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Applied Geochemistry 27 (2012) 16551665

Contents lists available at SciVerse ScienceDirect

Applied Geochemistry
journal homepage: www.elsevier.com/locate/apgeochem

Petroleum geochemistry of the Potwar Basin, Pakistan: II Oil classication


based on heterocyclic and polycyclic aromatic hydrocarbons
Muhammad Asif a,b,, Tahira Fazeelat b
a
b

Department of Basic Sciences and Humanities, University of Engineering and Technology, KSK Campus, GT Road, Lahore, Pakistan
Chemistry Department, University of Engineering and Technology, GT Road, Lahore, Pakistan

a r t i c l e

i n f o

Article history:
Received 8 September 2011
Accepted 17 April 2012
Available online 25 April 2012
Editorial handling by R. Fuge

a b s t r a c t
In a previous study, oils in the Potwar Basin (Upper Indus) of Pakistan were correlated based on the dissimilarity of source and depositional environment of organic matter (OM) using biomarkers and bulk
stable isotopes. This study is aimed at supporting the classication of Potwar Basin oils into three groups
(A, B and C) using the distribution of alkylnaphthalenes, alkylphenanthrenes, alkyldibenzothiophenes,
alkyldibenzofurans, alkyluorenes, alkylbiphenyls, triaromatic steroids, methyl triaromatic steroids,
retene, methyl retenes and cadalene. The higher relative abundance of specic methyl isomers of naphthalene and phenanthrene and the presence of diagnostic aromatic biomarkers clearly indicate the terrigenous and oxic depositional environment of OM for group A oil. Group B and C oils are of marine origin
and the aforementioned heterocyclic and polycyclic aromatic hydrocarbons (HCs) differentiate them
clearly into two different groups. The relative percentages of heterocyclic aromatic HCs reveal that the
distribution of these compounds is controlled by the depositional environment of the OM. Sulfur-containing heterocyclic aromatic HCs are higher in crude oils generated from source rocks deposited in suboxic
depositional environments, while oxygen-containing heterocyclic aromatic HCs in combination with
alkyluorenes are higher in marine oxic and deltaic oils. Biomarker and aromatic HC parameters do
not indicate signicant differences in the thermal maturity of Potwar Basin oils. Triaromatic and methyl
triaromatic steroids support the division of Potwar Basin oils into the three groups and their relative
abundances are related to source OM rather than thermal maturity. Signicantly higher amounts of
C20 and C21 triaromtic steroids and the presence or absence of long chain triaromatic steroids (C25, C26,
C27, and C28) indicates that these compounds are probably formed from different biological precursors
in each group. Different isomers of methyl substituted triaromatic steroids are present only for short
chain compounds (C20C22) and the origin of these compounds may be short chain methyl steranes from
unknown biological precursors.
2012 Elsevier Ltd. All rights reserved.

1. Introduction
The Potwar Basin (Upper Indus) is one of the main petroliferous
provinces of Pakistan and exploration activities in the basin began
more than a century ago. Although, the origin of Potwar Basin
petroleum has been the subject of discussion for last few decades
(Khan et al., 1986; Asif and Fazeelat, 2006; Ahmed and Alam,
2007; Fazeelat et al., 2009, 2011), geochemical information about
the source rocks and crude oils has not been extensively investigated until recently. A number of source rocks and reservoir rocks
from the basin have been studied and it is generally believed that
the Paleocene Patala shale is the source rock for most of the Potwar
Basin crude oils (Wandrey et al., 2004; Fazeelat et al., 2010). The

Corresponding author at: Chemistry Department, University of Engineering and


Technology, GT Road, Lahore, Pakistan.
E-mail address: asifchaudhrry@gmail.com (M. Asif).
0883-2927/$ - see front matter 2012 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.apgeochem.2012.04.006

correlation between source rocks and crude oils has not yet been
conrmed by any authentic organic geochemical study.
Potwar Basin oils are trapped in small to medium sized reservoirs and are suggested to have originated from tectonic activities
resulting from the collision between the Eurasian and Indian Plates
(Farah et al., 1984). The geological ages of the reservoir formations
of the Potwar Basin oils are quite variable (see Fig. 1) and the reservoir depths range from about 2000 to 4500 m (Table 1). Detailed
descriptions on the quality of the reservoir rocks of the Potwar Basin
oils are given elsewhere (Khan et al., 1986; Wandrey et al., 2004;
Asif et al., 2011). A brief description of the reservoir formations
follows. The ages range from Precambrian to Tertiary (Fig. 1). The
Cambrian rocks of the reservoirs consist of massive layers of carbonates and evaporates along with marine shales, while in Permian
times, siltstone, glacial tillites and shales were deposited in the Potwar Basin. The Jurassic strata of the Basin consist of siliciclastics and
a few non-marine sandstone deposits (Khan et al., 1986). Eocene
deposits are the most signicant reservoir rocks in the area and they

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M. Asif, T. Fazeelat / Applied Geochemistry 27 (2012) 16551665

Fig. 1. Location map with analyzed oils indicated, these are also marked on the stratigraphy corresponding to reservoir formations of the Potwar Basin. Possible source rocks
and reservoir rocks in the basin are also marked on the right of the stratigraphic unit. Modied and altered from Wandrey et al. (2004) and references therein.

consist of shallow marine carbonate, medium-bedded limestones,


and ne crystalline dolomites. These Eocene reservoirs are producing signicant amounts of petroleum (Fig. 1). The variability in geological data indicates more than one source rock for Potwar Basin
oils and that the migration of generated HCs may take place from
younger reservoirs to older reservoirs. These possibilities are further
supported by the API gravity values, ranging from 16 to 48, indicating the presence of heavy to very light oils. It is necessary to
determine the types of crude oils present in the Potwar Basin prior
to correlating the source rocks and the crude oils. Classication of
Potwar Basin crude oils using biomarkers and bulk stable isotopes
has previously been undertaken (Asif et al., 2011). In this study, organic geochemical parameters from aromatic HC fractions are used
to substantiate the previous oil groupings in the Potwar Basin.
Heterocyclic and aromatic HCs are reported to show that the distribution of these compounds is related to source and paleoenvironmental deposition of OM.
Aromatic structures are ubiquitous in sedimentary OM and suggest that these are the products of sedimentary reactions (Radke,
1987). These aromatic HCs show a characteristic part of the
naphthenic structure of natural products and are termed aromatic
biomarkers (Pttmann and Villar, 1987; Strachan et al., 1988; Alexander et al., 1992b). b-Amyrine from higher angiosperms has been

shown to be a precursor for alkylnaphthalenes (Pttmann and Villar, 1987; Strachan et al., 1988). Similarly, abietane and pimarane
type precursors from diterpenoids are most likely the source of
alkylphenanthrenes (Simoneit et al., 1986). The distribution and
relative abundance of aromatic HCs have been used to identify
the source OM, depositional environment, and as thermal maturity
indicators of source rocks and crude oils (Radke et al., 1982, 1986,
2000; Alexander et al., 1992b; Jinggui et al., 2005; Armstroff et al.,
2006). Heterocyclic aromatic HCs, i.e., dibenzothiophene (DBT),
dibenzofuran (DBF) and uorene (F) have similar structure skeletons and have been suggested to originate from a similar precursor,
biphenyl (Asif et al., 2010). The abundance of these compounds has
been related to the nature of the depositional environment of the
OM and has been applied to source and oil correlations of petroleum (Fan et al., 1990; Radke and Willsch, 1994; Radke et al.,
2000; Jinggui et al., 2005; Xiangchun et al., 2011).

2. Experimental
The sample preparation, liquid chromatography, and gas chromatography mass spectrometery (GCMS) analyses are similar to
those of Asif et al. (2011). Heterocyclic and aromatic HCs were

2680
2187
2063
3640
3545
2773
2694
3063

3318

2687
2179
2103

3612

4096

4174

4485
4450

P1
P2
P3
P4
P5
P6
P7
P8

P9

P10
P11
P12

P13

P14

P15

P16

P17
P18

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

Formation

Reservoir*

Jurrasic
Jurrasic

Eocene

Eocene

Eocene

Eocene

Cambrian
Eocene
Eocene

Cambrian

Cambrian
Eocene
Cambrian
Cambrian
Cambrian
Cambrian
Cambrian
Cambrian

Age

1.40
1.15

1.27

1.28

1.03

1.57

2.04
2.44
2.36

1.33

3.46
1.19
1.19
2.31
1.93
2.00
1.74
1.75

125-/127TMN

1.84
2.16

1.77

2.20

1.50

1.64

1.47
1.57
1.55

1.36

2.49
1.54
1.46
1.55
1.58
1.52
1.44
1.52

1,2,6-/1,2,4TMN

0.53
0.57

n.d.

0.60

0.70

0.74

n.d
1.17
n.d

0.88

1.73
0.76
0.78
1.12
1.12
1.16
1.09
0.92

1,2,5,6-/1,2,5,7TeMN**

10.2
9.0

n.d.

11.4

8.3

5.5

n.d.
1.4
n.d.

4.0

1.4
6.1
5.3
2.6
2.9
2.7
3.4
3.4

1,3,6,7-/1,2,5,6TeMN**

0.76
0.79

0.72

0.79

0.69

0.74

0.77
0.81
0.77

0.76

0.84
0.85
0.75
0.74
0.76
0.75
0.71
0.75

1-MP/9MP

0.34
0.33

0.34

0.32

0.28

0.27

0.25
0.25
0.25

0.28

0.53
0.27
0.28
0.24
0.28
0.25
0.26
0.27

1,7DMP/X

26
25

34

42

60

62

62
65
61

62

19
50
57
70
61
67
61
56

DBT

60
65

59

55

33

33

25
25
27

13

50
28
14
13
24
16
23
35

Relative
percentages

14
10

13
10
12

25

31
22
29
17
15
17
16
9

DBF

27
32

41

40

53

59

66
70
69

62

13
48
52
67
62
66
62
59

Alkyldibenzothiophenes

Relative percentages

54
54

50

53

40

35

24
21
22

28

49
41
35
22
27
22
27
33

Alkyluorenes

19
14

10
9
9

10

38
11
13
11
11
12
11
8

Alkyldeibenzofurans

TMN: trimethylnaphthalene; TeMN: tetramethylnaphthalene; 1-MP/9-MP: 1-methyl phenanthrene/9-methyl phenanthrene; 1,7-DMP/X; 1,7-dimethyl phenanthrene/(1,3- + 3,9- + 2,10- + 3,10-DMP);
Relative percentage of DBT: DBT/(DBT + F + DBF) and same for F and DBF;
Alkyldibenzothiophenes: dibenzothiophene + methyl dibenzothiophenes; alkyluorenes: uorene + methyl uorenes; alkyldibenzofurans: dibenzofuran + methyl dibenzofurans;
n.d.: not determined.
*
Data used from Asif et al. (2011).
**
Calculated from peak areas of chromatograms using GC WAX column (Asif et al., 2009).

Depth
(m)*

No*

Table 1
Geological information, heterocyclic and aromatic HC ratios and relative percentage data for analyzed Potwar Basin oils.

C
C

B
B
B

A
B
B
B
B
B
B
B

Group*

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MBP

identied using relative retention times, mass spectral data and


comparison with literature data (Radke et al., 1982, 2000; Lichtfouse, 1989; Budzinski et al., 1998; Asif et al., 2010).

DMBP
TMN

MN

3. Results and discussion

3.1. Heterocyclic and polycyclic aromatic HCs distribution in Potwar


Basin crude oils
Distributions of heterocyclic and polycyclic aromatic HCs are
determined from GCMS analysis of aromatic HC fractions. Representative total ion chromatograms (TICs) of aromatic fractions from
each delineated group of the Potwar Basin oils are shown in Fig. 2.
Diaromatic and triaromatic HCs are the main components present
in TICs (Fig. 2). Nevertheless, different classes of these components
show differences in their relative distributions between the groups.
The relative abundance of six main classes of heterocyclic and
aromatic compounds, i.e. alkylnaphthalenes, alkylphenanthrenes,
alkyldibenzothiophenes, alkyldibenzofurans, alkylbiphenyls, alkyluorenes is calculated and a histogram is constructed from
averaged values for the three oil groups (Fig. 3). It can be seen that
each class of compounds shows distinctive distributions in the three
groups. Group A and C oils show higher abundance of MN and DMN

BP
MF P
MP

TeMN

DMP
DMF
N
TMN

Group-B
(b) P-7

TMP
DMP
DMDBT
MDBT
MP

DMN

Relative intensity

Potwar Basin crude oils were evaluated for classication using


saturated and aromatic biomarker distributions and the results
having been presented previously (Asif et al., 2008). Some of these
crude oils show the affects of biodegradation on HCs and stable H
isotopes (Asif et al., 2009). Biomarkers and stable isotope distributions were used in the rst part of this study and revealed that
three types of crude oils are present in the basin based on variations in the source OM and depositional environment (Asif et al.,
2011). Group A is generated from source rocks deposited in highly
oxic/deltaic depositional environment and containing terrigenous
OM. Group B is sourced from marine OM deposited in a suboxic
depositional environment and a few oils of this group are inuenced by biodegradation up to level 23 making them heavier
(low API) than other oils of the basin. Group C is generated from
source rocks containing marine/algal OM, with little terrigenous
input, deposited in a marine oxic depositional environment and
not showing any biodegradation affects. It is important to mention
that biodegradation has not previously been correlated with this
classication scheme because some of the group B oils are affected
by biodegradation (Asif et al., 2009). This classication will be further supported in the following sections by heterocyclic and aromatic HCs distribution and data.

Group-A
(a) P-1

DMN

TAS

TeMN P

MN
DMN
MN

Group-C
(c) P-18

TMN

TeMN P

MP DMP
TMP

30

40

50

60

70

80

90

100

Relative retention times (min)


Fig. 2. TICs showing the distributions of heterocyclic and aromatic HCs in representative oil samples from each group of the Potwar Basin; N, naphthalene; MN, methyl
naphthalenes; DMN, dimethylnaphthalenes; TMN, trimethylnaphthalenes; TeMN,
tetramethylnaphthalenes; BP, biphenyl; MBP, methyl biphenyls; DMBP, dimethylbiphenyls; P, phenanthrene; MP, methyl phenanthrenes; DMP, dimethylphenanthrenes; TMP, trimethylphenanthrenes; MDBT, methyldibenzothiophenes; DMDBT,
dimethyldibenzothiophenes; MF, methyl uorenes; DMF, dimethyl uorenes; TAS,
triaromatic steroids.

(see Fig. 2. for abbreviations) than group B oils while the abundance
of TMN is higher in the latter group. The MP and DMP are equally
abundant in all groups while TMP is most abundant in group B
and C oils. It is notable that in group B oils the relative abundance
of alkylnaphthalenes and alkylphenanthrenes increases with
increase in methyl substitution, i.e. TMN > DMN > MN and

Fig. 3. Histogram showing the relative amounts of heterocyclic and aromatic HCs classes for each group of Potwar Basin oils. For abbreviations see Fig. 2.

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DMP > MP > P. In group C oils the alkylphenanthrenes have similar


distributions as in the group B oils while the alkylnaphthalenes have
different distributions. For group A oil the alkylnaphthalenes and
alkylphenanthrenes do not show any distributions related to group
B and C oils.
These results reveal that each group of oils is unique regarding
the relative amounts of alkylnaphthalenes and alkylphenanthrenes. BP and MBP are signicantly higher in their relative abundance in group A than in the other groups (Fig. 3). The most
likely natural product precursor for BP is thus suggested to be lignin phenol that is abundant in terrestrially-derived OM (Type III
kerogen) (Odier and Artaud, 1992; Fenton et al., 2007). Similarly,
DBF and MDBF are also abundant in group A oil. These O-containing heterocyclic aromatic HCs have been suggested to originate
from terrigenous rocks (Radke et al., 2000). The relative abundance
of these terrigenous aromatic compound classes clearly distinguishes group A from the other groups and reveals terrigenous
source OM for this oil. These results also indicate that group B
and C oils are of marine origin which is further supported by the
following observations. DBT, MDBT and DMDBT are signicantly
more abundant in group B oils than group C oils which have more
abundance of these compounds than group A oil (Fig. 3). The higher
abundance of S-containing heterocyclic aromatic HCs leads to an
indication of marine oils (Fan et al., 1990; Jinggui et al., 2005).
Moreover, BP, MBP, DBF and MDBF are less abundant in both group
B and C oils and this fact differentiates them from group A oil. The F
and MF are equally abundant in group A and C oils while they are
less abundant in group B oils (Fig. 3). These observations concerning the relative distributions of heterocyclic and polycyclic aromatic HCs indicate that at least three types of crude oil are
present in the Potwar Basin and that they are related to depositional settings and origin of source rocks.
3.2. Alkylnaphthalenes, alkylphenanthrenes, retene and related
compounds in Potwar Basin oils
Differences in the abundance of methyl isomers of naphthalene
and phenanthrene have been used to indicate the predominance of
particular source input (marine versus terrigenous) in sedimentary
OM. (Pttmann and Villar, 1987; Strachan et al., 1988; Alexander
et al., 1992b; Budzinski et al., 1995). Relative abundances of various isomers of alkylnaphthalenes and alkylphenanthrenes are
determined by ratio calculation from their peak areas and are reported in Table 1. Fig. 4a shows a cross plot of 1,2,5-/1,2,7-TMN
versus 1,2,5,6-/1,2,5,7-TeMN (see Table 1 for abbreviations), differentiating Potwar Basin oils into the three groups. Group A is placed
in the right top corner of the cross plot (Fig. 4a) indicating higher
abundance of 1,2,5-TMN and 1,2,5,6-TeMN relative to 1,2,7-TMN
and 1,2,5,7-TeMN, respectively. b-Amyrin and aromatic seco-hopanes have been reported to be the source precursors for 1,2,5TMN and 1,2,5,6-TeMN isomers (Pttmann and Villar, 1987). In
contrast, non-angiosperm biological precursors are also related to
the source origin of 1,2,5-TMN and 1,2,5,6-TeMN (Armstroff
et al., 2006). Abundance of the 1,2,5-TMN and 1,2,7-TMN isomers
have been related to higher plant angiosperm markers and derived
from oleanane type biological precursors (Strachan et al., 1988).
The 1,2,5-TMN isomer is also supposed to be formed from dehydrogenation of a different biological constituent present in gymnosperms (Thomas, 1969; Carman and Craig, 1971). Similarly, higher
abundance of both 1,2,5-TMN and 1,2,5,6-TeMN has been reported
in aromatic fractions of the uorinite lling of needles from Abietites linkii, a gymnosperm source (Heppenheimer et al., 1992).
These observations lead to the result that the predominance of
these isomers in aromatic HC fractions of crude oils and sediments
can be used for source characterization. In the Potwar Basin 1,2,7TMN is signicantly less abundant relative to 1,2,5-TMN in group A

(a)

4.0

3.5
3.0

2.5
2.0
C

1.5
1.0
0.5
0.0
0.0

0.5

1.0

1.5

2.0

1,2,5,6-/1,2,5,7-TeMN

(b)

0.6
A

0.5
0.4

0.3

0.2
0.3

0.4

0.5

0.6

0.7

0.8

0.9

1-MP/9-MP
Fig. 4. Classication of Potwar Basin oils using plots between the ratios of
naphthalene and phenanthrene isomers, a) 1,2,5-/1,2,7-TMN versus 1,2,5,6-/
1,2,5,7-TeMN ratios (b) 1,7-DMP/X versus 1-MP/9-MP ratios (Alexander et al.,
1992b).

oil which documents the presence of non-angiosperm biological


precursors for 1,2,5-TMN and hence 1,2,5,6-TeMN. This outcome
is, to some extent, further supported by the absence of oleanane
(an angiosperm biomarker) and its related natural products in
the saturated HC fraction (Asif et al., 2011). These results reveal
that the source of 1,2,5-TMN and 1,2,5,6-TeMN in group A oil is
most likely gymnosperms. The presence of higher plant aromatic
biomarkers is also indicative of this (see below). The fact that the
1,2,5,6-/1,2,5,7-TeMN ratio is mostly less than or equal to 1 for
group B and C oils suggests the predominance of 1,2,5,7-TeMN;
1,2,5,7-TeMN is suggested to originate from microbial methyl tetralins (Alexander et al., 1992a). This result supports the premise
that the source of groups B and C oils is marine OM. The relative
abundance of the 1,3,6,7-TeMN isomer in sedimentary OM is another indicator of microbial input (van Aarssen et al., 2000). The ratio between microbial to land plant origin isomers, i.e. 1,3,6,7-/
1,2,5,6-TeMN is calculated to determine the extent of microbial
OM contributions in Potwar Basin crude oils (Table 1). This ratio
is mostly higher than 3 for group B and 9 for group C oils, clearly
indicating a higher contribution of microbial input in these oils.
Moreover, different values of this ratio, for both group B and C oils,
differentiate them from each other and indicate differences in
source OM origin.
Differing relative abundances of various alkylphenanthrenes
have been related to source origins such as, a higher abundance of
9-MP has been attributed to marine OM while predominance of 1MP has been attributed to terrigenous OM (Budzinski et al., 1995).
The ratios between these different origin isomers could be used to
determine the contribution of source OM in sediments and crude
oils. 1,7-DMP has been suggested as a biomarker of pimarane type
diterpenoids abundant in ambers and resins (Thomas, 1969; Simoneit et al., 1986). The 1,7-DMP/X ratio (see Table 1) (Radke et al.,
1986) has been successfully used in oil correlation studies to determine different sources and ages of the OM (Alexander et al., 1992b).
A cross plot of 1-MP/9-MP versus 1,7-DMP/X ratios (Fig. 4b) also
separates Potwar Basin oils into the three groups, where group A

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1.8

Retene/9-MP

0.18

Retene/9-MP
2-methylretene/9-MP

Eromanga

0.12

1.2

Cooper

0.6
Gippsland

Potwar
group A

0.06

Carnarvon

DBT

2-Methylretene/9-MP

1660

B
C

Sydney
Zhanhua

0
0

0
2

Pr/Ph
Fig. 5. A three value plot showing the comparison of abundances of retene and 9methyl retene in Potwar Basin (group A oil) with oils from different basins of the
world (Bastow et al., 2001).

DBF

Fig. 6. A triplot of relative amounts of DBT, DBF and F differentiating Potwar Basin
oils into the same three groups.

is found to possess higher values for both ratios. This higher abundance of 1-MP and 1,7-DMP indicates a terrigenous source origin
for these isomers and hence for group A oil. Both group B and C oils
show close positions in the 1-MP/9-MP versus 1,7-DMP/X cross plot
(Fig. 4b) but the 1,7-DMP/X ratios are higher for group C oils separating them from group B oils.
The distributions of alkylnaphthalene and alkylphenanthrene
isomers show that the group A oil is terrigenous and group B and
C oils are marine. This is further supported by the presence of typical
terrigenous aromatic biomarkers, i.e. cadalene, retene and methyl
retenes. Retene has been suggested to be the diagenetic product of
abietic acid type biological precursors present as major constituents
of conifer resins (van Aarssen et al., 2000; Hautevelle et al., 2006).
Similarly, 2-methyl retene has been suggested to be derived from
higher plant diterpenoid biological precursors (Bastow et al.,
2001). Retene/9-MP and 2-methyl retene/9-MP ratios are plotted
against Pr/Ph from group A oil and some oils from the worlds different basins (Fig. 5). These oils have been reported to have originated
from OM of higher plant input (Ellis et al., 1995; Bastow et al., 2001).
Group A oil located in the middle of the plot (Fig. 5) shows the signicant presence of retene as well as 2-methyl retene relative to the
plotted oils of the world. This comparison shows that the group A oil
is generated from source rocks containing higher plant input. Moreover, the abundance of retene and 2-methyl retene in conjunction
with 1-MP and 1,7-DMP reveals that the origin of these compounds
is abietane type diterpenoids (Alexander et al., 1995; Tuo and Philp,
2005). Cadalene is another terrigenous marker in crude oils and sediments, but its origin is not specic and it occurs in various types of
vascular plants (van Aarssen et al., 2000; Romero-Sarmiento et al.,
2011). Cadalene is also observed in noticeable abundance only in
the group A oil aromatic hydrocarbon fraction. The occurrence of
these aromatic biomarkers clearly suggests that the source OM
of group A is terrigenous and this differentiates this group from
other groups of Potwar Basin oils.
3.3. Dibenzothiophenes, dibenzofurans and uorenes in Potwar Basin
oils
The distributions of heterocyclic aromatic HCs have been related
to the source rock lithology and depositional environment of the
OM (Hughes, 1984; Schou and Myhr, 1988; Jinggui et al., 2005).
Whereas, the abundance of S-containing heterocyclic aromatic
HCs, i.e. DBT and alkyldibenzothiophenes have been related to marine source rocks while abundance of O-containing heterocyclic
aromatic HCs, i.e. DBF and alkyldibenzofurans, and alkyluorenes

have been referred to oxic/freshwater source rocks (Fan et al.,


1990; Radke et al., 2000; Xiangchun et al., 2011).
The relative abundances of DBT, DBF and F are determined from
the sums of the peak areas of their diagnostic ions (m/z: 184, 168,
166, respectively) and are shown in Table 1. A triplot of these values
clearly discriminates Potwar Basin oils into three groups (Fig. 6).
Crude oils from group B that show marine suboxic depositional
environments are near to the DBT maximum. Crude oils from group
C that show marine oxic depositional environment are near to the F
maximum. The highly oxic/deltaic depositional environment oil
from group A is located away from the DBT and F maxima and is
found comparatively near to the maximum of DBF. These results
demonstrate the use of heterocyclic aromatic HCs for oil correlations on the basis of depositional environments. This interpretation
is further supported using relative percentages of alkyldibenzothiophenes, alkyldibenzofurans and alkyluorenes which are plotted
on a histogram as shown in Fig. 7. Group A shows higher relative
percentages of alkyluorenes and alkyldibenzofurans while group
B oils show signicantly higher amounts of alkyldibenzothiophenes. Group C oils show predominance of alkyldibenzothiophenes
and alkyluorenes. These results again classify Potwar Basin oils
into the same three groups. It is notable that source rocks of
oxic/deltaic depositional settings produced higher amounts
of alkyluorenes and alkyldibenzofurans. In contrast, predominance of alkyldibenzothiophenes reveal that source rocks from a
marine suboxic depositional environment produced higher
amounts of S-containing heterocyclic aromatic HCs. On the other
hand marine oxic to freshwater depositional environment source
rocks produced higher alkyluorenes and alkyldibenzothiophenes.
These interpretations fortify the use of heterocyclic aromatic HCs
for both oil correlations and the determination of source rock depositional environments.
3.4. Triaromatic steroids in Potwar Basin oils
The distribution of triaromatic steroids (m/z: 231) from each
group of Potwar Basin oils is shown in Fig. 8 and they are divided
into short chain (C19C22) and long chain (C25C28) compounds. As
can be seen, short chain C20 and C21 triaromatic steroids are present
in signicantly higher abundance than long chain triaromatic steroids in group B and C oils, while the distribution of long chain triaromatic steroids between the groups clearly differentiates Potwar
Basin oils into three groups (Fig. 8). The group A ion chromatogram

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alkyldibenzothiophenes

Alkylfluorenes

Triaromatic steroids m/z: 231

(a) Group A
P-1

alkyldibenzofurans
C20

P18

Group C

C21

P17
P16

C27,S

C28,S
C28,R
C27,R

P15
C20

P14

(b) Group-B
P-6

R C22
S

P13

Relative intensity

C26,R+C27,S

Group B

P12

Sample no

P11
P10

C21
C26,S
C28,S

C28,R

C25,S
C25,R

C27,R

C19

P9

(c) Group-C
P-18

P8
P7
P6
P5
P4
72

P3

Group A

P2
P1

20

40

60

76

80

84

92

88

Relative retention time (min)


Fig. 8. Distribution of the triaromatic steroids in Potwar Basin crude oils is shown
by mass selective ion 231 of the aromatic HC fractions. Carbon numbers on peaks
refer to triaromatic steroid compounds while S and R represent stereochemistry at
C20.

80

Relative percentage
Fig. 7. A histogram constructed from relative percentages of alkyldibenzothiophenes, alkyldibenzofurans and alkyluorenes (see Table 1 for data) in three groups of
oils from the Potwar Basin.

shows only C27 and C28 triaromatic steroids while the group B representative ion chromatogram shows C25C28 triaromatic steroids

Table 2
Thermal maturity and source OM parameters from saturated biomarkers, triaromatic and methyl triaromatic steroids for Potwar Basin oils.
No

(bb/aa + bb)
C29Stereranes

(S/S + R)
C29steranes

MPI1

Rc
(%)

Ts/
(Ts + Tm)

C28/C27
20R
steranes

C28/C27
diasteranes

C27/C28 20R
triaromatic
steroids

S/(S + R) C28
triaromatic
steroids

C21/C22 methyl
triaromatic
steroids

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

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

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

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

0.37
0.18
0.33
0.22
0.16
0.24
0.23
0.19
0.22
0.21
0.34
0.27
0.24
0.24
0.97
0.79
0.78
1.06

1.4
0.4
0.8
0.5
0.6
0.5
0.4
0.5
0.5
0.5
0.6
0.8
0.4
0.5
0.8
0.47
0.33
0.89

0.92
0.63
0.58
0.56
0.58
0.64
0.83
0.73
0.66
0.43
0.56
0.49
0.75

0.59
0.51
0.50
0.55
0.55
0.54
0.54
0.53
0.55
0.50
0.52
0.51
0.60

3.2
2.5
4.8
4.0
3.5
3.1
4.1
2.5
4.6
4.1
4.1
3.4
1.5
1.1
2.0
0.6
0.6

MPI-1: methyl phenanthrenes index {1.5  [3


steroids: Peaks 1/2 in Fig. 10.

MP + 2

MP]/[P + 1

MP + 9

MP]}; Rc: calculated vitrinite reectance (0.6  MPI

Relative
percentages
triaromatic
steroids
C19

C20

C21

42
5
5
3
3
3
4
3
6
2
2
2
4
12
14
14
12
12

37
52
53
63
62
61
60
61
57
66
68
69
57
43
42
44
46
45

21
43
42
34
35
36
36
36
37
32
30
29
40
45
44
42
41
43

1 + 0.4); C21/C22 methyl triaromatic

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3.5. Methyl triaromatic steroids in Potwar Basin oils


Methyl substituted triaromatic steroids are determined using
their characteristic ion 245 in aromatic HC fractions of the Potwar
Basin crude oils (Fig. 10). Only short chain C20C22 methyl

(a)

C19

C
B

C21
0.60

C20
1.8

C28/C27 20R, Steranes


Series1
C28/C27 diasteranes
Series2

1.4

C28 /C27, diasteranes

(b)
C28 /C27 20R, Steranes

(Fig. 8). The absence (or below detection limit) of long chain triaromatic steroids in the group C oil representative ion chromatogram
differentiates this group from other groups (Fig. 8). Therefore, it is
very reasonable to consider that three dissimilar distributions of
triaromatic steroids are present in the Potwar Basin oils.
Triaromatic steroids from C26 to C28 compounds are supposed to
originate from demethylation and aromatization of monoaroamtic
steriods from corresponding C27 to C29 compounds (Riolo et al.,
1986; Peters et al., 2005). On the other hand short chain triaromatic steroids appear to have been generated from homolytic scission
of long chain triaromatic steroids with an increase in thermal
maturity (Seifert and Moldowan, 1978; Mackenzie et al., 1981).
Signicantly higher abundances of C20 and C21 triaromatic steroids
relative to long chain triaromatic steroids and a comparatively
negligible presence of C19 and C22 triaromatic steroids indicate factors other than thermal maturity affecting short chain triaromatic
steroids distributions (Fig. 8). Biomarker thermal maturity parameters, the (bb/aa + bb) and S/(S + R) ratios for ethylcholestane falls
in narrow ranges of 0.590.66 and 0.410.48, respectively, suggesting no major differences in thermal maturity of the Potwar Basin
oils (Table 2). Aromatic HC maturity parameters such as MPI-1
and calculated vitrinite reectance (Rc) values indicate a small variation in thermal maturity of Potwar Basin oils. MPI-1 and Rc values
for group A oil are 0.75 and 0.85, respectively, indicating a peak oil
generation window of thermal maturity while higher values are
observed for group B and C oils (0.851.26, 0.881.2, respectively)
suggesting a peak to late oil generation window of thermal maturity (Table 2). These results indicate that group A oil is less mature
than group B and C oils. The triaromatic steroids maturity parameter, S/(S + R) for the C28 compound, is available for group A and B
oils (Table 2), while this compound is absent in group C oils. Values
(0.510.60) for this parameter are indicative of a similar range of
thermal maturity for these oils. Therefore, while the thermal maturity of Potwar Basin oils show little difference, the distribution of
short chain triaromatic steroids shows differences between the
oil groups. Oil correlation is further determined using a triplot of
relative abundances of C19, C20 and C21 triaromatic steroids available for all three groups (Fig 9a and Table 2) which clearly shows
that the same three groups are present in the Potwar Basin. Long
chain triaromatic steroids show an odd distribution, where the
presence of only two compounds (C27 and C28) is detected in the
group A oil, C25C28 compounds are detected in the group B oils,
and their complete absence is observed in the group C oils. The
source origin of these compounds in Potwar Basin oils is questionable. In combination with the results from thermal maturity evaluation and short chain triaromatic steroids, it is reasonable to
suggest that the long chain triaromatic steroids in Potwar Basin
oils are generated from different source precursors for each group.
Typical source precursors for these compounds, i.e. regular and
rearranged steranes (C27, C28, C29), are signicantly abundant in
all Potwar Basin oils (Asif et al., 2011). The C27/C28 ratio for 20R
triaromatic steroids has been shown to be source dependent and
has been used for source to oil correlations (Picha and Peters,
1998). This ratio from Potwar Basin oils is compared to source
OM biomarker parameters from steranes and diasteranes (Table
2) and a three values plot is shown in Fig. 9b. Both group A and
B oils are clearly discriminated from each other. These ndings reveal that the abundance of triaromatic steroids in Potwar Basin oils
are source/depositional environment dependent and this data is
valuable for making source to oil correlations.

0.40

1.0
0.6
0.20

0.2
0.00
0.00

0.40

-0.2
1.20

0.80

C27 /C28 , 20R, Triaromatic steroids

(c)

C21 /C22 methyltriaromtic steroids

1662

5.0
4.0
B

3.0

2.0
1.0
0.0
0.0

0.2

0.4

0.6

0.8

Ts/(Ts+Tm)
Fig. 9. Classication of Potwar Basin oils based on the triaromatic steroids
distribution, (a) triplot between the relative percentages of short chain triaromatic
steroids (C19, C20 and C21), (b) relationship of the three different ratios, one from
long chain triaromatic steroids i.e. C27/C28 20R and two, each from steranes and
diasteranes i.e. C28/C27 20R and C28/C27, respectively, (c) variation in C21/C22 ratio of
methyl triaromatic steroids (peaks 1/2, see Fig. 10) and Ts/(Ts + Tm) separating out
group B oils from group C oils.

triaromatic steroids were identied using mass spectra (Fig. 10)


while long chain methyl triaromatic steroids were absent or below
detection limit (see chromatogram at bottom of Fig. 10). These ion
chromatograms also show a repetition of clusters of peaks. These
are methyl isomers of a methyl triaromatic steroid compound tentatively identied from mass spectral data and the literature (Lichtfouse, 1989; Lichtfouse and Albrecht, 1994; vilaa et al., 2011).
Methyl substitution in isomers at different positions of triaromatic
nuclei, such as the 1-, 2-, 3-, 4- and 6-methyl positions, (see Fig. 10
for numbering) has been reported in sedimentary OM and these
are reasonably well related to biological origin (Lichtfouse et al.,
1990, 1993). Similar to triaromatic steroids, the methyl triaromatic
steroids are supposed to be formed from methyl steranes and
related precursors by aromatization in the sedimentary environments (Peters et al., 2005). Methyl substituted steranes have been
related to biological source precursors and are recommended for

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M. Asif, T. Fazeelat / Applied Geochemistry 27 (2012) 16551665

Group A

C 20 H 20

245

C21 H22

C22 H24

215

231

260

202
189
114

55

152

68

100

Group B
b

200

300

245

c
215

274

229
55

114
101

100

259

202
189

200

245

300

Group C
215
229
114

60

75

77

79

100

259

288

202
189

200

300

81

Relative retention time (min)

m/z: 245

Fig. 10. Representative ion chromatograms m/z 245 for methyl triaromatic steroids from each group of the Potwar Basin oils. The three methyl triaromatic steroids are
identied using mass spectra (small letters are used to show the mass spectra of corresponding peaks). Chromatogram at the bottom of the gure showing extended region of
ion 245 to show the absence (or presence below the detection limit) of long chain methyl triaromatic steroids.

correlation studies (Summons and Capon, 1988, 1991; Summons


et al., 1992; Lopes et al., 1997). In Potwar Basin oils, an interesting
aspect is the presence of only C20C22 compounds from the methyl
triaromatic steroids where C21 and C22 compounds are abundant
(Fig. 10). Group A contains only two methyl isomers, each from
C21 and C22 methyl triaromatic steroids that distinguishes this
group from other groups. Group B and C ion chromatograms show
at least four to ve methyl isomers of each of these compounds

(Fig. 10). It is apparent that reasonable difference in the distribution of methyl isomers of these compounds is present in group B
and C representative ion chromatograms. This observation is reinforced using a plot between the ratio of C21/C22 methyl triaromatic
steroids of selected methyl isomers and Ts/(Ts + Tm) (Fig. 9c and
Table 2), where the Ts/(Ts + Tm) ratio has been related to the
source/depositional environment of source rocks for the Potwar
Basin oils (Asif et al., 2011). The plot clearly differentiates group

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B and C oils and shows that the methyl triaromatic steroids distribution supports the classication of Potwar Basin oils.
The reason for the higher abundance of C20 and C21 triaromatic
steroids and C21 and C22 methyl triaromatic steroids in Potwar Basin oils is unknown. A possible explanation could be the extent of
thermal maturity, which would increase the abundance of short
chain triaromatic steroids (Peters et al., 2005). Conversely, thermal
maturity results do not show sufcient signicant variation to be
the reason for such differences in distribution between long chain
and short chain triaromatic steroids. Therefore, it is easy to suggest
that triaromatic and methyl triaromatic steroids in the Potwar Basin are source dependent. Short chain steranes and methyl steranes
may be the direct precursors for these short chain triaromatic and
methyl triaromatic steroids, respectively, in the Potwar Basin oils
from unknown biological origin (Lichtfouse et al., 1990, 1993).
4. Conclusions
The distribution and relative amounts of heterocyclic and polycyclic aromatic HCs support the previous classication of Potwar
Basin crude oils into the three groups (A, B and C). A highly oxic
environment of deposition and enrichment in terrigenous OM is
the characteristics of group A oil. Abundance of specic methyl isomers from naphthalene and phenanthrene indicate higher plant input from gymnosperms. Diagnostic aromatic biomarkers such as
retene, methyl retenes and cadalene also reveal the higher plant
resin contributions to group A oil OM. Groups B and C are marine
oils. Difference in source and depositional environment of OM discriminates them into two groups. Heterocyclic aromatic HCs provide good indicators for the depositional environments whereas
the abundance of alkyluorenes and alkyldibenzofurans can be related to the oxic/deltaic depositional environment and terrigenous
source OM. Source rocks deposited in marine suboxic depositional
environments generate an abundance of S-containing heterocyclic
aromatic HCs while marine oxic oils show an abundance of alkyluorenes in conjunction with S heterocyclic compounds. The distribution of triaromatic and methyl triaromatic steroids clearly
classied Potwar Basin oils into the same three groups. The relative
abundance and odd distribution of these compounds in the Potwar
Basin is source and depositional environment dependent. The thermal maturity of Potwar Basin oils is indicative of a peak to late oil
generation window which is determined from biomarker, aromatic
HC and triaromatic steroid maturity parameters.
Acknowledgements
The authors are very grateful to the Director WA-OIGC Perth,
Australia for provided an opportunity to conduct this research
work. The authors also thank Mr. G. Chidlow for assistance with
GCMS analysis. The Higher Education Commission, Islamabad,
Pakistan is thanked for an IRSIP fellowship and a travel award
Grant (IRSIP-5-Ps-20) to M. Asif. The authors are grateful to the following exploration companies for providing crude oil samples: Oil
and Gas Development Cooperation Ltd. (OGDCL), Islamabad, Pakistan Petroleum Ltd. (PPL) and Pakistan Oilelds Ltd. (POL). Asif is
thankful to his friends Karl J. Jalkanen from California and Muneeb
Rathore from UET, KSK campus for help in revision of this manuscript. Professor Simon George, Dr. Zhibin Wei, Dr. Haiping Huang
and Professor Ron Fuge are acknowledged for constructive reviews
and editorial handling.
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