Source correlation between biodegraded oil seeps and a commercial crude oil from

the Punjab Basin, Pakistan

Tahira Fazeelat , Muhammad Asif, Muhammad Irfan Jalees, Abdus Saleem, Arif Nazir, Hina Saleem,
Shagufta Nasir, Shahid Nadeem
Chemistry Department, University of Engineering & Technology, Lahore-54890 Pakistan
a b s t r a c t a r t i c l e i n f o
Article history:
Received 30 June 2008
Accepted 10 January 2011
Available online 26 January 2011
Keywords:
GCMS
biodegraded oil seep
asphaltenes
hydrous pyrolysis
biomarkers
correlation
The biomarker composition of biodegraded petroleum in an oil seep was determined using GC and GCMS
techniques. The results show that many important biomarker compounds are eliminated or highly altered by
biodegradation. In order to establish a correlation between the seep sample and a non-biodegraded crude oil
sample from the Dhurnal eld, asphaltenes were isolated from the seep and subjected to hydrous pyrolysis.
The biomarker composition of the pyrolysate and the Dhurnal oil is similar, suggesting that they are generated
by similar source rocks.
2011 Elsevier B.V. All rights reserved.
1. Introduction and geology of samples
The study area encompasses the Potwar Basin (also called Potwar
Plateau) and the Salt Range (Fig. 1). The Potwar Plateau is located in
the western foothills of the Himalayas in northern Pakistan. It is an
active exploration area because of its substantial reservoir potential,
and it contains many commercial oil elds including Dhurnal (the
largest oil eld discovered in Pakistan) which is produced from the
Eocene Sakesar Formation (Jaswal et al., 1997). The Salt Range forms
the southern boundary of the Potwar Plateau. The seep oil used in this
study was obtained as surface bitumen from the Salgi area of the Salt
Range. The oldest formation penetrated in the Potwar Basin is Salt
Range Formation of Infra-Cambrian age, which outcrops in the locality
of seep. The major source rocks in the basin occur in Cambrian,
Permian, Paleocene and Eocene sediments (Shah et al., 1977; Khan
et al., 1986; Wandrey et al., 2004). The generalized stratigraphy of the
Potwar Basin is shown in Fig. 2.
The geology of the Potwar Basin is very complex. This portion of
the Indian plate was deformed during collision with the Eurasian plate
and overthrust of the Himalaya Mountains on the N and NW. The
collision began in the Late Eocene and resulted in a 2000 km
convergence (Law et al., 1998). Moreover, extensive tectonic activity
caused intense deformation of the rocks; formations of signicantly
different ages (e.g. Precambrian and Tertiary) are juxtaposed. As a
result, correlating oils and source rocks (particularly for biodegraded
oils) is very difcult.
Both light and heavy crude oils have been discovered in the Potwar
Basin. In most petroliferous basins, shallowheavy oil pools commonly
are genetically related to deeper pools of lighter oil: i.e., the heavy oil
originated during biodegradation of originally lighter oil. However,
the absence of compositional data makes it difcult to determine the
origin of the biodegraded petroleumat the Salgi seep (which previous
studies show is depleted in n-alkanes, isoprenoids, and most
steranes). The more resistant compound classes (e.g., 17(H)-
hopanes; 25-norhopanes; 8,14-secohopanes; and cheilanthanes)
have survived and occur in higher relative concentration. These
ndings indicate that the Salgi seeps are severely biodegraded
(Fazeelat et al., 1994).
Pyrolysis of asphaltenes previously has been used to release
biomarkers for oil-source rock correlation purposes (Bhar et al.,
1984; Philp and Gilbert, 1985; Cassani and Eglinton, 1986). The
pyrolysate, despite some structural differences, carries information
about the source rock that generated it (Bhar and Pelet, 1985; Solli
and Leplat, 1986). Because asphaltenes are formed as intermediate
products during hydrocarbon generation (Rubinstein et al., 1979;
Tissot and Welte, 1984; Pelet et al., 1986) and because biodegradation
is a secondary process, they carry important geochemical information
about the origin of biodegraded oil.
In this study hydrous pyrolysis of asphaltenes isolated from a Salgi
seep was performed to release hydrocarbons that presumably were
present in the oil prior to biodegradation. The branched and cyclic
saturate fraction of the pyrolysate is examined for biomarkers. The
Journal of Petroleum Science and Engineering 77 (2011) 19
Corresponding author. Tel.: +92 42 36821304; fax: +92 42 6822566.
E-mail address: fazeelat.tahira@gmail.com (T. Fazeelat).
0920-4105/$ see front matter 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.petrol.2011.01.003
Contents lists available at ScienceDirect
Journal of Petroleum Science and Engineering
j our nal homepage: www. el sevi er. com/ l ocat e/ pet r ol
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2 T. Fazeelat et al. / Journal of Petroleum Science and Engineering 77 (2011) 19
biomarker ngerprints of the pyrolysate and a non-biodegraded crude
oil are compared to establish a source relationship between them. The
study helps to understand the origin of seeps in the Salgi area of the
Salt Range in Pakistan.
2. Experimental
2.1. Sample preparation
The samples were separated into saturate, aromatic, and NSO
fractions by column chromatography using silicic acid. The saturate
fraction (10 mg) was treated with ZSM-5 (1 g) to separate branched
and cyclic compounds. The detailed procedures are described in
Fazeelat et al. (1994). The residual mono-aromatics were removed
from the branched and cyclic fractions by TLC using a 0.5 mm thick
layer of alumina as the adsorbent and n-hexane as the solvent.
2.2. Isolation of asphaltenes
Asphaltenes were precipitated by mixing seep oil with 50 times
excess of n-hexane. The mixture was left overnight at room
temperature. The precipitated asphaltenes were recovered by
ltration and washed several times with n-hexane.
2.3. Hydrous pyrolysis of asphaltenes
Hydrous pyrolysis was performed according to the method of
Winters et al. (1983).
2.4. Capillary gas chromatography (GC)
Analysis of the saturate fraction was carried out using a Hewlett-
Packard (HP) 5890 gas chromatograph, with a 50 m0.2 mm i.d.
fused silica capillary column coated with crosslinked methyl silicone
AGE/EPOCH
LITHOLOGY &
GEOCHEMICAL DESCRIPTION
FORMATION
NAME & POTENTIAL
Pliocene Siwalik
NEOGENE
Miocene Kamlial
Murree#
Oligocene unconformity
unconformity
unconformity
Eocene Chorgali#
Sakesar#
Nammal&Panoba#
PALEOGENE
Fluvial sandstones and conglo-
merates.
Fluvial sandstones & clays.
Fluvial sandstones and siltstone
This is the youngest producing
reservoir in the basin.
Marine shales and interbedded
limestones.
Marine limestones and shales.
Eight oil/gas fields produce
from this formation
Shallow marine-lagoonal shales
and interbedded limestones.
Shallow marine to deltaic shales
& subordinate carbonate,
Type II & III kerogen
Paleocene Patala*#
Lockhart*#
Hangu*#
Shales & carbonates .. anoxic
environment
Mesozoic & late Permian
PERMIAN
Early
Permian
Amb
Sardhai
Warcha
Dandot
Tobra#
Carboniferous to Ordovician
Shelf carbonates
Mainly fine-grained sandstones
with occasional shales.
Coarse-grained argillaceous sand-
stones and occasional shales.
Alluvial/glacial coarse grained
sandstones and shales
Glacial tillites, siltstones & shales
Cambrian
Baghanwala
CAMBRIAN
TO
PRE-
CAMBRIAN
Infra
Cambrian
Sandy carbonates & nearshore
sandstones, marine environment.
Jutana
Kussak#
Khewra*#
Salt Range*#
Sandstones and siltstones, marine
Marine shales and massive sand-
stones.
Upper - Mainly evaporites. It has
source potential & oil show.
Middle -Carbonates dominated.
Lower - Clastics dominanted.
#: reservoir potention; *: source rock potential; : reservoir in Dhurnal Field
Shales & carbonates .. anoxic
environment
Sandy carbonates & nearshore
sandstones, marine environment.
Fig. 2. Stratigraphy and geochemical description of sediments of the Potwar Basin.
Modied from Fazeelat et al. (2010) and Wandrey et al. (2004).
3 T. Fazeelat et al. / Journal of Petroleum Science and Engineering 77 (2011) 19
(BP-1, SGE Australia). The sample in n-hexane was injected in splitless
mode at 60 C. Detector (FID) and injector temperatures were 300 and
280 C respectively. The oven temperature was programmed from 60
to 300 C at 4 C/min. Hydrogen at a linear velocity of 28 cm/s was
used as the carrier gas.
2.5. Gas chromatographymass spectrometry (GCMS)
GCMS analysis of branched and cyclic (B/C) saturates was carried
out using a HP 5887 GC-quadrupole MS-computer data system. The
GCMS was tted with a 60 m0.25 mm i.d. WCOT fused silica
crosslinked methyl silicone column with lm thickness of 0.25 m
(DB-l, J & W scientic), and an OCI-3 on-column injector. Hydrogen
was used as the carrier gas. Typical operating conditions were: scan
range of 50 to 450 Daltons in 1.3 s cycles; EM voltage of 2400 V;
electron energy of 70 eV; and source temperature of 250 C. The
samples were analyzed in the selective ion monitoring mode. The GC
temperature program was 50274 C at 8 C/min and 274280 C at
1 C/min.
3. Results and discussion
Asphaltenes are interpreted as a kerogen moiety that exhibit
signatures of source rock that generated them. However, hydro-
carbons generated from asphaltenes under hydrous pyrolysis condi-
tions exhibit some compositional differences inuenced by maturity
and migration parameters (Orr, 1986; Bjory et al., 1988; Peters et al.,
1990). Therefore the biomarker composition of asphaltenes in a
pyrolysate can be used to correlate biodegraded crude oils with non-
biodegraded oil by excluding those parameters. The same strategy has
been adopted in this study to establish a source relationship between
the Salgi seep and a non-biodegraded crude oil sample from the
Dhurnal eld: i.e., the biomarker composition of petroleum obtained
during hydrous pyrolysis of asphaltenes isolated from the Salgi seep
was determined using GC and GCMS techniques and compared to
those of a non-biodegraded Dhurnal crude oil.
A comparison of the basic geochemical data (Table 1) and location
of the samples on a triangular diagram(Fig. 3; Tissot and Welte, 1984)
reveals a high relative percentage of C
15+
saturate compounds in
Dhurnal crude oil whereas more aromatics and polars are present in
the seep and pyrolysate. The hydrocarbon composition of crude oils is
controlled by kerogen type and maturity. For example, Type II kerogen
generates oil that is more enriched in saturates (compared to
aromatics and polar compounds) at higher maturity. These factors
account for the higher relative concentration of saturates and low
aromatics and polars in Dhurnal crude oil compared to asphaltene
pyrolysate.
The gas chromatogram of the seep demonstrates that it consists of
severely biodegraded crude oil (Fig. 4; Fazeelat et al., 1994). The
chromatograms of asphaltene pyrolysate and Dhurnal crude oil (Fig. 5)
in contrast are dominated by n-alkanes and the distribution of pristane,
phytane and other acyclic isoprenoids and maxima at n-C13 are very
similar. The Pr/Ph ratios (Table 1) for pyrolysate and Dhurnal crude oil
are consistent with the deposition of organic matter under oxic
conditions in the source rocks that generated oil. The carbon preference
index (CPI) of the n-alkanes is 1, indicating a typical mature
hydrocarbon distribution. Pristane/n-C
17
and phytane/n-C
18
ratios
show an increase in value with increasing maturity (Tissot and Welte,
1984), because of thermal degradation of n-alkanes faster than
isoprenoids. The hydrocarbons in asphaltenes are found in bound
form, hence better protected fromthe effects of thermal alteration than
released bitumen. These ratios are often affected by depositional
environment. These factors count for slightly different values of Pr/Ph,
Pr/n-C
17
and Ph/n-C
18
in Dhurnal and asphaltene pyrolysate, which is in
agreement with earlier study (e.g., Russell et al., 2004).
Biodegradation has a signicant effect on biomarker compounds.
Five different groups of saturate biomarkers (drimanes/homodrimanes,
tricyclic terpanes, hopanes, 25-norhopanes and steranes) were used to
study the Salgi seep oil, asphaltene pyrolysate and Dhurnal crude oil.
Relationships among these samples were discerned comparing their
biomarker ngerprints and using biomarker parameters. Fig. 6 shows
the distribution of drimanes and homodrimanes. Compounds were
identied using literature data (Noble et al., 1987). No signicant peak
in the chromatogram of the Salgi seep could be assigned to C
16
Table 1
Geochemical parameters based on aliphatic hydrocarbons.
No Parameters Salgi seep
oil
Salgi asp.
pyrolysate
Dhurnal
crude oil
1 Saturates: aromatics: NSO+
asp+resins (relative %)
39:32:29 36:39:25 63:19:18
2 API gravity 14 nd 38
3 Pr/Ph nd 1.8 2
4 Pr/n-C
17
nd 0.4 0.5
5 Ph/n-C
18
nd 0.2 0.3
6 CPI nd 1 1
7 Ts/Ts+Tm 0.28 0.03 0.66
8 C
30
/(+) hopanes 0.76 0.77 0.96
9 C
30
/ hopane 0.3 0.29 0.04
10 C
31
22S/(22S+22R) homohopanes 0.59 0.54 0.69
11 C
32
22S/(22S+22R) homohopanes 0.59 0.42 0.61
12 C
31
C
35
HHI 37:21:20:
12:10
43:27:20:
(6:4)
48:23:
(12:12:5)
13 C
31
C
35
homohopanes/C
30
hopane 1.4 0.8 1.5
14 C
29
hopane/C
30
hopane 0.91 0.59 0.55
15 Ts+Tm/C
30
hopane 0.83 0.68 0.62
16 C
24
TeT/C
30
hopane 0.24 0.13 0.38
17 C
24
TeT/C
25
TT 1.77 1.77 1.67
18 C
24
TeT/C
26
TT 2.44 2.53 2.38
19 C
24
TeT/C
23
TT 0.76 0.78 0.72
20 C
24
TeT/C
24
TeT+C
23
TT 0.43 0.44 0.42
21 C
26
/C
25
TT 0.7 0.5 0.7
22 C
31
R/C
30
hopane 0.21 0.15 0.22
24 C
23
/C
21
TT 1.24 1.07 1.06
25 C
2326
/C
1921
TT 1.68 0.96 0.96
26 C
19
/C
19
+C
23
TT 0.12 0.30 0.31
27 TT/hopane 0.68 0.23 1.54
28 C
27
: C
28
: C
29
steranes nd 20: 30: 50 19: 28: 53
29 C
27
/C
29
-20R steranes nd 0.5 0.6
30 C
27
/C
29
(20S+20R) diasteranes 0.72 bdl 0.86
31 C
27
(20S+20R) diasterane/sterane nd b0.05 0.39
32 C
29
/+ steranes nd 0.31 0.49
33 C
29
20S/(20S+20R) steranes nd 0.39 0.49
Data of seep oils was reproduced from Fazeelat et al. (1994) for comparison with Salgi
asphaltene pyrolysate and Dhurnal crude oil; 36: Pr/Ph, Pr/n-C
17
and Ph/n-C
18
and CPI:
(C
21
+C
23
+C
25
+C
27
)+(C
23
+C
25
+C
27
+C
29
)/2(C
22
+C
24
+C
26
+ C
28
) calculated using
n-alkanes peak area from GC-FID; 7: 18(H)-neohopane (Ts)/18(H)-neohopane (Ts)+
17(H)-22,29,30-trisnorhopane (Tm); 8: C
30
17(H), 21 (H)-hopane/C
30
17(H), 21
(H)-hopane+C
30
17 (H), 21 (H)-moretane; 9: C
30
17 (H), 21 (H)-moretane/C
30
17(H), 21 (H)-hopane; 1011: C
31
and C
32
22S 17(H), 21 (H)-homohopane/22(S+
R) 17(H), 21 (H)-homohopane; 12: C
31
-C
35
homohopane index (HHI) e.g. C
35
HHI: C
35
/
C
31
to C
35
17(H), 21 (H)-homohopanes 22(S+R) expressed as percent; 13: C
31
to C
35
17(H), 21 (H)-homohopanes 22(S+R)/C
30
17(H), 21 (H)-hopane; 14: C
29
17(H),
21 (H)-30-norhopane/C
30
17(H), 21 (H)-hopane; 15: 18(H)-neohopane (Ts)+
17(H)-22,29,30-trisnorhopane (Tm)/C
30
17(H), 21 (H)-hopane; 1626: C
19-29
TT: C
19
toC
29
tricyclic terpane; C
24
TeT: C
24
tetracyclic terpaneORC
24
17, 21-secohopane; 27: C
19
to
C
29
tricyclic terpane/C
27
to C
35
17(H), 21(H)-hopanes. Parameters 727 were calculated
using m/z 191 mass chromatogram.
28: C
27
to C
29
steranes e.g. C
27
steranes: 20(S+R) 5(H), 14(H), 17(H)-cholestanes+
20(S+R) 5(H), 14(H), 17(H)-cholestanes/C
27
to C
29
steranes 20(S+R) 5(H),
14(H), 17(H)+20(S+R) 5(H), 14(H), 17(H) expressed as percent; 29: 20R-
5(H), 14(H), 17(H)-cholestane/20R-5(H), 14(H), 17(H)-ethylcholestane; 30:
C
27
20(S+R)-5(H), 13(H), 17(H)-diastane/C
29
20(S+R)-5(H), 13(H), 17(H)-
diasterane; 31: C
27
20(S+R)-5(H), 13(H), 17(H)-diasterane/C
27
20(S+R)-5(H),
14(H), 17(H)-sterane 32: 20(S+R)-14(H), 17(H)-ethyldiacholestane/20(S+R)-
14(H), 17(H)-ethylcholestane+(20S+20R)-14(H), 17(H)-ethylcholestane; 33:
20S-5(H), 14(H), 17(H)-ethylcholestanes/20(S+R)-5(H), 14(H), 17(H)-
ethylcholestanes. Parameters 2833 were calculated using m/z 217 mass chromatogram.
nd: could not be determined because of biodegradation/very low concentration; bdl:
diasteranes belowdetection limits. Bracketed values showlowcertainty because of low
abundance of these compounds; asp: asphaltenes.
4 T. Fazeelat et al. / Journal of Petroleum Science and Engineering 77 (2011) 19
homodrimane, but small peaks corresponding to C
15
drimane are
present. Other peaks in this chromatogram are biodegradation residue.
Although, drimane and homodrimanes are interpreted to be molecular
fossils produced by higher plants (Alexander et al., 1983a), however,
these compounds have also been identied in samples of prokaryotic
origin and thought to be degradation products of bacteriohopanoids
(Volkman, 1988). Despite their origin, the relative abundance 8(H)- to
8(H)-epimers of these compounds is associatedwiththermal maturity
with 8(H)-conguration more abundant in more mature samples
(Noble et al., 1987).
These results suggest that seep and oil samples are derived from
source rocks containing signicant amounts of terrigenous organic
matter. The presence of 8(H)-epimers in pyrolysate and their
absence in the Dhurnal crude oil along with high abundance of 8(H)-
conguration in Dhurnal suggest low maturity of the pyrolysate. A
comparison of the chromatograms however show some common
features: e.g., greater relative abundance of drimanes compared to
homodrimanes suggests a common source. The presence of rear-
ranged drimanes and homodrimanes (black peaks) in the Dhurnal oil
sample and their absence in the pyrolysate can be explained if
rearranged drimanes formby clay catalyzed reactions (Williams et al.,
1986).
The C
19
to C
29
tricyclic terpanes (TT) of the cheilanthane series are
present in all three samples (Fig. 7); however their demethylated
analogs were not detected. Additionally a substantial concentration of
C
24
17, 21-secohopane (peak 24* abbreviated as C
24
TeT) is present in
the seep, pyrolysate and the Dhurnal. Aquino Neto et al. (1983)
examined tricyclic terpanes in all oil samples they studied except
those from terrigenous source. Philp and Gilbert (1986) also observed
the absence of tricyclic terpanes in Australian oils that were
predominantly derived from terrigenous source material. C
24
TeT is
an indicator of a carbonate-evaporate depositional environment
(Palacas et al., 1986; Clark and Philp, 1989).
The distribution of tri- and tetracyclic terpanes and almost similar
values of derived parameters, e.g. C
24
TeT/C
25
TT, C
24
TeT/C
26
TT, C
24
TeT/
C
23
TT, C
23
/C
21
TT (Table 1) suggest no signicant source variation. Peters
et al. (2005) used a cross plot of C
26
/C
25
TT vs. C
31
R/C
30
hopane to
distinguish between marine shale, carbonate and marl, a similar
approach has been adopted in this study. The values, 0.50.7 for C
26
/
C
25
and 0.150.22 for C
31
R/C
30
hopane suggest marine shale and
carbonateas sourcerocks lithology. Highabundanceof tricyclic terpanes
along with land plant derived drimane and homodrimanes indicates
that source rocks containing both terrestrial and algal bacterial organic
matter may have generated these crude oils in the Upper Indus Basin.
The presence of relatively high concentration of cheilanthanes, C
24
tetracyclic terpane along with drimane and homodrimanes therefore
supports both terrestrial and algal bacterial organic matter while source
rocks were marine shale and carbonate depositional settings.
Cheilanthanes are formed by cracking of kerogen at temperature
higher than hopanes (Farrimond et al., 1999) and exhibit thermal
stability more than hopanes. Therefore, high tricyclic terpanes to
hopane ratios are expected for more mature oils. Because of this factor
Dhurnal shows high TT/hopane ratio compared to Salgi and
pyrolysate. Some discrepancy in the relative abundance of C
19
and
Saturates
Aromatics
NSO+Asph
+ Resins
Seep oil
Pyrolysate
Dhurnal oil
Key
Fig. 3. Ternary diagram showing the compound class distribution samples.
Fig. 4. Capillary gas chromatograms of alkane fractions of Salgi seep oil; retention time
of n-eisosane is indicated as C
20
.
* : pristane
o : phytane
Retention time (min)
*
o
25
30
32
20 40 60
*
o
20
13
10
9
30
25
32
9
Pyrolysate
Dhurnal
F
I
D

R
e
s
p
o
n
s
e
Fig. 5. Gas chromatograms of alkane fractions from asphaltenes pyrolysate and Dhurnal
crude oil.
5 T. Fazeelat et al. / Journal of Petroleum Science and Engineering 77 (2011) 19
C
20
cheilanthanes and derived parameters were observed for Salgi.
However, based on similar values of C
19
based parameters for
pyrolysate and Dhurnal (e.g., parameters 25 and 26; Table 1) this
difference was attributed to biodegradation of these compounds in
Salgi seep oil.
Most steranes are absent in the seep oil (Fig. 8), only minor peaks
due to rearranged steranes are present (a characteristic feature of
extremely biodegraded oils) in m/z 217 chromatogram. The presence
of rearranged steranes in the Salgi seep shows that these compounds
are more resistant to biodegradation than the regular steranes (e.g.
Seifert and Moldowan, 1979; Cassani and Eglinton, 1991). The
presence of C
27
C
29
regular steranes in the asphaltene pyrolysate
and their absence in the seep reect that these compounds were
present in the seep before it was biodegraded by microbes. Dhurnal
crude oil contains both regular and rearranged steranes (diasteranes),
however rearranged steranes are in low relative amount as indicated
by diasteranes/sterane ratio of 0.39. The rearranged steranes are
below detection limits in the pyrolysate. It is well established that
rearranged steranes are produced by rearrangement of regular
steranes on acidic catalytic surfaces of clay minerals (Moldowan
et al., 1986). The presence of rearranged steranes in crude oil and their
absence in pyrolysate relates to the limited occurrence of acid
catalyzed rearrangement of regular steranes in the pyrolysate.
The prevalence of C
27
C
29
steranes was observed in the order
C
29
NC
28
NC
27
for both Dhurnal and asphaltene pyrolysate. High
abundance of C
29
sterane could be due to substantial landplant
input, which indicates an origin of oils from mixed terrestrial and
marine organic sources. The closeness of C
27
C
29
steranes distribution
and C
27
/C
29
-20R steranes ratio for Dhurnal and pyrolysate is
consistent with a common source. The maturity parameters, e.g., C
29
/+ and C
29
20S/(20S+20R) steranes, 0.49 for
Dhurnal and 0.31 and 0.39 for pyrolysate suggest high maturity for the
former, which is in agreement with the previous results from
drimanes/homodrimanes and cheilanthanes.
The homologous series of 17(H)-hopanes is dominant and
present in all the samples (Fig. 9). It encompasses carbon number
C
27
and from C
29
to C
35
. The seep sample contains an additional series
of 25 nor-17(H)-hopanes from C
28
C
32
, as shown by m/z 177
fragmentogram. The higher members of the series might be present
however in low concentration. The pyrolysate contains only hopanes
and moretanes and 25-norhopanes were not present. The absence of
25-norhopanes in pyrolysate as well as in non-biodegraded oil
(Dhurnal) is in agreement with the previous studies suggesting that
25-norhopanes are biodegradation product (Volkman et al., 1983;
Obermajer et al., 2004).
Moretanes are in high relative concentration in seep and pyrolysate
and below detection limits in the Dhurnal (Fig. 9). Moretane to
corresponding hopane ratio, e.g., C
30
moretane/hopane is 0.3 for Salgi
Fig. 6. Mass chromatograms m/z 123 showing drimanes and homodrimanes in a) Salgi
seep; b) Asphaltene pyrolysate and c) Dhurnal crude oil.
Fig. 7. Mass chromatograms m/z 191 showing the distribution of tricyclic terpanes in a)
Salgi seep; b) Asphaltene pyrolysate and c) Dhurnal crude oil. *: 17, 21-secohopane;
numbers denote carbon number.
6 T. Fazeelat et al. / Journal of Petroleum Science and Engineering 77 (2011) 19
and pyrolysate and 0.03 for Dhurnal crude oil suggesting high relative
maturity of the latter. The values of 22S/22S+22R for C
31
and C
32
-
homohopanes are 0.6 to 0.7 for Salgi and Dhurnal crude oil and 0.5 for
pyrolysatesuggest lowthermal maturity of pyrolysate (Mackenzie et al.,
1980; Seifert and Moldowan, 1980). Ts/Tm ratio also increases with
ongoing maturation. The values Ts/Ts+Tm (Table 1) along with
maturity parameters based on steranes, cheilanthanes, and drimanes/
homodrimanes suggest low maturity of asphaltene pyrolysate com-
pared to Dhurnal and probable hint expulsion of seep hydrocarbons out
of immature source rocks caused by high tectonic pressure related to
deformation (Fazeelat et al., 2010 and references therein). A substantial
concentration C
35
-homohopane is an indicator of highly reducing
marine conditions, however, C
3435
homologues of homohopanes
were found in very low concentration, suggesting oxidizing water
conditions during deposition which is supported by high Pr/Ph ratio
(Peters and Moldowan, 1991). Close values of C
29
hopane/C
30

hopane for pyrolysate and Dhurnal (0.59 and 0.55) suggest a similar
source. A signicant aspect of this study is the presence of drimanes/
homodrimane, full series of cheilanthanes, steranes andhopanes similar
toDhurnal andasphaltene pyrolysate inthe SOMof sediments of Eocene
andPaleoceneage inthearea; whichpoints tothesesequences as source
rocks for these oils (unpublished data from Fazeelat, 1994).
Substantial concentration of neohopanes is detected in crude oil
and seep, although these compounds are below detection limits in
pyrolysate; the explanation for these variations is similar to that
described for 20S and 20R and moretanes. The preferential degrada-
tion of steranes compared to hopanes suggests that seeps have been
degraded on or close to the surface (Alexander et al., 1983b).
4. Conclusions
Geochemical study of the saturate fractions from weathered oil
seeps, asphaltene pyrolysate, and Dhurnal crude oil resulted in the
following conclusions:
Similarities in the composition of drimanes, homodrimanes,
tricyclic terpanes, steranes and hopanes suggest a common source
for the crude oil and the seep sample. The asphaltene pyrolysate
represents a source of lower maturity for oil seeps than commercial
Fig. 8. Mass chromatograms m/z 217 showing the distribution of steranes in a) Salgi seep; b) Asphaltene pyrolysate and c) Dhurnal crude oil.
7 T. Fazeelat et al. / Journal of Petroleum Science and Engineering 77 (2011) 19
crude oil. The composition of the oil seep is consistent with a crude oil
that has been severely biodegraded on or close to the surface.
Acknowledgements
We thank Prof. Robert Alexander and Prof. Robert Kagi for their
suggestions on the rst draft of this manuscript. Thanks are also due to
Geoff Chidlow for GCMS analysis. Financial support provided by
AIDAB Australia is highly appreciated.
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