SOURCE OIL CORRELATION BY USING BIOMARKER METHOD

( GAS CHROMATOGRAPH MASS SPECTROMETRY )

Vida Irine Rossa1) Bela Akene2)
Geological Engineering UPN Veteran Yogyakarta
1)2)

Jl. SWK 104 (Lingkar Utara), Condongcatur, Kec. Sleman, Daerah Istimewa Yogyakarta 55283,
Indonesia
email: irinevida@yahoo.com1) , belaakene@rocketmail.com 2)

Abstract

A group compounds and classes that we find in bitumens and crude oils are called
biological markers, an acronym for biomarker. Biomarker can be used to infer characteristics of
the source rock that generated the oil with or without examining the source rock itself. When the
samples of source rock are not available, biomarker can determine the type of material organic
through oil sample. The organic materials type can be determined by analyzing data that shows
in GC-MS (Gas Chromatograph Mass Spectrometry). GC-MS shows the relative abundance
according to C element content, which are shown by various type of biomarker compounds
(steranes, triterpanes, and bicyclic). In interpreting, sterane can be used to discover depositional
environment and biological precursor, triterpane can be used to discover depositional environment,
biological precursor, and also maturity, while bicyclic can be used to discover biological precursor.
Specifically, biomarker can reveal the type of biological precursors, depositional environment,
diagenetic environment and circumstances, and thermal maturity level of the source rock in which
shows the correlation between oil and its source rock candidate. Beside, isotope parameters are
(present in the ratio of 12C and 13C stable carbon isotopes) also used as supporting data to
strengthen the interpretation.
Interpretation using biomarker data in the form of case study is done by examining two
rock samples (B1 and B2) and oil seepage (A) which is analyzed by GC-MS. The results shows
that oil sample has a strong similarity with rock sample (B2). It can be explained by seeing the
similarity of depositional environments, biological precursors, the level of maturity as well as the
similar fingerprint of the fragmentogram which is resulted.

Keyword : Biomarker, Correlation, GC-MS, Biological precursor, Isotope

INTRODUCTION source rock (Li et al., 2003, vide

Biomarkers are consisting of complex
organic compound which the compound
(composed of hydrocarbon, hydrogen and
other elements) itself derives from formerly
living organism. They useful for chemical
fingerprinting, even they could reveal a lot
more information about their origins than
other compound. They may provide
information on the organic matter in the
Sosrowidjojo, 2011). Thats why biomarkers
can be used to infer the depositional
environment, thermal maturity, and in some
cases can even be used to place age
constraints on the source rock (Peter and
Moldowan, 1993). Biomarkers actually are
the next step after we done eliminating the
nonsource rocks (using TOC, Rock-Eval
pyrolysis analysis). The oils and source

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 rocks then would be further analyzed using Those main compounds have their own
GC (Gas Chromatography) and GC-MS function in defining maturity level,
(Gas Chromatography Mass depositional environment, biological
Spectrometry) which is already the part of precursors, and type of organic material
biomarker, and the last using the more host. To support the interpretation below,
powerful isotope parameters to strengthen we include isotope correlation as an
the GC-MS results. addition to strengthen the interpretation
between source rock candidate and oil
GC-MS is a really good method, even one sample.
of the best. It actually uses high molecular
biomarker such as bicyclics, steranes and
triterpanes. As a detector, the combination DISCUSSION
of a gas chromatograph with a mass
spectrometer provides the instrumentation Gas Chromatograph (GC) Biomarker
to perform resolution and detection of Data
these molecules. By using the GC-MS, we
The principal concept in Gas
would be able to correlate the source rock
Chromatograph is designed to analyzed
and the oil. We would actually know
saturated hydracarbon fractions in rock
whether they are good correlate, or poor
samples and oil sample. The identification
correlate.
of the compound represented by the
various peaks are carried out by
comparison of retention time (time
METHODOLOGY required for components to emerge from
Biomarker analysis is generally using a the column) (Waples, 1985). Gas
tool called gas chromatograph mass chromatograph recorded the individual
spectrometry. The tools must be calibrated peaks of saturated hydrocarbon fractions
before be used. This intend to the result (methane (C1), ethane (C2), propane C3),
(fragmentogram) which shown in recoder and heavier hydrocarbons (C5+). GC
is compatible with specified standard. analyses is done before Mass Spectrometry
(MS) be measured.
GC-MS Gas Chromatograph Mass
. Spectrometry (GC-MS) is designed to
characterize and identify chemical
compounds by breaking them up into
electrically charged fragments (ions)
Waples 1985). This tool can identifiy
chemical compounds by reading its ratio of
mass to charge for an ion in mass
spectrometer (m/z). (Waples, 1985).
Triterpanes (m/z 191) , steranes (m/z 217),
and bicyclic (m/z 123) are the examples of
main compunds that is used in this study.

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 Figure 1. C5+ Whole Oil Gas Chromatography
Gas Chromatography (Fig.1) shows
distributions of n-alkanes/n-parrafins
(saturated hydrocarbon). The whole oil gas
chromatogram above represents full series of
normal alkanes (n-alkanes) in the range of n-
C7 n-C35. Chromatogram fingerprint
characterized moderately high waxy alkane
distributions (ranging from n-C11 to n-C35.
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Pristane and phytane can be recognized by
their double peaks on C17 and C18
respectively. Pristane/phytane have a low
ratio (1.64) and combined with a high
concentration of waxy alkanes (n-C22+)
indicates the organic material derived from
mixed source rock facies containing algal and
terrestrialy-organic matter.
Figure 2. C10+ Saturated Hydrocarbon Chromatogram

Figure 3. C10+ Saturated Hydrocarbon Chromatogram

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Pristane/Phytane Ratios (Pr/Ph)
Pristane/Phytane ratios are useful for
correlation parameters because they are
believed to be sensitive to diagenetic
environment (Illich, 1983 vide Waples
1985). Very high pristane/phytane ratios
indicates the depositional environment
associated with terrestrialy influenced
sediments (Waples, 1985). Pr/Ph ratios can
also be used in determining type of organic
material. Figure 4 below shows Pr/Ph ratios
as parameter in interpreting diagenetic
environment and organic materials type.

Table 1. Phytane/Pristane Ratio of Oil Seepage (A) and Rock Samples (B1&B2)

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 Figure 4. Pristane/nC17 versus Phytane /nC18 Diagram (After Connan and Cassou, 1980, vide Cox et al., 1986)

According to GC fingerprints the rock sample
B1 and B2 and oil sample A shows a
resemblance in bimodal n-parrafin
distribution (both odd and even number of n-
parrafins) which are skewed in range n-C20 to
n-C35 (fig. 1 and 3). This distinction is usually
associated with terrestrial higher plant waxes.
In contrast to the rock sample B2 (fig. 2), the
chromatogram exhibits a predominance of
odd-numbered n-parrafins below n-C20
represent lacustrine sediment-derived source
facies.

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GC-MS Biomarker Data
1. Triterpane (m/z 191)
Table 2. Triterpane Data

Figure 5. GC-MS of Triterpane (m/z 191) of Oil Seepage (A)

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Figure 6. GC-MS of Triterpane (m/z 191) of Rock Sample (B1)

Figure 7. GC-MS of Triterpane (m/z 191) of Rock Sample (B2)

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a) Source Facies
From Figure 5, 6 and 7 we could see
that 17(H)-hopanes present in oil
sample and in rock extracts sample,
where the C30(H)-hopane (labelled
6 in the fragmentogram) and the
C29(H)-hopane (labelled 4 in
fragmentogram) are more dominant
than others 17(H)-hopanes.
Bicadinanes (C30, Cyclic Alkane
labelled R in fragmentogram) presents
significantly in all samples as
characteristic of resin input and are
frequent constituents of higher plant
sourced oil/rock extracts throughout
Southeast Asia (Cox et al., 1986).
Gammacerane (labelled GM in
fragmentogram) presents relative
moderate in rock extracts samples and
relative low in oil sample. Its
compound peak may signify
hypersaline water during deposition of
the source rock (Peter and Moldowan,
1993), or its commonly associated
with anoxicity. The 18(H)-Oleanane
(labelled OL in the fragmentogram)
also presents in moderate abundance
from the oil sample and the rock
extracts samples. The presence of
oleanana could be a higher plant
angiosperm marker, and indicates a
Tertiary to Cretaceous age (Peter and
Moldowan, 1993). The low abundant
of Gammacerane and Oleanane in the
oil and the rock extract imply a mixed
terrestrial/lacustrine origin. The
regular stair-step progression of C31
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to C35 homohopanes (labelled 8 to 18
in the fragmentogram) is consistent
with suboxic bottom waters during
deposition (Peter and Moldowan,
1993).
b) Maturity
The Moretanes are highly specific for
immatures to early oil generation. The
moretanes are thermally less stable
than hopanes, and abundance of the
C29 and C30 moretanes decrease
relatively to the corresponding
hopanes with thermal maturity (Peter
and Moldowan, 1993). From Table 2
shows that the ratio of moretanes to
hopanes for the C29 and C30
hopanes are low for the rock extracts
(0.14 and 0.12; 0.06 and 0.18), and are
also low for the oil (0.10 and 0.15).
They suggest that the oil sample and
the rock extracts are mature.
The ratio of two C27 triterpanes (Tm
and Ts) is a good measure of maturity.
Tm/Ts ratios below 1.0 indicates
maturity (Peter and Moldowan, 1993).
From Table 2 we could see that the
value of the Tm/Ts ratios of the oil
sample (0.43) represents a mature oil.
While the value of the Tm/Ts ratios of
both rock samples represent difference
meaning. The value of sample B2
(0.81) represents a mature sample,
whereas the value of sample B1 (1.55)
represents an immature sample.
Steranes (m/z 217)
Table 3. Sterane Data

Figure 8. GC-MS of Sterane (m/z 217) of Oil Seepage (A)

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Figure 9. GC-MS of Sterane (m/z 217) of Rock Sample (B1)

Figure 10. GC-MS of Sterane (m/z 217) of Rock Sample (B2)

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Figure 11. Sterane Composition and Source Rock Depositional Environment (Huang & Meinshein, 1979)

a) Depositional Environment depositional environment. Both rock

The low-moderate molecular weight
steranes (C21 and C22 pregnane and
homopregnanes) present in
significant amounts. These
compounds shows the rock samples
associated with hypersaline
environment (ten Haven et al., 1986,
vide Peter & Moldowan 1993).
Moderate-high contents of rearranged
steranes (diasteranes) and regular
steranes ratios indicate the oil sample
contain moderate clay content in the
source sediment.
Terniary diagram above showing the
relative abundances of C27, C28, and
C29 often be used to determine the
samples (B1 and B2) and oil sample
(A) represent estuarine/shallow
marine depositional environment
based on C27, C28, and C29 values.
b) Biological Precursors
According to the regular
sterane distribution from the oil
sample shows normal steranes with
C29(R) has the highest abundance
(43.05%) compared with C27(R)
steranes (32.02%) and C28(R)
steranes (24.92%). These implies a
significant input of higher plant
material to the pregnitor source rock
(fig. 8-10). Both rock samples (B1 and
B2) shows the highest C29(R)

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 steranes (37.02 and 44.98) with high determined as significant
hopane/sterane ratios (16.28 and contribution of organic material from
19.16). Hopane/sterane ratio in oil plankton and / or benthic algae-
samples has 30.39 ratio, can be derived from source rock facies.

Bicyclic (m/z 123)

Table 4. Bicyclic Data

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Figure 12. GC-MS of Bicyclic (m/z 123) of Oil Seepage (A)

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 Figure 13. GC-MS of Bicyclic (m/z 123) of Rock Sample (B1)

Figure 14. GC-MS of Bicyclic (m/z 123) of Rock Sample (B2)

a) Biological Precursor
Based on the 123 m/z fragmentogram for the
oil sample dominated by homodrimane and
drimane (labelled by 15D and 16D). The
presence of these compounds indicated the
presence of higher plant input.
Rock sample contains homodrimane
(labelled 16D) and drimane (labelled 15D)
present significant amount. This indicates to
bacterial reworking, but also the presence of
drimane of homodirimane attributed to some
higher plant input (Philip, 1985)

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Isotope Data
Table 5. Carbon Isotope Data

Figure 15. Plot of Carbon Isotope Data (After Sofer, 1984)

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 Figure 16. Stable Carbon Isotope Curve (Sofer, 1984)
The ratio of C12 and C13 stable carbon
isotope in rock and oil samples could be used
as a tool in doing source-oil correlation. The
ratio of C12 and C13 is determined by
injecting saturated hydrocarbon sample into
isotope-ratio-mass spectrometer.
Sofer (1984) has used carbon-isotope
measurements on two fractions (saturates and
aromatics) of a crude oil to classify it as high
and low wax (Waples, 1985). From Table 5
above, stable isotope carbon analysis was
done on the aromatic and saturated fractions
from the rock samples and the oil sample.
The isotope values of oil sample (saturate -
35.70%o and aromatic -33.80%o) are
showing that the oil sample is derived from
terrestrial organic matter with possible minor
algal input. While the isotope values of both
rock samples (saturate -25.80%o and -
37.00%o, and aromatic -32.70%o and -
35.10%o) are showing that they are also
derived from terrestrial organic matter with
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minor algal input. Cv (Canonical values)
obtained from comparing the carbon isotope
values for saturate and aromatic fractions are
variable (Cv = -2.53 d13CSat + 2.22 d13CAro
11.65 (Sofer, 1984 vide Waples 1985)). Cv
values > 0.47 indicates terrestrially-derived
oils and Cv values < 0.47 indicates marine or
non-marine algal-derived oils. From Table 5,
the Cv values shows that the oil sample is
terrestrially-derived oil.
Based on Figure 15 and Figure 16, we could
see that the oil sample and the B2 rock
sample are good correlate, while the oil
sample and the B1 rock sample are poor
correlate.
Conclusion
Source oil correlation using biomarker
method is done by reading and analyzing the
fragmentogram which is generated by GC-
MS. Triterpane, sterane and bicyclic
compounds are commonly used as parameter homodrimane and drimane
in doing those correlation. compounds
The fragmentogram of triterpane Determining whether the source rock and the
compound is used to discover such as, oil is good correlate or poor correlate, is
i) Depositional environment and based on similar depositional environments,
biological precursor, by seeing biological precursors, the level of maturity as
gammacerana, oleanana, well as the similar fingerprint of the
bicadinanes and C31 to C35 fragmentogram which is resulted.
homohopanes compounds.
Based on the case study examples which is
ii) Maturity, by seeing moretanes
already explained, the GC and biomarker
and C27 triterpanes (Tm and Ts)
show that the oil sample is derived from a
compounds.
source rock facies containing terrestrial
The fragmentogram of sterane
organic matter with minor algal input. Based
compound is used to discover
on GC-MS and stable carbon isotope data,
depositional environment and
the oil shows a strong similarity with the B2
biological precursor by seeing the
rock sample.
value of C27 to C29 compounds, the
ratio of hopane and sterane, and
diasterane compound.
The fragmentogram of bicyclic
compound is used to discover
biological precursor by seeing

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REFERENCES
Waples, D. (1985). Geochemistry in
Petroleum Exploration, International Human
Resources Development Corporation,
Boston.
Peters, K.E. and Moldowan, J.M. (1993). The
Biomarker Guide: Interpreting Molecular
Fossils in Petroleum and Ancient Sediments,
Prentice hall, Englewood cliffs, NJ.
Sosrowidjojo IB (2011). Geographic
Location of Crude Oils based on Biomarker
Compositions of the Sunda-Asri Basins,
Indonesia. International Journal of the
Physical Sciences Vol. 6(31), pp. 7291
7301.
McCarthy, K., Niemann,M., Palmowski, D.,
Petters, K., Stankiewicz, A., (2011) Basic
Petroleum Geochemistry for Source Rock
Evaluation, p.11.
19
Sofer Z. (1984) Stable Isotope Compositions
of Crude Oils: Application to Source
Depositional Environments and Petroleum
Alteration. Bull. Am. Assoc. Pet. Geol.
Huang, W. Y., Meinschein, W. G., 1979.
Sterols as Ecological Indicators. Geochimia
et Cosmochimica Acta.
Philip, R. P., 1985. Biological Markers in
Fossil Fuel Production. Mass Spectrometry
Reviews.
Cox H. C., de Leeuw J. W., Schenck P. A.,
van Koningsveld H., Jansen J. C., van de
Graaf B., van Geerestein V. J., Kanters J. A.,
Kruk C. and Jans A. W. H. (1986)
Bicadinane, a C30 Pentacyclic Isoprenoid
Hydrocarbon Found in Crude Oil. Nature.