.M. WENGER, C.L. DAVIS, AND G.H. ISAKSEN
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 contributes 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
the present) may downgrade quality. Thus knowledge of
generation and charge timing and reservoir temperature
history can help improve pre-drill predictions of oil quality.
Oil and Gas Quality
Oil and gas quality reflects 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), development or
facility costs (e.g., additional wells required, emulsion
processing, use of special steels, etc.) or may even cause the
oil to be unrecoverable. Typical oil quality 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
non-hydrocarbon 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.
Generally, the increased value of individual natural gas liquids
encourages the separation of wet gas components during gas
processing. Gas biodegradation decreases GOR (Fig. 1) and
wet gas content (Fig. 2), and increases the relative proportion
of CO2 (Fig. 3).
H2S in gas causes significant handling and processing
expense due to 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 water-flood operations and the
consequent activities of sulfate-reducing bacteria1,2,3,4. High
H2S contents may be the result of thermochemical sulfate
reduction in gas-bearing, high-temperature, carbonate and
SPE 71450
anhydrite reservoirs, or off-structure in an over-mature
drainage area.
CO2 levels in natural gas have a variety of sources and
controls: 1) High contents of CO2 (> ~15%) in natural gases
may result from high temperature thermal decomposition of
carbonate rocks (limestone and dolomite). 2) 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 due 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. 3) 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 due to
acidity when dissolved in water and can require the use of
special steels when contents are > ~5%. High CO2 contents
also increases the cost of surface gas processing.
Source and Maturity Controls on Hydrocarbon
Products and Composition
Organic-matter type, depositional environment, and level of
thermal maturity of the source rock determine primary
(generative) oil quality. Organic-matter-type provides initial
constraints on the expected hydrocarbon products and their
distribution. Land-derived 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, as some types are more oil-prone (e.g., Niger Delta
and Southeast Asia are know 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
composition. Source rocks are most commonly deposited sub-
aqueously in anoxic-to-dysoxic bottom-water conditions that
promote the preservation of organic matter. In marine
depositional settings, sulfate-reducing bacteria rework
sedimentary organic matter under anaerobic conditions,
producing H2S as a by-product. Clays usually provide iron to
the depositional environment that 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
SPE 71450 MULTIPLE CONTROLS ON PETROLEUM BIODEGRADATION AND IMPACT ON OIL QUALITY
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 level of maturity 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 high, gas may be
produced rather than oil). For an equivalent level of
biodegradation, higher maturity oil typically maintains better
oil quality than lower maturity oil from the same source.
Biodegradation and Impact on Oil Quality
Bacterial degradation of oils in reservoirs has long been
recognized5,6,7. Many of the early examples that cited in-
reservoir biodegradation and oil quality decline were from
shallow, onshore oil fields where 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 reservoir8,9,10. 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 literature11,12,13,14,15,16,17 have verified that sulfate-
reducing bacteria, iron oxide-reducing 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 in order 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.
3
The reservoir temperature range is critical to bacterial
degradation. Above temperatures of approximately 82o C,
petroleum-degrading bacterial activity is significantly
inhibited. At temperatures just below this limit, bacteria are
generally operating at lessened efficiency. Lower temperature
reservoirs (e.g., < 50oC) are much more likely to undergo
heavy-to-severe degradation. Formation-water salinity may
also impact the efficiency of biodegrading bacteria,
necessitating consideration of the combined temperature-
salinity environment. High formation water salinities appear to
lower the maximum temperature at which petroleum
biodegradation can occur11. 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, as
formation water salinity levels are know to be highly variable
around salt diapirs18, and adequate water sample or log data to
map iso-haline contours rarely exists. In addition, re-charging
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
reservoirs19,20. 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 due to high water salinity, or 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 1.
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) illustrating the impact of increasing
biodegradation level on GC appearance and bulk fluid
properties, is illustrated in Fig. 5. All of these oils are from the
same basin and have been generated from the same source
rock facies at similar maturities. The multi-ringed biomarker
compounds tend to be resistant through moderate-to-heavy
biodegradation levels, and provide an excellent means of
correlating biodegraded and unbiodegraded oils. Large
differences in GC distributions and bulk properties of the oils
shown in Fig. 5 are directly tied to 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 at mainstage oil window maturity levels
(~36-37o 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
4 L.M. WENGER, C.L. DAVIS, AND G.H. ISAKSEN
biodegradation, n-alkanes in the approximately C8 - C15 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 of the oils in the biodegradation series shown in
Fig. 5, the multi-ring biomarkers remain unaltered, even at
heavy levels of biodegradation. These compounds are not
typically detected in GCs, but rather 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 of correlation of unbiodegraded and
biodegradaed 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 1).
If biodegradation reaches extremely severe levels, a series of
compounds (25-nor-demethylated hopanes) are 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 multi-
generation 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 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 due to biodegradation may render a
discovery uneconomic without proceeding to levels where 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 (85oC) is too high to support
SPE 71450
on-going biodegradation. Therefore, the shallower oil was
probably emplaced when the reservoir was shallower and
cooler than it is today. Severe biodegradation was then
followed by later re-charge. 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 ten degrees 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 multi-ring hydrocarbons and non-
hydrocarbon 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 are also 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.
As waxes are high molecular weight n-alkanes, they are
attacked at slight-to-moderate 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 petroleum22. Due to
solubility differences, low molecular weight (~C1-C5) acids
occur predominantly in associated formation waters23, 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 total acid number (TAN) determined by
potentiometric-titration as per the ASTM D-664 method. This
method is wrought with potential interferences and
interpretive problems24, but remains a standard method by
which oils are assayed and valued. TAN generally increases
with increasing level of biodegradation. The current activity
of biodegrading organisms may be most important in
determining organic acid contents as acids may dissipate
rapidly due to relatively high water solubility and reactivity.
Elevated naphthenic acid contents (TAN > ~1 mgKOH/goil)
are detrimental to crude oil value, as acids cause corrosion to
refinery equipment at high temperatures25,26,27. This can result
in an additional valuation debit. Naphthenic acids and their
salts (naphthenates) may also 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
deepwater, can further challenge field economics. Low-
SPE 71450 MULTIPLE CONTROLS ON PETROLEUM BIODEGRADATION AND IMPACT ON OIL QUALITY
molecular-weight organic acids in water often impart very foul
odors and can cause waste water 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, 2, and 3. Biodegradation may also cause
CO2 contents to increase (by-product of bacterial oxidation).
In addition to compositional changes, bacterial degradation
causes carbon isotopic changes in individual gas components.
Geochemical analyses of reservoired gases from around the
world have shown that propane is preferentially attacked by
bacteria during the initial stages of biodegradation27,28. The
decrease in absolute 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
by-product (daughter) is isotopically enriched in 12C. These
compositional and isotopic changes are controlled by
bacterial-enzymatic processes and C-C bond energies. Less
energy is required to break a 12C-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 (Table 2;
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. 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:
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 salinity29,30. Water washing often
5
occurs simultaneously with biodegradation in reservoirs < 80o
C. 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 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 gas-soluble (e.g., aromatic
hydrocarbon) components of similar molecular weights.
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.
Gas de-asphalting. De-asphalting of oils in the refinery is
often accomplished by bubbling natural gas through the oil.
This de-stabilizes 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 (> ~150o), usually due to 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
level of biodegradation to oil quality parameters provide the
groundwork for pre-drill predictions. Local calibration of
parameters is critical as degradation trends are dependent on
effective hydrocarbon system(s) and tied to source-type,
source-depositional environment, maturity, and filling
history34.
Field Development. Geochemical analyses and
interpretations, when integrated with pressure trends and the
geologic and geophysical framework, provide important input
to development and production planning. For example,
identification of reservoir segmentation is critical to efficient
placement of injector-producer pairs when pressure
maintenance by water injection is planned. Differences in
6 L.M. WENGER, C.L. DAVIS, AND G.H. ISAKSEN
biodegradation level can sometimes indicate segmented
compartments. Geochemical analyses can also detect gradients
in hydrocarbon properties within continuous reservoirs (e.g.,
due to gravity segregation). Recognition of such gradients is
important for reservoir models and field planning.
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 produced fluids
on deepwater production sites will continue to impact and
challenge economic scenarios. An increased understanding of
biodegradation processes, including the origin and molecular-
weight range distributions of organic acids and related
compounds in oils and waters, is critical to this effort.
Bioremediation/Pollution Cleanup. Bacteria rapidly degrade
large amounts of petroleum from both natural (seeps) and
anthropogenic sources. Studies examining biodegradation
rates of oil spilled from the Exxon Valdez indicate losses of
approximately 70 % over a 14-month period35,36,37. This rate is
presumed to reflect aerobic biodegradation, as the studies were
focused on intertidal beaches where replenishment of oxygen
is continuous. Laboratory experiments of anaerobic
biodegradation of contaminated aquifer waters indicated oil-
removal of 14% after 65 days38.
Summary
Oil and gas quality determine 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 de-
asphalting, and thermal cracking can also impact hydrocarbon
quality. Biodegradation, active at reservoir temperatures <
~80ºC, 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 downsream handling
problems. Bacterial activity is strongly controlled by
SPE 71450
temperature, but may also be impacted by formation-water
salinity, availability of free or combined oxygen, reservoirs
characterisitcs, and the timing of charge(s).
Gas biodegradation results in the decline and loss of wet
components and often production of undesirable gases such as
CO2. The stage of gas biodegradation is not necessarily linked
to that of the associated oil.
Geochemical analyses are relatively quick and inexpensive
and provide critical information regarding oil and gas quality.
If calibration data is available, predictive models of oil and gas
degradation can often be constructed. It is therefore critical to
collect and analyze representative samples.
Acknowledgements
The authors would like to thank the Management of
ExxonMobil Upstream Research Company for permission to
publish this work. Productive discussions with Steve Hinton
and Winston Robbins at ExxonMobil Corporate Strategic
Research Company 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. Jan Herbst is
acknowledged for assistance with figure preparation.
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8 L.M. WENGER, C.L. DAVIS, AND G.H. ISAKSEN SPE 71450

Level of Biodegradation
very slight slight moderate heavy severe
methane
C 1-C5 gases

ethane
propane
iso -butane
n -butane
pentanes

n -alkanes
C 6-C 15 HCs

iso -alkanes
isoprenoids
BTEX aromatics
alkylcyclohexanes
n -alkanes, iso -alkanes
C 15-C 35 HCs

isoprenoids
napthalenes (C 10+)
phenanthrenes, DBTs
chrysenes
regular steranes
C 30-C 35 hopanes
C 27-C 29 hopanes
C15-C 35 biomarkers

triaromatic steranes
monoaromatic steranes
gammacerane
oleanane
C 21-C 22 steranes
tricyclic terpanes
diasteranes
diahopanes
25-norhopanes*
seco-hopanes*
*appearance, rather than removal of compounds (these compounds believed to be created during biodegradation)

Table 1. Removal of selected compound groups at various levels of biodegradation. 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 reservoir oils and sea bottom seeps. (BTEX
refers to benzene, toluene, ethylbenzene, and xylene; DBTs = dibenzothiophenes).
SPE 71450 MULTIPLE CONTROLS ON PETROLEUM BIODEGRADATION AND IMPACT ON OIL QUALITY 9

Field Well Sample No. Methane Ethane Propane i-Butane n-Butane

A 1 1 -47.30 -30.05 -28.67 -28.89 -28.33
A 1 2 -47.09 -30.38 -28.62 -28.34 -27.68
A 2 3 -45.28 -28.98 -28.38 -27.98 -27.69
A 2 4 -47.78 -30.04 -28.64 -27.27 -27.67

B 3 6 -44.14 -29.15 -27.11 -27.16 -27.03

B 3 7 -43.82 -29.08 -27.02 -27.52 -27.16
B 3 8 -43.43 -28.99 -27.16 -27.32 -27.01
B 3 9 -42.86 -28.54 -26.91 -26.88 -26.97
B 4 10 -43.28 -28.92 -28.16 -28.08 -27.51
B 4 11 -43.29 -28.89 -27.66 -27.98 -26.99
B 4 12 -43.44 -29.05 -27.36 -26.63 -26.55
B 4 13 -44.00 -28.52 -27.15 -26.50 -27.07
B 5 14 -43.59 -28.60 -27.30 -27.32 -26.69
B 5 15 -43.01 -28.60 -27.59 -28.06 -27.11
B 5 16 -44.58 -28.52 -27.35 -26.79 -26.65
B 5 17 -43.42 -27.98 -27.05 -26.57

C 6 18 -45.05 -25.04 -25.45 -26.93 -26.17

C 6 19 -44.32 -23.93 -24.70 -26.80 -26.49
Note: Precision of analysis is ± 0.2‰
Units in parts per million relative to the NBS-22 standard

Table 2: Carbon isotope ratios for gases from North Sea fields.
Reservoir Temperature ( oC)

90

80

70
Level of Gas
60 Biodegradation
None
Slight
Moderate
50 Heavy
Severe
40
200 400 600 800 1000
GOR (SCF/STB)

Figure 1. Reservoir temperature vs. gas-oil ratio (GOR) by level of solution gas
biodegradation for oil reservoirs in the same basin with a marine-organic-
matter-type source. GOR generally declines with increasing level of
biodegradation.
10 L.M. WENGER, C.L. DAVIS, AND G.H. ISAKSEN SPE 71450

100

Reservoir Temperature ( oC)

90

80

70
Level of Gas
60 Biodegradation
None
Slight
50 Moderate
Heavy
Severe
40
0 7 %C 2+ HCs 14 21

Figure 2. Reservoir temperature vs. %C2+ hydrocarbons by level of solution gas

biodegradation for solution gases from oil reservoirs in the same basin with marine
organic-matter-type source. Gases become drier with increasing level of biodegradation.
Reservoir Temperature ( oC)

Level of Gas
Biodegradation
90 None
Slight
Moderate
80 Heavy
Severe
70

60

50

40
0.0 2.0 4.0 6.0 8.0 10.0 12.0
%CO2

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

biodegradation for solution gases from oil reservoirs in the same basin with
marine organic-matter-type source. CO2 content generally increases with
increasing level of biodegradation.
SPE 71450 MULTIPLE CONTROLS ON PETROLEUM BIODEGRADATION AND IMPACT ON OIL QUALITY 11

Oil Quality

Specific Biodegradation Controls on Oil Biodegradation

Microorganisms Reservoir Properties

Growth Requirements

- Different microbes degrade - Availability of alternative form of

different oil components oxygen (e.g., FeO, SO , HCO )
4 3
- Reservoir properties restrict - Salinity
the variety of HC degrading - Temperature
microbes - Porosity / permeability / surface area

Figure 4. Connections between oil quality, microbes, and reservoir properties. Figure provided by Steve Hinton,
ExxonMobil Corporate Strategic Research Company.
SPE 71450

Slight-Moderate Biodegradation
MCH

Unbiodegraded
36.1°API; 93°C 29.2°API; 65.6°C
Pr/Ph=1.52; Pr/n-C1 7=0.63 Pr/Ph=1.25; Pr/n-C1 7=3.89
MCH

Pr
nC6

nC10

Ph
nC15

nC17
nC18

nC20
nC20

nC25
Pr

nC25
Ph

nC30
MCH

Very Slight Biodegradation Moderate Biodegradation

MCH
L.M. WENGER, C.L. DAVIS, AND G.H. ISAKSEN

31.5°API; 68°C 26.5°API; 74°C

Pr/Ph=1.32; Pr/n-C1 7=4.97
nC15

Pr/Ph=1.29; Pr/n-C17=0.97
Pr
Ph
nC20

Pr
nC6

Ph
nC25

nC30
MCH

Slight Biodegradation
30.8°API; 67.7°C
Pr/Ph=1.29; Pr/n-C1 7=1.29

Pr
nC15

Ph
nC6

nC20

nC25
Heavy Biodegradation
21.4°API; 47.4 °C
Pr/Ph= not present
UCM
Pr/n-C 17= not present
Figure 5. Whole oil gas chromatograms illustrating progression of increasing biodegradation and 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 C 8-C15 range are attacked first. ( Pr=pristane;
Ph=phytane; MCH=methyl cyclohexane ; n-C6...=homologous n-alkane series; UCM=unresolved complex mixture of branched and cyclic compounds)
12
SPE 71450 MULTIPLE CONTROLS ON PETROLEUM BIODEGRADATION AND IMPACT ON OIL QUALITY 13

C29H
pA
80000 m/z 177

C28DM
Well 'A' 1945m

OL + C30 DM (1)
400 Whole Oil Gas Chromatogram

C30H + C30 DM(2)

Well 'A' 1945m; 85°C Demethylated

C29Ts
350 24 °API; 0.80% S Hopanes Present
Pr/Ph=1.32; Pr/n-C17=0.82 Regular Hopanes
300 Present

C29M
MCH
nC6

250

C29DM
nC15

nC17

200
Ph nC18
nC20
nC10

C31 DM
Pr

150

C31 H
nC25

C32 DM
C32 H
C33 H
nC30

C34 H
C35 H
100

50
10000

0
0 10 20 30 40 50 60 70 min 0
25.00 30.00 35.00 40.00 45.00 50.00 55.00 60.00 65.00

140 0 Whole Oil Gas Chromatogram

Well 'A' 3030m; 124°C
120 0
34 °API; 0.30% S m/z 177

C29H
Pr/Ph=1.23; Pr/n-C17 =0.81 120000
Well 'A' 3030m
100 0 Demethylated
Hopanes Absent

C29Ts
800 Regular Hopanes
Present
nC6
MCH

600

C29M
C30H
nC15
nC17
Pr nC18
nC10

400
nC20

OL
C31 H
nC25
Ph

nC30

C32 H
C33 H

C35 H
200 C34 H

10000
0

0
10 20 30 40 50 60 70 min
25.00 30.00 35.00 40.00 45.00 50.00 55.00 60.00 65.00

Figure 6. Comparison of whole oil gas chromatograms and 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 re-charge 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=C29-25-nor-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-nor-demethylated hopanes; C32H=C32 hopanes;
C33H=C33 hopanes; C34H=C34 hopanes; C35H=C35 hopanes; peak labels on whole oil gas chromatograms as per Figure 5.)
14 L.M. WENGER, C.L. DAVIS, AND G.H. ISAKSEN SPE 71450

-24
sample 1

-25 Field C sample 3

sample 5
-26
sample 10
δ13C (‰ vs. PDB)

-27 Field B sample 13

sample 17
-28

-29

Field A
-30

-31
Ethane Propane n -Butane i -Butane
Figure 7: Average wet gas isotope compositions for select North Sea fields. Stable carbon
isotopic values plotted against the wet-gas components.

2
Well 1-4
18 Well 5-8
1.5
n
atio Well 9-12
d
1 gra
e Well 13-16
od
δ13C propaneδ-13C n-butane

Bi
ng 17 Well 17-18
0.5 asi
e
cr
In 6
5
0
1 12 8
14 7
9 15 16
-0.5 3 13
10
4 11
-1 2

-1.5
-29 -28 -27 -26 -25 -24
δ13C propane (‰ vs. PDB)
Figure 8. Biodegradation of wet gases in select North Sea Fields. The difference in isotopic values between propane
and n-butane is plotted against the stable carbon isotopic value of propane to show the increase in biodegradation of
wet gases towards the upper right in the plot. Sample labels refer to sample numbers in Table 1.