Organic Geochemistry 42 (2011) 12261240

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Organic Geochemistry
journal homepage: www.elsevier.com/locate/orggeochem

Petroleum geochemistry of the Potwar Basin, Pakistan: 1. Oiloil correlation

using biomarkers, d13C and dD
Muhammad Asif a,b,, Tahira Fazeelat c, Kliti Grice b
a

Department of Basic Sciences and Humanities, University of Engineering and Technology, KSK Campus, Lahore, Pakistan
WA Organic and Isotope Geochemistry Centre, The Institute for Geoscience Research, Department of Chemistry, Curtin University, GPO Box U1987, Perth, WA 6845, Australia
c
Chemistry Department, University of Engineering and Technology, GT Road, Lahore, Pakistan
b

a r t i c l e

i n f o

Article history:
Received 16 January 2011
Received in revised form 21 April 2011
Accepted 5 August 2011
Available online 16 August 2011

a b s t r a c t
Geochemical characterisation of 18 crude oils from the Potwar Basin (Upper Indus), Pakistan is carried
out in this study. Their relative thermal maturities, environment of deposition, source of organic matter
(OM) and the extent of biodegradation based on the hydrocarbon (HC) distributions are investigated. A
detailed oiloil correlation of the area is established. Gas chromatographymass spectrometry (GC
MS) analyses and bulk stable carbon and hydrogen isotopic compositions of saturated and aromatic
HC fractions reveals three compositional groups of oils. Most of the oils from the basin are typically generated from shallow marine source rocks. However, group A contains terrigenous OM deposited under
highly oxic/uvio-deltaic conditions reected by high pristane/phytane (Pr/Ph), C30 diahopane/C29Ts,
diahopane/hopane and diasterane/sterane ratios and low dibenzothiophene (DBT)/phenanthrene (P)
ratios. The abundance of C19-tricyclic and C24-tetracyclic terpanes are consistent with a predominant terrigenous OM source for group A. Saturated HC biomarker parameters from the rest of the oils show a predominant marine origin, however groups B and C are clearly separated by bulk d13C and dD and the
distributions of the saturated HC fractions supporting variations in source and environment of deposition
of their respective source rocks. Moreover, various saturated HC biomarker ratios such as steranes/
hopanes, diasteranes/steranes, C23-tricyclic/C30 hopane, C28-tricyclic/C30 hopane, total tricyclic terpanes/hopanes and C31(R + S)/C30 hopane show that two different groups are present. These biomarker
ratios show that group B oils are generated from clastic-rich source rocks deposited under more suboxic
depositional environments compared to group C oils. Group C oils show a relatively higher input of algal
mixed with terrigenous OM, supported by the abundance of extended tricyclic terpanes (up to C41+) and
steranes.
Biomarker thermal maturity parameters mostly reached to their equilibrium values indicating that the
source rocks for Potwar Basin oils must have reached the early to peak oil generation window, while aromatic HC parameters suggest up to late oil window thermal maturity. The extent of biodegradation of the
Potwar Basin oils is determined using various saturated HC parameters and variations in bulk properties
such as API gravity. Groups A and C oils are not biodegraded and show mature HC proles, while some of
the oils from group B show minor levels of biodegradation consistent with high Pr/n-C17, Ph/n-C18 and
low API gravities.
2011 Elsevier Ltd. All rights reserved.

1. Introduction
The Potwar Basin is the main source of petroleum hydrocarbons
in northern Pakistan. A number of small and medium sized oil and
gas elds have been discovered from both terrigenous and marine
source rocks in the basin. These oil elds are in Precambrian to Tertiary aged reservoir units. The Paleocene Patala Formation type II
and III kerogens have been assumed to be the primary source of
Corresponding author at: Department of Basic Sciences and Humanities,
University of Engineering and Technology, KSK Campus, Lahore, Pakistan.
Tel.: +92 3218850163.
E-mail address: asifchaudhrry@gmail.com (M. Asif).
0146-6380/$ - see front matter 2011 Elsevier Ltd. All rights reserved.
doi:10.1016/j.orggeochem.2011.08.003

hydrocarbons in the area, but other potential source rocks may

have also contributed to different parts of the petroleum systems
within the basin (Wandrey et al., 2004; Fazeelat et al., 2010). The
oldest potential source rocks are from the Precambrian Salt Range
Formation with a mixture of clastic, carbonate and evaporite dominant sections. Similarly, Permian Sardhai and Chhidru formations
have signicantly higher total organic carbon (TOC) contents and
are possible source rocks (Quadri and Quadri, 1997). In the past,
a limited number of studies have been carried out mainly based
on RockEval pyrolysis data (Ahmed and Alam, 1990; Fazeelat
et al., 2010) and studies of the saturated hydrocarbon (HC) distributions (Fazeelat, 1994; Ahmed and Alam, 2007) from the area. Recently, a biodegraded oil seep and a crude oil from the Potwar

Table 1
Geological information, n-alkanes, isoprenoid ratios and bulk isotope data.
Pr/Pha

Pr/n-C17b

Ph/n-C18c

CPId

OEPe

Cambrian
Eocene
Cambrian
Cambrian
Cambrian
Cambrian
Cambrian
Cambrian
Cambrian
Cambrian
Eocene
Eocene

48.0
36.2
33.0
19.3
22.7
26.6
25.0
23.2
25.0
18.4
16.0
16.1

3.2
1.5
2.0
1.2
1.3
1.3
1.5
1.3
1.4
1.2
1.0
1.0

0.4
1.0
1.0
1.3
1.3
1.4
1.2
1.1
0.8
1.3
1.3
1.3

0.2
0.7
0.5
0.9
0.9
0.9
0.8
0.8
0.6
0.9
1.0
1.0

1.0
0.9
1.0
1.0
1.0
1.0
1.0
1.0
1.0
0.9
0.9
0.9

1.0
1.0
1.0
1.0
1.0
1.0
0.9
0.9
1.0
0.9
0.9
0.8

Eocene

16.0

1.2

1.1

0.8

1.0

Eocene

40.0

1.5

0.8

0.5

Eocene

45.0

1.4

0.9

Eocene

46.0

1.4

Jurassic
Jurassic

38.4
41.1

1.6
1.6

Depth
(m)

Reservoir
Formation

Age

P1
P2
P3
P4
P5
P6
P7
P8
P9
P10
P11
P12

2680
2187
2063
3640
3645
2773
2694
3063
3318
2687
2179
2103

P13

3612

P14

P15

4096

P16

4174

P17
P18

4485
4450

Khewra
Chorgali
Jutana
Jutana
Jutana
Khewra
Khewra
Khewra/Tobra
Khewra/Tobra
Khewra
Chorgali
Chorgali/
Sakaser
Chorgali/
Sakaser
Chorgali/
Sakaser
Chorgali/
Sakaser
Chorgali/
Sakaser
Datta
Datta

: not determined.
a
Pr/Ph, pristane/phytane.
b
Pr/n-C17, pristane/n-C17 alkanes.
c
Ph/n-C18, phytane/n-C18 alkanes.
d
CPI, carbon preference index.
e
OEP, odd even predominance.
f
d13C () with respect to VPDB reported with in standard deviation of 0.2.
g
dD () with respect of VSMOW with in standard deviation of 3.
h
d13Caver:age (d13Csats+ d13Caros)/2; dDaver: (dDsats + dDaros)/2.
i
DBT/P, dibenzothiophene/phenanthrene.
j
BL, biodegradation level (Wenger et al., 2001).

d13Csatsf
()

d13Caros
()

26.4
23.1

24.5
20.8

dDsats
()

dDaros
()

BLj

A
B
B
B
B
B
B
B
B
B
B
B

0
0
0
2
2
3
2
1
1
3
3
3

126
132
136
130

132
141
136
134

22.5
22.2
21.7
21.6

129
137
136
132

0.9

22.3

21.0

145

129

21.8

137

0.31

1.0

1.0

23.1

20.5

145

139

23.5

142

0.27

0.7

1.0

1.0

25.0

22.0

148

139

23.6

143

0.26

0.9

0.7

1.0

1.0

25.1

22.1

0.26

0.6
0.8

0.4
0.6

1.0
1.0

1.0
1.0

26.1
26.1

21.5
21.4

0.25
0.16

C
C

0
0

21.0

23.0

132

21.1

125

149

21.7

135

122

128

22.0

129

114
142

Group

22.2
21.9
21.1
21.1

22.4

25.4
21.9

DBT/Pi

22.9
22.6
23.0
22.3

111
130

dDaver
()

0.16
0.17
0.22
0.52
0.45
0.43
0.37
0.39
0.33
0.66
0.84
0.93

117
155

d13Caverh
()

142

23.8

23.7
25.4

126

M. Asif et al. / Organic Geochemistry 42 (2011) 12261240

API
gravity

Sample
name

1227

1228

M. Asif et al. / Organic Geochemistry 42 (2011) 12261240

Basin have been correlated based on their biomarker distributions

(Fazeelat et al., 2011). Organic geochemical data, particularly biomarkers from potential source rocks in the Potwar Basin, have
never been reported, nor has a detailed oiloil correlation ever
been undertaken.
The application of biomarkers and stable isotope analyses has
been recognised as a powerful tool in exploration petroleum geochemistry (e.g. Dawson et al., 2005, 2007; Asif et al., 2009; Maslen
et al., 2011). Biomarkers (based on structural grounds) in bituminous organic matter (OM) can provide valuable information on:
(i) the source of their natural product precursors (i.e. Eukaryotes,
Prokaryotes and Archaea), (ii) paleoenvironmental depositional
conditions (marine, lacustrine, hypersaline or uvio-deltaic), (iii)
lithology of potential petroleum source rocks (carbonate versus
shale), (iv) relative thermal maturity of potential source rocks
and (v) extent of biodegradation of petroleum HCs. However, many
of the above factors are often interrelated and have been considered collectively for correlation studies (e.g. Murray and Boreham,
1992). Variation in biomarker abundance has been used successfully for oil correlation between source rocks and/or other oils
(e.g. Jiang and Li, 2002; Obermajer et al., 2002; Pasadakis et al.,
2004; Zhang and Huang, 2005). Bulk isotope analysis (carbon and
hydrogen) of crude oils, bitumens and kerogen is also useful. The
bulk isotope composition of saturated and aromatic fractions of
crude oils has been applied to determine the source of OM (terrigenous versus marine) for many oils worldwide (Sofer, 1984; Chung
et al., 1992; Andrusevich et al., 1998). However, a recent study has
showed limitations of bulk d13C data and reported a d13C values of
individual aromatic HCs to determine the source OM of Western
Australian crude oils (Maslen et al., 2011).
In the current study, organic geochemical parameters based on
biomarker distributions and stable carbon and hydrogen isotopes
of saturated and aromatic HC fractions have been used to investigate the source and thermal maturity of OM, depositional paleoenvironment, lithology and extent of biodegradation of HCs from the
Potwar Basin (Upper Indus Basin, Pakistan). Heavy to light crude
oils have been identied in a small region of the Potwar Basin.
The causes for these differences in physical properties are presently unknown. The possible reasons for these different crude oil

types are related to the complex geology of the area and/or differences in the source of OM and its environment of deposition.

2. Experimental
2.1. Samples and geological setting
Eighteen crude oils were selected from the Potwar Basin
(Table 1). The oils cover half of the Potwar plateau, which is the
largest HC producing zone in northern Pakistan (Upper Indus Basin). The source of these crude oils has not been fully correlated
with any specic source rocks of the Upper Indus Basin. A few
studies using organic geochemical properties from cuttings, outcrops and core samples of different geological formations were
undertaken and correlated partially with Potwar crude oils (Ahmed
and Alam, 1990, 2007). Both heavy and light oils have been discovered in the basin (API gravity, Table 1). The heavy oils are genetically related to light oils, and bear a close spatial relationship
(Asif et al., 2008). The locations of crude oils used in this study
are shown in Fig. 1 and marked on a stratigraphic chart in corresponding geological formations in Fig. 2.
The geological structure of the Potwar Basin is very complex
due to the result of the Tertiary Himalayan collision between the
Eurasian and Indian plates (Farah et al., 1984). This intense tectonic
activity has signicantly over thrust the Himalayan in the north
and northwest and a series of faulted and unfaulted anticlines
developed as the result of the multiple detachments of deep surfaces from Cambrian. The Potwar Basin contains mostly carbonate
reservoir rocks of Precambrian to Tertiary ages. The basin inll
started with thick Precambrian evaporite deposits overlain by relatively thin Cambrian to Eocene age deposits followed by thick
MiocenePliocene deposits. The Precambrian salt deposits provided an easy detachment of Eocene-to-Cambrian (EC) sequences
as a result of intense tectonic activity during Himalayan Orogeny
during the Pliocene to middle Pleistocene. This EC sequence in
the Potwar Basin affected by compressional forces has generated
a large number of folds and faults in the area (Aamir and Siddiqui,
2006). These folds and faults have formed many small reservoirs

Fig. 1. Map of the Potwar Basin indicating locations of oils used in this study (Wandrey et al., 2004; modied from USGS Bulletin 2208B and references therein).

M. Asif et al. / Organic Geochemistry 42 (2011) 12261240

1229

Fig. 2. Stratigraphy of the Potwar Basin. The reservoir formations corresponding to oil samples used in this study are also shown in the right column (Wandrey et al., 2004;
modied from USGS Bulletin 2208B and references therein).

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M. Asif et al. / Organic Geochemistry 42 (2011) 12261240

and thus crude oils discovered in the Potwar Basin have shown to
be derived from a range of geological formations (Fig. 2).
The generalised stratigraphy of the Potwar Basin is shown in
Fig. 2. The oldest producing reservoir is a Precambrian Salt Range
formation. It consists of thick carbonates overlain by evaporites.
Marine shales and massive sandstones have been reported in the
Khewra Formation of the Lower Cambrian Jhelum Group. The Khewra Formation has yielded the P1 and P6P10 oils analysed in the
present study. The overlying Jutana Formation consists primarily of
sandy carbonates and nearshore sandstones and reservoirs that
have led to the P3P5 oils. The Permian Tobra Formation consists
of glacial tillites, siltstone and shales, and samples P8 and P9 are
derived from the Tobra and the Khewra formations. The Jurassic
strata include the Datta and Shinawari formations, which are nearshore consisting of siliciclastics that contain some non-marine
sandstone intervals (Khan et al., 1986). The Datta Formation has
led to the production of the P17 and P18 oils. Shallow marine carbonate strata of the Eocene Chorgali and Sakaser formations form
an important HC producing horizon in the Potwar Basin. Chorgali
and Sakaser formations consist of medium-bedded limestones
and ne crystalline dolomites. Both formations are oil and gas producing reservoirs and the P2 and P11P16 oils are derived from the
Chorgali and Sakesar formations.
2.2. Sample preparation, liquid chromatography and 5A molecular
sieving
The sample preparation and liquid chromatography procedures
used were similar to those described in Asif et al. (2009). Briey,
crude oils were separated using liquid chromatography on silica
gel. Saturated HC fractions were eluted with n-hexane (30 ml), aromatic fractions with a mixture of n-hexane:CH2Cl2 (7:3, 30 ml) and
polars with a mixture of CH2Cl2:CH3OH (1:1, 30 ml). Saturated and
aromatic fractions were used for bulk d13C analyses and a portion
of the saturated HC fraction was subjected to 5A molecular sieving.
Straight chain HCs were separated from branched and cyclic HCs
by treating the saturated fractions with 5A molecular sieve
(Murphy, 1969) using the procedure described elsewhere (Grice
et al., 2008; Maslen et al., 2009).
2.3. GCMS
GCMS was performed using similar conditions as in Asif et al.
(2009). Briey, we used a HewlettPackard (HP) 5973 Mass Selective Detector (MSD) interfaced to a HP6890 gas chromatograph
equipped with a column (60 m, 0.25 mm ID) with a 0.25 lm 5%
phenyl 95% methyl polysiloxane stationary phase (DB-5MS, J&W
scientic). The injector was operated at 280 C and the He carrier
gas was maintained at a constant ow of 1.1 ml/min. The GC oven
was programmed from 40310 C at 3 C/min with initial and nal
hold times of 1 and 30 min, respectively. The transfer line between
the gas chromatograph and the MSD was held at 310 C. The MS
source and quadrupole temperatures were 230 C and 106 C,
respectively. The saturated and aromatic HCs were identied using
relative retention times, mass spectral data and comparison with
literature data (Trolio et al., 1999; Grice et al., 2001, 2005; Grimalt
et al., 2002; Peters et al., 2005 and references therein).
2.4. Elemental analysis-isotope ratio mass spectrometry (bulk isotope
analysis)
Bulk stable isotope compositions of both the saturated and aromatic HC fractions of Potwar Basin oils were analysed. Bulk stable
isotope analyses were performed on a Micromass IsoPrime isotope
ratio mass spectrometer interfaced to a EuroVector EuroEA3000
elemental analyser. For bulk d13C analyses, each sample was

weighed accurately (0.050.15 mg) into a small tin capsule which

was then folded and compressed carefully to remove any tracers of
atmospheric gases. The tin capsule containing the sample was
dropped into a combustion reactor at 1025 C with the aid of an
autosampler. The sample and capsule melted in an atmosphere
temporarily enriched with oxygen, where the tin promoted ash
combustion. The combustion products, in a constant ow of helium, passed through an oxidation catalyst (chromium oxide).
The oxidation products then passed through a reduction reactor
at 650 C containing copper granules, where any oxides of nitrogen
(NO, N2O and N2O2) are reduced to N2 and SO2 were separated on a
3 m chromatographic column (Poropak Q) at ambient temperature.
After removing the oxides of nitrogen, oxidation products are then
passed through a thermal conductivity detector (TCD) and into the
irMS. Average values of at least two analyses and standard deviations are reported. Isotopic compositions are given in delta notation relative to Vienna Peedee belemnite (VPDB).
For bulk dD analysis, the sample was weighed accurately (0.05
0.15 mg) into a small silver capsule which was then folded and
dropped into a pyrolysis reactor containing glassy carbon chips
held at 1260 C. The sample was pyrolysed to form H2 and CO,
along with N2 if applicable. The pyrolysis products were separated
on a 1 m 5A molecular sieve, packed chromatographic column held
in an oven at 80 C (isothermal), before passing through a TCD,
then into the irMS. dD values were calculated and reported in delta
notation relative to Vienna Standard Mean Ocean Water (VSMOW).
3. Results and discussion
3.1. Normal alkanes and regular isoprenoid distributions
The crude oils analysed in this study are listed in Table 1. The
total ion chromatogram (TIC) of a representative sample is shown
in Fig. 3. n-Alkanes range from C1037 along with isoprenoids from
C1420 (except i-C17) are observed while n-alkanes less than C10 are
absent, probably because of evaporative loss during sample processing. The peak areas from the TIC are used to calculate n-alkane
and isoprenoid parameters listed in Table 1. All the samples show
Pr/Ph ratios from 1.02.0, representing marine oxic/dysoxic depositional environment of OM, with the exception of the P1 oil which
shows a value >3.2, suggesting more oxic depositional conditions.
Carbon preference index (CPI) and odd/even predominance
(OEP) are good indicators for OM type in immature samples where
higher abundance of C1618 n-alkanes indicate an aquatic source
while a C2733 odd abundance of n-alkanes reects terrigenous
OM (Hunt, 1995). Maturation of OM signicantly alters n-alkane
abundance, and CPI and OEP tend towards 1 in typical mature
crude oils. The CPI and OEP values for most of the Potwar Basin oils
are close to 1 (Table 1) indicating mid-oil window thermal maturities of the source at time of expulsion.
3.2. Stable carbon and hydrogen isotopic compositions
The stable isotopic composition of crude oil is mainly dependent on the d13C and dD value of the kerogen which, in turn, depends on the biological OM and the depositional environment
(Schoell, 1984; Chung et al., 1992; Collister and Wavrek, 1996). A
series of oils ranging from low API condensate (API, 48) to high
API oils (API, 16) from the Potwar Basin were examined for bulk
d13C and dD. These results are reported in Table 1. d13C and dD of
saturated and aromatic HC fractions were analysed to delineate
different groups of petroleum in the Potwar Basin. The crude oils
from eastern Potwar are characterised by less negative values of
d13C (isotopically heavy) and cluster together based on d13C of saturated and aromatic HC fractions (Fig. 4a; group B). More negative

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M. Asif et al. / Organic Geochemistry 42 (2011) 12261240

Relative abundance

C17

Pr

C25

d
c
Ph
b

20

40

60

80

100

120

Retention Times
Fig. 3. Representative total ion chromatogram of saturated hydrocarbon fractions of the crude oils, showing distribution of n-alkanes (n-C1037) and isoprenoids (a: 2,6dimethylundecane; b: 2,6,10-trimethylundecane (nor-farnesane); c: 2,6,10-trimethyldodecane (farnesane); d: 2,6,10-trimethyltridecane; e: 2,6,10,-trimethylpentadecane
(nor-pristane); Pr: pristane and Ph: phytane).

(a)

-20.0

13CAros ()

-21.0

-22.0

-23.0

-24.0

-25.0
-27.0

-26.0

-25.0

-24.0

-23.0

-22.0

13CSats ()

(b)

-100

Daver ()

-110

-120

a single oil, group B contains 13 crude oils and group C contains

four crude oils. The stable isotopic composition of group A oil is
most probably controlled by both source and depositional settings
as indicated by n-alkanes and isoprenoid distributions and biomarker parameters (see below). Group B oils show enrichment in
13
C for the saturated HC fraction having values up to 34 heavier
compared to the saturated HC fraction d13C values of group C
(Fig. 4a; Table 1). The differences observed between d13C of saturated HC fractions of groups B and C indicate a difference in source
organisms for the saturated HCs. Another plot represents the differences between d13C and dD average values of both saturated
and aromatic HC fractions of crude oils (Table 1) and is shown in
Fig. 4b. This plot separates the crude oils into three similar groups
providing additional evidence for the existence of at least three oil
groups in the Potwar Basin. The difference in d13C and dD of the
Potwar Basin oils most likely suggests source variations.
The biomarker parameters listed in Tables 13 are used to obtain information regarding source OM, thermal maturity of crude
oils, depositional environment and lithology of OM and the extent
of biodegradation in the Potwar Basin crude oils. The following sections explain these geochemical characteristics one by one, again
differentiating the Potwar Basin crude oils into three groups.

-130

3.3. Thermal maturity of Potwar Basin crude oils

-140

-150
-26.0

-25.0

-24.0

-23.0

-22.0

-21.0

13Caver ()
Fig. 4. Plots to delineate the three oil groups from the Potwar Basin (a) d13Csats
versus d13Caros and (b) d13Caver versus dDaver from average values of d13C and dD of
saturated and aromatic hydrocarbon fractions.

(isotopically lighter) d13C values ( 25 to 26.1) are observed

for P15P18 crude oil samples (Fig. 4a; group C). Among the sample suite of oils analysed, P1 oil is the lightest (most negative) in
d13C of saturated and aromatic HC fractions and is classied as
group A (Fig. 4a). The group designation assigned to each crude
oil from the Potwar Basin is shown in Table 1. Group A comprises

A combination of saturated and aromatic HC biomarkers was

used to determine the thermal maturity of the Potwar Basin oils.
The data in Table 2 were obtained from GCMS analysis of the
branched/cyclic fractions. The hopane based parameters were calculated from peak areas of 191 Dalton mass chromatograms. The
C32 homologue ratio 22S/(22S + 22R) varies between 0.57 and
0.64, indicating equilibrium values for this ratio, suggesting that
the maturity is at least equal to early oil generation window for
all the oil samples of the Potwar Basin (Table 2). However this ratio
reaches equilibrium in the oil window so has limited application
for studying the relative maturities of crude oils and condensates
(Peters et al., 2005). Another hopane based maturity parameter is
the ratio of 17a(H),21b(H)-hopane relative to corresponding
17b(H),21a(H)-moretanes [ab/(ab + ba)] for C29- and C30-compounds, which equilibrate at somewhat higher thermal maturities
(Seifert and Moldowan, 1980; Peters et al., 2005). The values for

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M. Asif et al. / Organic Geochemistry 42 (2011) 12261240

Table 2
Saturated and aromatic hydrocarbon biomarker thermal maturity parameters.
Sample name
P1
P2
P3
P4
P5
P6
P7
P8
P9
P10
P11
P12
P13
P14
P15
P16
P17
P18

Ts/(Ts + Tm)a
0.53
0.40
0.36
0.36
0.37
0.38
0.41
0.40
0.45
0.35
0.31
0.38
0.45
0.73
0.67
0.66
0.70
0.70

ab/(ab + ba),

ab/(ab + ba),

bb/(aa + bb)
C29-Stere

S/(S + R)
C29-sterf

TNR-1h

TNR-2i

Rcbj (%)

MPI-1k

Rcl (%)

C30-Hopc

S/(S + R)
C32-Hopd

DNR-1g

C29-Hopb
0.83
0.93
0.92
0.94
0.93
0.93
0.94
0.93
0.92
0.96
0.94
0.93
0.97
1.00
1.00
1.00
1.00
0.90

0.81
0.86
0.86
0.87
0.88
0.90
0.87
0.88
0.88
0.89
0.90
0.85
0.92
1.00
1.00
1.00
0.92
0.92

0.62
0.61
0.62
0.60
0.58
0.56
0.57
0.59
0.61
0.57
0.59
0.60
0.60
0.64
0.63
0.63
0.61
0.61

0.59
0.66
0.65
0.64
0.63
0.61
0.63
0.61
0.64
0.59
0.59
0.62
0.63
0.63
0.61
0.61
0.63
0.62

0.41
0.43
0.41
0.44
0.45
0.45
0.45
0.47
0.47
0.48
0.46
0.45
0.45
0.47
0.45
0.43
0.44
0.47

6.8
7.6
7.2
6.3
5.7
6.2
7.8
8.1
8.0
8.4
5.7
6.9
5.5
6.8
7.7
7.1
7.4
8.5

1.04
1.43
1.38
1.61
1.44
1.64
1.50
1.85
1.61
1.96
2.31
2.17
1.39
1.25
1.29
1.23
1.39
1.23

0.94
1.04
1.02
1.03
0.98
1.05
1.00
1.12
1.12
1.14
1.24
1.18
0.95
0.95
0.91
0.96
1.00
0.94

1.02
1.02
0.99
1.03
1.00
0.96
1.08
1.15
1.11
0.97
1.07
1.07
0.95
0.97
1.01
0.98
1.00
0.96

0.75
1.07
1.02
0.80
0.90
0.85
0.92
1.04
0.89
0.91
0.85
0.90
1.26
1.14
1.16
1.14
1.07
1.09

0.85
1.04
1.01
0.88
0.94
0.91
0.95
1.03
0.93
0.94
0.91
0.94
1.16
1.08
1.10
1.08
1.04
1.05

: not determined.
a
Ts/(Ts + Tm), 18a(H)-22,29,30-trisnorneohopane/(18a(H)-22,29,30-trisnorneohopane + 17a(H)-22,29,30-trisnorhopane).
b
ab/(ab + ba) C29 Hop: 17a(H),21b(H)-30-norhopane/(17a(H),21b(H)-30-norhopane + 17b(H),21a(H)-30-norhopane).
c
ab/(ab + ba), C30 Hop: 17a(H),21b(H)-hopane/(17a(H),21b(H)-hopane + 17b(H),21a(H)-hopane).
d
S/(S + R), C32 Hop, 22S/(22S + 22R), 17a(H)-bishomohopane.
e
(bb/aa + bb) C29-Ster: 14b(H),21b(H)/[14a(H),21a(H) + 14b(H),21b(H)] 20R-ethylcholestane.
f
S/(S + R) C29 ster: 20S/(20S + 20R) 14a(H),21a(H)-ethylcholestane.
g
DNR-1: dimethylnaphthalene ratio 1 (2,6- + 2,7-DMN/1,5-DMN), Radke, 1987.
h
TNR-1: trimethylnaphthalene ratio 1 (2,3,6-TMN/1,4,6- + 1,3,5-TMN), Alexander et al., 1985.
i
TNR-2: trimethylnaphthalene ratio 2 (2,3,6- + 1,3,7-TMN)/1,4,6- + 1,3,5- + 1,3,6-TMN).
j
Rcb: 0.40 + 0.6  (TNR-2) Radke et al., 1986.
k
MPI-1: methylphenanthrenes index {1.5  [3-MP + 2-MP]/[P + 1-MP + 9-MP]}, Radke et al., 1982.
l
Rc: calculated vitrinite reectance (0.6  MPI-1 + 0.4), Radke and Welte, 1983.

Table 3
Source OM parameters for Potwar Basin oils.

a
b
c
d
e
f
g
h
i
j
k
l
m

Sample
name

C19/
(C19 + C23)
TTa

C24TeT/
(C24TeT + C23TT)b

C23
TT/C30
Hopc

C24TeT/
C30
Hopd

C28TT/
C30Hope

C29/
C30 ab
hopf

Dia/
hop
C30g

C30
Dia/
C29
Tsh

C31(R + S)/
C30 hopi

Steranes/
hopanesj

Dia/
ster
C27k

Dia/
Ster
C29l

Total
Dia/
Sterm

C27
abb

C28
abb

C29
abb

P1
P2
P3
P4
P5
P6
P7
P8
P9
P10
P11
P12
P13
P14
P15
P16
P17
P18

0.88
0.49
0.46
0.40
0.40
0.39
0.38
0.41
0.45
0.33
0.30
0.38
0.44
0.49
0.34
0.33
0.36
0.32

0.77
0.47
0.49
0.56
0.55
0.54
0.52
0.57
0.52
0.61
0.63
0.55
0.55
0.51
0.44
0.45
0.40
0.44

0.07
0.40
0.31
0.32
0.37
0.37
0.46
0.33
0.28
0.24
0.23
0.43
0.38
1.93
1.54
1.16
0.86
0.50

0.24
0.35
0.30
0.42
0.45
0.44
0.49
0.44
0.30
0.38
0.39
0.52
0.47
2.03
1.22
0.93
0.58
0.40

0.00
0.00
0.00
0.11
0.12
0.10
0.17
0.10
0.09
0.08
0.07
0.13
0.11
0.64
0.71
0.55
0.41
0.27

0.65
0.58
0.55
0.74
0.78
0.76
0.75
0.65
0.69
0.79
0.87
0.75
0.75
0.64
0.61
0.51
0.48
0.57

0.38
0.26
0.22
0.15
0.15
0.17
0.22
0.15
0.18
0.11
0.07
0.20
0.19
0.86
0.32
0.29
0.26
0.23

2.23
1.44
1.78
0.83
0.75
0.86
1.13
0.80
0.64
0.72
0.56
1.24
0.83
1.34
1.44
1.59
1.29
0.91

0.77
0.75
0.75
0.94
0.97
0.89
0.90
0.82
0.86
0.88
0.96
0.98
0.83
0.89
0.44
0.44
0.47
0.50

0.29
0.23
0.24
0.23
0.28
0.27
0.34
0.27
0.35
0.23
0.20
0.33
0.35
1.24
1.50
1.45
0.74
0.58

0.53
0.76
0.53
0.55
0.50
0.59
0.50
0.50
0.61
0.44
0.45
0.55
0.55
0.65
0.38
0.40
0.43
0.38

0.97
0.60
0.63
0.57
0.51
0.54
0.60
0.49
0.68
0.40
0.38
0.59
0.58
0.78
0.06
0.19
0.26
0.27

1.15
0.91
0.80
0.76
0.73
0.76
0.76
0.77
0.82
0.65
0.63
0.83
0.74
0.97
0.31
0.40
0.35
0.34

43
37
39
40
41
40
40
48
38
42
42
39
41
45
24
22
31
30

18
13
21
17
16
17
20
8
22
12
12
19
19
18
34
34
32
31

39
50
40
43
43
43
40
45
40
46
47
42
40
37
41
44
37
39

C19/(C19 + C23) TT, C19-tricyclic terpane/(C19-tericyclic terpane + C23 tricyclic terpane).

C24TeT/(C24TeT + C23TT), C24-tetracyclic terpane/(C24-tetracyclic terpane + C23 tricyclic terpane).
C23 TT/C30-hop: C23 tricyclic terpane/C30-ab hopane.
C24 TeT/C30-hop: C24 tetracyclic terpane/C30-ab hopane.
C28TT/C30-Hop, C28 tricyclic terpane/C30 ab hopane.
C29/C30 ab hop, C29 30-norhopane/C30 ab-hopane.
Dia/Hop C30, C30 ba diahopane/C30 ab-hopane.
C30 Dia/C29 Ts: C30, ba diahopane/18a(H)-30-norneohopane.
C31 (R + S)/C30 hop, C31 ab-homohopane (22S + 22R)/C30 ab-hopane.
Steranes/hopanes: total steranes/total hopanes.
Dia/ster C27: ba/(aa + bb) cholestane.
Dia/ster C29: ba/(aa + bb) ethylcholestane.
Total dia/ster, total ba steranes/(ab + aa) steranes; C27, C28, C29 abb steranes.

1233

M. Asif et al. / Organic Geochemistry 42 (2011) 12261240

(a)

1B
Equilibrium

0.90

Early oil generation

0.85
0

0.0

1.0

B&C

2.0

0.80

3.0

4.0

Pr/Ph

0.75
0.75

3.5

(b)
0.80

0.85

0.90

0.95

1.00

Pr/Ph

2.5

1.2

C
2

1.5

Late

1.1

/(+), C29-Hop

(b)

1A: marine Carbonate

1B: marine carbonate and marl
2: Lacustrine hypersaline
3: marine shale and lacustrine
4:fluvio-deltaic shale
Hughes et al, 1995

1A
3

0.95

DBT/P

/(+), C30-Hop

(a) 1.00

Rc (%)

1.0
0.5
0.9

10

20

30

Peak

40

50

API gravity ()

(c)

Early

0.7
0.6
0.6

0.7

0.8

0.9

1.0

1.1

1.2

Rcb (%)
Fig. 5. (a) Hopane maturity parameter plot between C29 versus C30 of ab/(ab + ba)
(cf. George et al., 2001) (b) calculated vitrinite reectance diagram from Rcb (TNR-2;
Radke et al., 1986) and Rc (MPI-1; Radke and Welte, 1983) showing different
thermal maturation stages of oil generation window.

Diasterane/steranes, C29

0.8
1.0

0.8

P14

0.6
0.4

C
0.2
0.0

0.0

0.2

0.4

0.6

0.8

1.0

Diahopane/hopane, C30
both C29- and C30-moretanes, [ab/(ab + ba)] ratios are in the range
of 0.81 to 1.0 (mostly >0.9, Table 2) typical for oils generated from
mature source rocks (cf. George et al., 2004). The plot of hopane
based maturity parameters between C29- and C30-ab/(ab + ba) is
shown in Fig. 5a (cf. George et al., 2001), where most of the oil samples fall close to equilibrium and higher than equilibrium level
indicating higher thermal maturity except P1, which shows relatively low thermal maturity. The slight difference in ab/(ab + ba)
ratios for the Potwar Basin oils shows the affects of source and
depositional environment variations on these values (Rullktter
and Marzi, 1988; Isaksen and Bohacs, 1995). The Ts/(Ts + Tm) ratio
continuously varies from the immature to postmature (Peters
et al., 2005). The values for Ts/(Ts + Tm) ratio range from 0.31
0.73 for the oils indicating an immature to mature range of thermal
maturity, however a narrow range of this ratio is observed for individual groups. For example, group B show a Ts/(Ts + Tm) ratio in
the range of 0.310.45 while group C shows values in the range
of 0.670.70. The single Group A oil (P1) has an intermediate value
(0.53, Table 2). One oil sample (P14, Table 2) from group B shows a
higher value for Ts/(Ts + Tm), 0.73, indicating signicant effects of
source and depositional environments (Moldowan et al., 1986).
Different Ts/(Ts + Tm) values for each group of oils indicate that
this ratio is controlled by factors other than thermal maturity, most
probably source and depositional environments (Moldowan et al.,
1986) that are shown to affect the source OM of Potwar Basin oils
(see below).
The sterane based thermal maturity parameters such as 20S/
(20S + 20R) ethylcholestane and bb/(aa + bb) ethylcholestane
range tightly at 0.410.48 and 0.590.66 respectively, supporting

Fig. 6. (a) Pr/Ph versus DBT/P indicating lithology and depositional environment
(Hughes et al., 1995) (b) a cross plot of API gravity and Pr/Ph separating the Potwar
Basin oils into three groups, (c) C30 diahopane/hopane versus C29 diasterane/sterane
ratios.

a similar thermal maturity for these samples while the equilibrium

occurs between 0.520.55 and 0.670.7,1 respectively (Seifert and
Moldowan, 1986). These values suggest that none of the oils have
reached full maturity with respect to equilibrium values suggested
by Seifert and Moldowan (1986). However these lower than equilibrium values for both sterane parameters are consistent with the
peak oil generation window for the Potwar Basin oils (Peters et al.,
2005). Despite the fact that 20S/(20S + 20R) ratio is very useful to
indicate thermal maturity, factors other than thermal maturity
can affect this ratio. For example, reversal of this ratio within
highly mature intervals could be responsible for the lower values
(cf. Bishop and Abbott, 1993; Edwards et al., 1997).
It has been shown that many biomarker maturity parameters
reach equilibrium at the onset of the oil window and therefore
may not be useful for highly mature oils and condensates (van
Graas, 1990). In this scenario, parameters based on aromatic HCs
may be more effective for evaluation of thermal maturity. The
methyl phenanthrene index (MPI-1; Radke et al., 1982) appears
to be useful to estimate vitrinite reectance (Radke et al., 1982;
Radke, 1988). The MPI-1 and calculated vitrinite reectance (Rc)
values from Potwar Basin oils are reported in Table 2. The MPI-1
is in the range of 0.751.26 and Rc in the range of 0.851.15%.
The Rc for P1 (0.85%, Table 2) suggests a maturity equivalent to

1234

M. Asif et al. / Organic Geochemistry 42 (2011) 12261240

30H

(a) Group-A
Sample: P1
19
24*

30H
29H

Relative intensity

Tm
24*
23

Ts

29Ts

21
19 20

31H
S
32H
R
S
R 33H
34H
S
R S
R

30H
24

21

35H
S R

(c) Group-C
Sample: P15

23
20

(b) Group-B
Sample: P10

29H

24*
19
25

28

29

30 31
32 33

61

71

81

91

34
35 36

38 39

40 41

101

Relative retention time (min)

Fig. 7. Mass chromatograms (m/z 191) showing distribution of tricyclic, tetracyclic and pentacyclic terpanes (hopanes, H) in typical Potwar Basin crude oils. Numbers on
peaks (1941) indicate tricyclic terpanes; numbers with H (29H35H) indicate hopanes; S and R indicate stereochemistry at carbon 22 of homohopanes (31H35H);
Ts: 18a(H)-22,29,30-trisnorneohopane; Tm: 17a(H)-22,29,30-trisnorhopane; C29Ts: 18a(H)-30-norneohopane; 24: C24-tetracyclic terpane.

peak oil generation while all other Potwar Basin oils indicate a
maturity of late oil generation window (>0.9) (cf. Radke, 1987).
Methylnaphthalene thermal maturity parameters are also listed
in Table 2. The dimethylnaphthalene ratio (DNR-1, Table 2) >5.5
(Table 2, mostly 78) clearly indicates that the thermal maturity
of the Potwar Basin oils has reached the late oil generation window. The trimethylnaphthalene ratio 1 (TNR-1, Table 2) has been
calibrated with the sterane isomerisation ratio (20S/20R), showing
that the sterane isomerisation ratio of oils reaches equilibrium
when TNR-1 ratio is >1 (Alexander et al., 1985). TNR-1 values for
Potwar Basin oils are >1 (mostly >1.2) for all samples, indicating
that the maturity of source rocks generating these oils reached to
higher than the peak oil generation window (cf. Alexander et al.,
1985). Similarly, the trimethylnaphthalene ratio 2 (TNR-2, Table
2) is another useful aromatic HC thermal maturity parameter
which has been calibrated with mean vitrinite reectance (Ro)
and shows good agreement with increase in thermal maturity
(Radke et al., 1986). The TNR-2 value (0.91.2, Table 2) and calculated vitrinite reectance Rcb values (>0.95, Table 2) from TNR-2
indicate thermal maturity of the oil samples from the Potwar Basin
reached the late oil generation window (Radke et al., 1986). A cross
plot (Fig. 5b) of calculated vitrinite reectance values i.e. Rcb (TNR2) versus Rc (MPI-1) clearly indicates that the thermal maturity of
Potwar Basin oils reaches to the late oil generation window. It has
been shown that the biomarker maturity parameters reveal early

to peak oil generation window for Potwar Basin oils, however these
parameters mostly reached equilibrium values so showed limited
application for maturity assessment. Finally, it is concluded that
equivalent vitrinite reectance calculated from aromatic HC maturity parameters reveal source rocks of Potwar Basin oils reached
maturities of late oil generation window.
A few anomalies are observed in the alkylnaphthalene maturity
parameters. For example, TNR-1 shows a wide range of values from
1.042.31 although most of the values lie between 1 and 2. High
values (TNR-1 >2.0, Table 2) for some of the oils are probably
due to secondary effects such as biodegradation. Affects of biodegradation on alkylnaphthalenes have been shown to affect different
isomers and thus different susceptibilities towards biodegradation
(Asif et al., 2009) and thermal maturity parameters are altered
when using certain isomers in thermal maturity ratio calculations
(van Aarssen et al., 1999; Obermajer et al., 2004).
3.4. Lithology and depositional environments
The crude oils listed in Table 1 were examined for lithology and
depositional environment using aliphatic and aromatic biomarker
parameters. The Pr/Ph ratio shows a range of values from 12 (except sample P1, Pr/Ph = 3.2) for the Potwar Basin oils (Table 1).
DBT/P ratio is a good indicator of lithology and the values for the
ratio are <1 for all samples supporting a shale lithology for the

1235

0.8

A
0.7

tricyclic terpane)

(a)

C24 tetracyclic terpane/(C24 tetracyclic terpane+C23

M. Asif et al. / Organic Geochemistry 42 (2011) 12261240

Terrigenous

0.6

0.5

0.4

0.3

0.2
0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

C19/(C19+C23) Tricyclic terpanes

1.0

C28/C27,20R, , steranes

(b)

0.8

0.6

B
0.4

0.2

0.0
0.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

C27/C29, 20R, , steranes

Fig. 8. (a) C19/(C19 + C23) tricyclic ratio versus C24 tetracyclic/(C24 tetracyclic + C23 tricyclic) terpane ratio, and (b) C27/C29 aaa versus C27/C28 abb diagrams; both differentiate
these oils into three groups.

Potwar Basin oils (Hughes et al., 1995). The Pr/Ph and DBT/P data
from Potwar Basin oils are plotted based on the Hughes diagram
(Hughes et al., 1995) and these results are shown in Fig. 6a. The
largest set of oils from the Potwar Basin (group B and C) are shown
to originate from marine shale and lacustrine source rocks (Fig. 6a)
while the single group A oil (P1) indicates a highly oxic uvio-deltaic depositional environment. However no molecular evidence is
observed for a lacustrine depositional environment of source rocks
for Potwar Basin oils. These results indicate that most of the oils in
the Potwar Basin were generated from marine shale source rocks
and the single oil of group A was generated from uvio-deltaic
source rocks.
Depositional environments based on Pr/Ph ratio and HC compositional variations based on API gravity are used to differentiate the
Potwar Basin oils. A cross plot of API gravity and Pr/Ph is shown in
Fig. 6b. The single oil positioned in the right top corner of the plot
indicates higher Pr/Ph and API values consistent with an oxic depositional environment and light oil typically generated from
terrigenous OM. An interesting feature of the plot (Fig. 6b) is the
separation of the group B and C oils that were shown to be similar
in the Hughes diagram (Fig. 6a). The group B oils show lower Pr/Ph
(mostly <1.4) and low API values while group C oils show

intermediate Pr/Ph values (1.41.6) and high API values. The Pr/
Ph ratio and API gravity relationship differentiates Potwar Basin
crude oils into similar three groups. However, sample P14 from
group B is positioned in group C (arrow in Fig. 6b).
The depositional environment and lithology interpretations
indicate three groups of oils are present in the Potwar Basin. This
result is further evaluated and supported using various biomarker
parameters (Fig. 6c). A plot of C30 diahopane/hopane versus C29
diasterane/sterane ratios is shown in Fig. 6c and samples from
the Potwar Basin fall into the same three groups. Group B shows
relatively higher diasterane/sterane ratios compared to the group
C indicating that the group B oils are generated from more clastic
rocks, while group C shows higher C30 diahopane/hopane ratios
indicating that the group C oils were generated from more oxic
depositional environment source rocks. The oil from group A (P1)
shows higher values of diahopane/hopane and diasterane/sterane
ratios (0.38 and 0.97, respectively) separating this oil from all the
other oils (Fig. 6c), and indicating a clay rich, oxic depositional
environment. The P1 oil sample was likely generated from oxic/
clay rich source rocks, which is consistent with its C30 diahopane/C29Ts ratio. The C30 diahopane/C29Ts ratio has been suggested
as a good indicator of oxic/suboxic depositional settings of OM

1236

M. Asif et al. / Organic Geochemistry 42 (2011) 12261240

(Peters et al., 2005) and this ratio for group A is very high (2.23, Table 3) indicating an highly oxic depositional environment.
Although data for both groups B and C oils imply marine source
rocks based on lithology and environments of deposition (see
above), relative abundance of hopanes differentiates the groups
(Fig. 6c): group B is more reduced than group C. The C30 diahopane/C29Ts ratio (61.0 for most of oils) and C31 (R + S) hopane/
C30 hopane ratio (>0.75) for group B oils indicate more dysoxic
depositional settings for OM than for group C oils (cf. Peters and
Moldowan, 1993). An anomalously high value relative to the group
B oils is observed for the P14 sample in the C30 diahopane/hopane
versus C29 diasteranes/sterane diagram (Fig. 6c). The reason for this
anomaly could be related to the depositional environment (high
Pr/Ph ratio for this sample) and source organic facies (Moldowan
et al., 1991; Peters et al., 2005 and references therein).

3.5. Source of OM
The sources of OM were determined from the distributions of
tricyclic, tetracyclic and pentacyclic terpanes and steranes. Fig. 7
shows m/z 191 chromatograms of the representative oil samples
from all delineated groups from the Potwar Basin. The source biomarker parameters are listed in Table 3. The group A oil shows a
signicantly lower relative abundance of tricyclic and tetracyclic
terpanes except for C19 tricyclic terpane and C24 tetracyclic terpane
(Fig. 7), both indicators of terrigenous OM (Philp and Gilbert, 1986;
Grice et al., 2001; Peters et al., 2005; Volk et al., 2005; Nabbefeld
et al., 2010a). The oil correlation diagram of C19/(C19 + C23) tricyclic

versus C24 tetracyclic/(C24 tetracyclic + C23 tricyclic terpane) is

shown in Fig. 8a where group A indicates clearly a different source
of OM compared to the other groups (cf. Edwards et al., 1997; Volk
et al., 2005). The presence of the aromatic plant biomarker retene
also tends to support a terrigenous source of OM for the group A
oil, although this biomarker can also be ascribed to algae (Nabbefeld et al., 2010b and references therein). The low values for the C23
tricyclic/C30 hopane (<0.1) and C28 tricyclic/C30 hopane ratios (0;
Table 3) also indicate a lower contribution of marine OM for the
group A oil (cf. Peters et al., 2005). These values indicate that the
group A oil was generated from source rocks containing terrigenous OM.
A representative ion chromatogram (191) from group B oils is
shown in Fig. 7b and shows a distribution of both tricyclic and pentacyclic terpanes as observed in typical mature marine crude oils.
The highest components in the group B oils are C29 and C30 hopanes; they are in higher abundance than tricyclic terpanes
(Fig. 7b) differentiating group B from the other groups. The comparative abundances of the homohopanes has been associated with
suboxic depositional environments (Peters and Moldowan, 1993)
and a higher abundance of C35 and other homohopanes are observed in group B oils relative to group C oils (Fig. 7b and c). The
distribution of steranes and rearranged steranes is used for further
differentiation in source OM. Sterane and diasterane distributions
are shown by mass chromatograms (m/z 217) from representative
oil samples of each oil group in Fig. 9. While group A has a terrigenous source, there is no signicant difference observed in the distribution pattern of regular steranes. The group A mass
chromatogram (m/z 217) shows a higher abundance of diasteranes

C17
C 29

Group-A

Group-A

13 , 17

C25

14 , 17
14 , 17
C 27
C 28

C28

C29

C 27

C10

Steranes

Group-B

Group-B

Diasteranes

Relative intensity

Relative Response

C35

Group-C

UCM

Group-C

81

85

89

Relative Retention time

Fig. 9. Mass chromatograms (m/z: 217) showing distribution of steranes and
diasteranes from representative oil samples from the three delineated groups of
oils. Numbering on peaks refers to steranes and diasteranes compounds. Sample P1
represents group A, sample P7 represents group B and sample P16 represents group
C.

20

40

60

80

100

120

Relative retention time (min)

Fig. 10. Representative total ion chromatograms (TICs) of the saturated hydrocarbon fractions from each group of the Potwar Basin oils. Number on peaks refers to
the n-alkane carbon number. UCM, unresolved complex mixture.

1237

M. Asif et al. / Organic Geochemistry 42 (2011) 12261240

terpanes in sedimentary OM of varying ages has been related to

numerous source origins (Farrimond et al., 1999). The occurrence
of tricyclic terpanes in the Potwar Basin C oils is probably related
to an algal source which is supported by comparative abundance
of regular C28 steranes in group C oils (Table 3; Fig. 8b). Higher
abundance of tricyclic terpanes than hopanes has also been related
to terrigenous input (Philp et al., 1989) that is consistent with
higher abundance of C29 steranes in group C oils. Similarly, a higher
total sterane/hopane ratio >0.6 (1.0 for most of the oils) may reect a greater eukaryotic input (both algae and terrigenous) to
group C oils source rocks. The C23 tricyclic/C30 hopane and C24 tetracyclic/C30 hopane ratios (0.51.5 and 0.41.2, respectively, Table
3) indicate typically marine OM input for group B and C oils where
higher values for group C oils shows a higher marine input (algal
input) (cf. Peters et al., 2005). This differentiation in numerous
source OM parameters shows a different origin for source input
for each group and it is concluded that petroleum from Potwar Basin contained three source oil families.
The data set presented here indicates a few contradictions with
respect to the classication of crude oils from the Potwar Basin. In
the above correlations (Fig. 6b and c), sample P14 (group B) positioned with group C oils. Similarly many source parameters for
the same sample such as C23 tricyclic/C30 hopane, C24 tetracyclic/
C30 hopane, C23 tricyclic/C28 tricyclic terpane and steranes/hopanes
place this oil close to the group C oils (Table 3). Moreover, the C27,
C28 and C29 abb steranes show a different distribution trends for
each group i.e. group A shows C27 P C29  C28, group B shows
C29 P C27  C28 and group C shows C29 > C28 > C27 (Table 3). The
relative distribution prole of abb steranes (C27 P C29  C28) from
group A reveals higher lacustrine source input while it has been
shown that this group has a terrigenous origin. The abb steranes
prole from group B oils shows higher C29 compounds, indicating
terrigenous input in contrast to results drawn from this study that

compared to regular steranes consistent with a clastic source rock

common in deltaic/oxic depositional settings (Peters et al., 2005).
The regular steranes show almost equal abundance to the diasteranes in group B oils while in group C oils the former is signicantly
less abundant than the latter. These distribution differences are
indicating that the group B oils were generated from more clastic
source rocks than the group C oils, consistent with above results
(Section 3.4). The C29 and C28 regular steranes are present in significantly higher abundance than other steranes and diasteranes in
the group C oils (Fig. 9) indicating the signicant contribution of
terrigenous and algal OM, respectively. These interpretations of
terrigenous and algal contribution to group C oils are consistent
with presence of higher concentrations of tricyclic terpanes than
hopanes (see below) (cf. Philp et al., 1989) and high API values
for these oils (Peters et al., 2005). The regular sterane correlation
diagram between C27/C29 aaa versus C28/C29 abb steranes is
shown in Fig. 8b which differentiates the Potwar Basin oils into
the same three groups where group C shows higher C28 regular
steranes representing a higher algal input. The distribution of rearranged steranes also differentiate B from C oils (Table 3). Group B
shows higher C27 and C29 ba/(bb + aa) ratios (>0.45 and >0.4,
respectively) indicating comparatively more marine clastic source
input than group C oils.
The representative 191 ion chromatogram for group C oils
shows signicantly higher abundance of tricyclic terpanes than hopanes (Fig. 7c). The C23 tricyclic terpane is the most abundant m/z
191 compound in the group C oils and the presence of extended tricyclic terpanes up to C41 and possibly higher is an important feature of these oils, which can be used to differentiate group C
from groups A and B. Various organisms have been suggested as
the source of tricyclic terpanes in oils and bitumens (Ourisson
et al., 1982; Volkman et al., 1989; Peters and Moldowan, 1993;
Simoneit et al., 1993) and the ubiquitous occurrence of tricyclic

(a)

Biodegradation

1.2

P11,P12

Ph/n-C18

0.6

P7

P2
P3

P14,P18

0.4

P6

P10

P8
P13

P15
P16

0.8

P17

0.2

P1

0
0.2

0.4

0.6

0.8

1.2

1.4

1.6

Pr/n-C17

(b)

60

API gravity ()

50

P1

P15,P16

40

P14,P18

P17

P2
P3

30

P9

P6

1.2

P8

20

P4-5
P11-12

P13
10

Biodegradation
0
0.2

0.4

0.6

0.8

1.2

1.4

1.6

Pr/n-C17
Fig. 11. (a) Pr/n-C17 and Ph/n-C18 (b) API value versus Pr/n-C17 showing a decrease in the API gravity of crude oils with increasing biodegradation.

1238

M. Asif et al. / Organic Geochemistry 42 (2011) 12261240

this group is marine. Reasons for these contradictory ndings could

be solved by evaluating the source rocks of Potwar Basin oils, but
source to oil correlation along with migration affects, reservoir
connectivity and oil mixing in Potwar Basin are still to be
determined.
3.6. Extent of biodegradation
Biodegradation is a process that alters the molecular composition and bulk properties (API gravity) of petroleum and sediments
(Connan, 1984; Fisher et al., 1998). A number of commonly used
parameters have been used to assess the extent/level of biodegradation in the Potwar Basin oils. Representative TICs of the saturated fractions from each group of oils are shown in Fig. 10. The
distribution pattern of saturated HC fraction from group A and C
shows the presence of a full suite of n-alkanes and the absence
of any unresolved complex mixture (UCM), indicating no biodegradation. While TIC from the a representative group B oil shows a
substantial UCM in the saturated fraction and a lack of n-alkanes
indicating that these oils have been biodegraded and the remaining
fraction has become enriched in high molecular weight unresolved
components. Similarly, isoprenoids show resistance to biodegradation compared to the n-alkanes because the n-alkanes are removed
faster than isoprenoids during biodegradation (Peters et al., 2005).
Hence isoprenoid/n-alkane ratios from saturated fractions increase
with an increase in biodegradation (Winters and Williams, 1968)
and Pr/n-C17 and Ph/n-C18 ratios > 1 typically indicates the effect
of biodegradation on crude oils. The plot of Pr/n-C17 versus Ph/nC18 (Fig. 11a) shows a trend consistent with biodegradation; these
ratios increase with increasing biodegradation. The API gravity is a
bulk property that directly relates to gross compositions of crude
oils. The Potwar Basin crude oils show a wide range of API gravities
(1648; Table 1). A plot of API gravity versus Pr/n-C17 (Fig. 11b)
shows an inverse relationship, a high Pr/n-C17 and lower API gravity (Fig. 11b) indicative of the oils affected by biodegradation. The
results show that extent of biodegradation for some of the crude
oils in this study reaching up to a level of 3 on the Wenger et al.
(2001) scale. The extent of biodegradation of each crude oil from
the Potwar Basin is represented with level of biodegradation in Table 1. It is observed that some of the oils from group B are affected
by minor biodegradation while group A and C are non-biodegraded
(Fig. 11a and b).
The representative group B chromatogram shows a high UCM
but also the presence of n-alkanes (Fig. 10). This type of saturated
HC prole indicates the possibility of mixing of biodegraded and
non-biodegraded crude oils in the reservoir. Assessment of biodegradation and in-reservoir mixing in the Upper Indus oils (Potwar
Basin) has been reported using biomarker parameters (Asif et al.,
2009).

4. Conclusions
Geochemical characterisation and classication of the Potwar
Basin crude oils were performed using biomarker and stable isotope distributions. Saturated HC biomarkers indicate at least early
to peak oil generation window of thermal maturity while aromatic
HC parameters and calculated vitrinite reectance from these
parameters reveal late oil generation window thermal maturity
for Potwar Basin oils. Stable carbon and hydrogen isotopes of saturated and aromatic HC fractions delineated three groups in the
Potwar Basin oils. These three groups of crude oils are differentiated based on source OM, depositional environment and lithology.
 Group A oil suggests terrigenous source OM generated from
uvio-deltaic source rocks deposited in an oxic depositional

environment. Group A oil shows more negative (isotopically

lighter) d13C of both saturated and aromatic HC fractions compared to all other oils. The abundance of C19 tricyclic and C24
tetracyclic terpanes along with a higher abundance of a diagnostic aromatic HC biomarker, retene, suggests a terrigenous
source OM for group A oil.
 The other oils from the Potwar Basin analysed in this study are
marine in origin. However d13C and dD of bulk HC fractions and
based on tricyclic, tetracyclic and pentacyclic terpane and sterane distributions separate these oils into groups B and C. Group
B oils show the heaviest d13C for both saturated and aromatic
HC fractions. Some of the group B crude oils are biodegraded
(level 23) and the OM of this group was deposited in a suboxic/dysoxic depositional environment.
 Group C oils are typically non-biodegraded, mature crude oils
generated from source OM rich in algae with terrigenous input
deposited under marine oxic environments, which is supported
by the presence of extended tricyclic terpanes and regular steranes. This group shows light d13C in the saturated HC fraction
relative to group B oils; however d13C of the aromatic fraction
of group B and C are not very different from one another.

Acknowledgements
The authors thank Mr. G. Chidlow for assistance with GCMS
and S. Wang for bulk isotope analysis and maintenance. The Higher
Education Commission, Islamabad, Pakistan is thanked for an IRSIP
fellowship and a travel award Grant (IRSIP-5-Ps-20) to MA. KG
acknowledges the ARC for a QEII fellowship (DP0211875,
DP0877167). The authors thank the following exploration companies for providing oil samples: Oil and Gas Development Cooperation Ltd. (OGDCL), Islamabad, Pakistan Petroleum Ltd. (PPL) and
Pakistan Oilelds Ltd. (POL). J. Curiale and H. Huang are acknowledged for constructive reviews of the initial version of this paper.

Associate EditorMaowen Li

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