This article appeared in a journal published by Elsevier.

The attached copy is furnished to the author for internal non-commercial research and education use, including for instruction at the authors institution and sharing with colleagues. Other uses, including reproduction and distribution, or selling or licensing copies, or posting to personal, institutional or third party websites are prohibited. In most cases authors are permitted to post their version of the article (e.g. in Word or Tex form) to their personal website or institutional repository. Authors requiring further information regarding Elseviers archiving and manuscript policies are encouraged to visit: http://www.elsevier.com/copyright

Author's personal copy

Organic Geochemistry 42 (2011) 12261240

Contents lists available at SciVerse ScienceDirect

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

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.

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

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. API gravity dDsats () 117 155 132 149 126 132 136 130 145 145 148 129 129 139 139 122 21.8 23.5 23.6 23.8 23.7 25.4 137 142 143 126 111 130 125 135 132 141 136 134 25.4 21.9 21.7 22.0 22.5 22.2 21.7 21.6 114 142 128 142 129 137 136 132 0.16 0.17 0.22 0.52 0.45 0.43 0.37 0.39 0.33 0.66 0.84 0.93 0.31 0.27 0.26 0.26 0.25 0.16 dDaros () dDaver () 48.0 36.2 33.0 19.3 22.7 26.6 25.0 23.2 25.0 18.4 16.0 16.1 16.0 40.0 45.0 46.0 38.4 41.1 1.6 1.6 0.6 0.8 0.4 0.6 1.0 1.0 1.0 1.0 26.1 26.1 21.5 21.4 1.4 0.9 0.7 1.0 1.0 25.1 22.1 1.4 0.9 0.7 1.0 1.0 25.0 22.0 1.5 0.8 0.5 1.0 1.0 23.1 20.5 1.2 1.1 0.8 1.0 0.9 22.3 21.0 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 26.4 23.1 22.4 23.0 22.9 22.6 23.0 22.3 24.5 20.8 21.0 21.1 22.2 21.9 21.1 21.1 Pr/Pha Pr/n-C17b Ph/n-C18c
g

Sample name

Depth (m)

Reservoir

CPId

OEPe

Formation

Age

d13Csatsf ()

d13Caros ()

d13Caverh ()

DBT/Pi

Group

BLj

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

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

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

A B B B B B B B B B B B B B C C C C

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

P13

3612

Eocene

P14

Eocene

P15

4096

Eocene

P16

4174

Eocene

Author's personal copy

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

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

Jurassic Jurassic

: 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).

1227

Author's personal copy

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).

Author's personal copy

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).

Author's personal copy

1230

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

Author's personal copy

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

1231

C17

Relative abundance

Pr d c Ph b a e

C25

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)
13CAros ()

-20.0

B C

-21.0

-22.0

-23.0

-24.0

-25.0 -27.0

-26.0

-25.0
13

-24.0

-23.0

-22.0

CSats ()

(b)
Daver ()

-100

-110

-120

C
-130

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. 3.3. Thermal maturity of Potwar Basin crude oils 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

-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

Author's personal copy

1232

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),
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

ab/(ab + ba),
C30-Hopc 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

S/(S + R) C32-Hopd 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

bb/(aa + bb) C29-Stere 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

S/(S + R) C29-sterf 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

DNR-1g 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

TNR-1h 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

TNR-2i 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

Rcbj (%) 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

MPI-1k 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

Rcl (%) 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. Sample name C19/ (C19 + C23) TTa 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 C24TeT/ (C24TeT + C23TT)b C23 TT/C30 Hopc 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 C24TeT/ C30 Hopd 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 C28TT/ C30Hope 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 C29/ C30 ab hopf 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 Dia/ hop C30g 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 C30 Dia/ C29 Tsh 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 C31(R + S)/ C30 hopi Steranes/ hopanesj Dia/ ster C27k 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 Dia/ Ster C29l 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 Total Dia/ Sterm 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 C27 abb C28 abb C29 abb

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

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

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

0.77 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

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.

Author's personal copy

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

1233

(a) 1.00
/(+), C30-Hop
0.95

(a)
Equilibrium

1A
3

1B

DBT/P

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

0.90

Early oil generation

0.85

2
0 0.0 1.0

3
2.0

B&C
3.0

A
4.0

0.80 3.5 3 2.5

Pr/Ph

0.75 0.75

(b)
0.80 0.85 0.90 0.95 1.00

/(+), C29-Hop Pr/Ph

C
2 1.5 1

(b)

1.2 1.1 1.0

Late

Rc (%)

0.5 0.9 0.8

10

20

30

40

50

Peak

API gravity () Diasterane/steranes, C29

0.7 0.6 0.6

Early

(c)
0.8 0.9 1.0 1.1 1.2

1.0 0.8

A B P14

0.7

0.6 0.4

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.

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

Author's personal copy

1234

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

30H

(a) Group-A Sample: P1

19 24*

30H 29H

(b) Group-B Sample: P10

Tm

Relative intensity

24* 23 21 19 20 Ts 29Ts

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

35H S R

23 20 21 19 25 28 29 30 31 32 33 34 24 24* 30H 29H

(c) Group-C Sample: P15

35 36

38 39

40 41

61

71

81

91

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

Author's personal copy

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

1235

(a)

C24 tetracyclic terpane/(C24 tetracyclic terpane+C23

0.8

A
0.7

Terrigenous

tricyclic terpane)

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

(b)
C28/C27,20R, , steranes

1.0

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

Author's personal copy

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

Group-A

C 29

13 , 17 14 , 17 14 , 17

Group-A
C25

C 27 C28 C 27 C 28

C29

C10

C35

Group-B Relative Response

Diasteranes

Steranes

Group-B

Relative intensity

UCM

Group-C

Group-C

81

85

89 20 40 60 80 100 120

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.

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.

Author's personal copy

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

1237

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

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

(a)

1.2 1 0.8 0.6 0.4 0.2 0 0.2 0.4 0.6 0.8 1 1.2

Biodegradation
P11,P12 P15 P16 P14,P18 P17 P1 P2 P3 P8 P13 P10 P7 P6

Ph/n-C18

1.4

1.6

Pr/n-C17

(b)
API gravity ()

60 50 40 30

P1 P17

P15,P16 P14,P18 P2 P3 P8 P13 1.2 P4-5 P11-12 P6

P9
20 10

Biodegradation
0 0.2 0.4 0.6 0.8 1 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.

Author's personal copy

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).

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

References
Aamir, M., Siddiqui, M.M., 2006. Interpretation and visualization of thrust sheets in a triangle zone in eastern Potwar, Pakistan. The Leading Edge January 2006, pp. 2437. Ahmed, W., Alam, S., 1990. Organic geochemistry of crude oil from Potwar-Kohat region. Pakistan Journal of Hydrocarbon Research 2, 115. Ahmed, W., Alam, S., 2007. Organic geochemistry and source rock characteristics of Salt Range Formation, Potwar Basin, Pakistan. Pakistan Journal of Hydrocarbon Research 17, 3759. Alexander, R., Kagi, R.I., Rowland, S.J., Sheppard, P.N., Chirila, T.V., 1985. The effects of thermal maturity on distributions of dimethylnaphthalenes and trimethylnaphthalenes in some ancient sediments and petroleums. Geochimica et Cosmochimica Acta 49, 385395. Andrusevich, V.E., Engel, M.H., Zumberge, J.E., Brothers, L.A., 1998. Secular, episodic changes in stable carbon isotope compositions of crude oils. Chemical Geology 152, 5972. Asif, M., Grice, K., Fazeelat, T., Dawson, D., 2008. Oiloil correlation in the Upper Indus Basin (Pakistan) based on biomarker distributions and compound-specic d13C and dD. In: 15th Australian Organic Geochemistry Conference, 812th September, National Wine Centre, Adelaide, SA, Australia. Asif, M., Grice, K., Fazeelat, T., 2009. Assessment of petroleum biodegradation using stable hydrogen isotopes of individual saturated hydrocarbons and polycyclic aromatic hydrocarbon distributions in oils from the Upper Indus Basin, Pakistan. Organic Geochemistry 40, 301311. Bishop, A.N., Abbott, G.D., 1993. The interrelationship of biological marker maturity parameters and molecular yields during contact metamorphism. Geochimica et Cosmochimica Acta 57, 36613668. Chung, H.M., Rooney, M.A., Toon, M.B., Claypool, G.E., 1992. Carbon isotope compositions of marine crude oils. American Association of Petroleum Geologist Bulletin 76, 10001007. Collister, J.W., Wavrek, D.A., 1996. d13C compositions of saturated and aromatic fractions of lacustrine oils and bitumen: evidence for water column stratication. Organic Geochemistry 24, 913920.

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

Author's personal copy

M. Asif et al. / Organic Geochemistry 42 (2011) 12261240 Connan, J., 1984. Biodegradation of crude oils in reservoirs. In: Brooks, J., Welte, D.H. (Eds.), Advances in Petroleum Geochemistry, vol. 1. Academic Press, London, pp. 299335. Dawson, D., Grice, K., Alexander, R., 2005. Effect on maturation on the indigenous dD signatures of individual hydrocarbons in sediments and crude oils from the Perth Basin (Western Australia). Organic Geochemistry 36, 95104. Dawson, D., Grice, K., Edwards, D.S., Alexander, R., 2007. The effect of source and maturity on the stable isotopic compositions of individual hydrocarbons in sediments and crude oils from the Vulcan Sub-basin, Timor Sea, Northern Australia. Organic Geochemistry 38, 10151038. Edwards, D.S., Summons, R.E., Kennard, J.M., Nicoll, R.S., Bradshaw, M., Foster, C.B., OBrien, G.W., Zumberge, J.E., 1997. Geochemical characteristics of Palaeozoic petroleum systems in Northwestern Australia. Australian Petroleum Production & Exploration Association Journal 37, 351379. Farah, A., Abbas, G., DeJong, K.A., Kees, A., Lawrence, R.D., 1984. Evolution of the lithosphere in Pakistan. Tectonophysics 105, 207227. Farrimond, P., Bevan, J.C., Bishop, A.N., 1999. Tricyclic terpane maturity parameters: response to heating by an igneous intrusion. Organic Geochemistry 30, 1011 1019. Fazeelat, T., 1994. 8,14-secohopanes and related compounds: their occurrence in sediments and applications to oil-source correlation. PhD thesis, Curtin University of Technology, Perth, Australia. Fazeelat, T., Jalees, M.I., Bianchi, T.S., 2010. Source rock potential of Eocene, Paleocene and Jurassic deposits in the subsurface of the Potwar basin, northern Pakistan. Journal of Petroleum Geology 33, 8796. Fazeelat, T., Asif, M., Jalees, M.I., Saleem, A., Saleem, H., Nazir, A., Nasir, S., Nadeem, S., 2011. Source correlation between biodegraded oil seeps and a commercial crude oil from Punjab Basin, Pakistan. Journal of Petroleum Science and Engineering 77, 19. Fisher, S.J., Alexander, R., Kagi, R.I., Oliver, G.A., 1998. Aromatic hydrocarbons as indicator of biodegradation in north western Australian reservoirs. In: Purcell, P.G., Purcell, R.R. (Eds.), The Sedimentary Basins of Western Australia 2: Proceedings of Petroleum Exploration Society of Australia Symposium. Perth, WA, pp. 185194. George, S.C., Ruble, T.E., Dutkiewicz, A., Eadington, P.J., 2001. Assessing the maturity of oil trapped in uid inclusions using molecular geochemistry data and visually-determined uorescence colours. Applied Geochemistry 16, 451473. George, S.C., Lisk, M., Eadington, P.J., 2004. Fluid inclusion evidence for an early, marine-sourced oil charge prior to gas-condensate migration, Bayu-1, Timor Sea, Australia. Marine and Petroleum Geology 21, 11071128. Grice, K., Audino, M., Alexander, R., Boreham, C.J., Kagi, R.I., 2001. Distributions and stable carbon isotopic compositions of biomarkers in torbanites from different palaeogeographical locations. Organic Geochemistry 32, 1952110. Grice, K., Backhouse, J., Alexander, R., Marshall, N., Logan, G.A., 2005. Correlating terrestrial signatures from biomarker distributions, d13C, and palynology in uvio-deltaic deposits from NW Australia (TriassicJurassic). Organic Geochemistry 36, 13471358. Grice, K., De Mesmay, R., Wang, S., de Glucina, A., 2008. New 5A molecular sieving method for CSIA. Organic Geochemistry 39, 284288. Grimalt, J.O., Campos, P.G., Berdie, L., Lopez-Quintero, J.O., Navarrete-Reyes, L.E., 2002. Organic geochemistry of the oils from the southern geological province of Cuba. Applied Geochemistry 17, 110. Hughes, W.B., Holba, A.G., Dzou, L.I., 1995. The ratio of dibenzothiophene to phenanthrene and pristane to phytane as indicators of depositional environment and lithology of petroleum source rocks. Geochimica et Cosmochimica Acta 59, 35813598. Hunt, J.M., 1995. Petroleum Geochemistry and Geology. W.H. Freeman and Company, New York, pp. 743. Isaksen, G.H., Bohacs, K.M., 1995. Geological controls of source rock geochemistry through relative sea level; Triassic, Barents Sea. In: Katz, B.J. (Ed.), Petroleum Source Rocks. Springer, Berlin, pp. 2550. Jiang, C., Li, M., 2002. Bakken/Madison petroleum systems in the Canadian Williston Basin, Part 3: geochemical evidence for signicant Bakken-derived oils in Madison group reservoirs. Organic Geochemistry 3, 761787. Khan, M.A., Ahmed, R., Raza, H.A., Kemal, A., 1986. Geology of petroleum in KohatPotwar Depression, Pakistan. American Association of Petroleum Geologists Bulletin 70, 396414. Maslen, E., Grice, K., Gale, J., Hallmann, C., Horseld, B., 2009. Crocetane: a potential marker of photic zone euxinia in thermally mature sediments and crude oils of Devonian age. Organic Geochemistry 49, 117. Maslen, E., Grice, K., Dawson, D., Le Metayer, P., Edwards, D., 2011. Stable carbon isotopic compositions of individual aromatic hydrocarbons as source and age indicators in oil from Western Australian Basins. Organic Geochemistry 42, 387398. Moldowan, J.M., Sundararaman, P., Schoell, M., 1986. Sensitivity of biomarker properties to depositional environment and/or source input in the Lower Toarcian of SW, Germany. Organic Geochemistry 10, 915926. Moldowan, J.M., Fago, F.J., Carlson, R.M.K., Young, D.C., Duvne, G.A., Clardy, J., Schoell, M., Pillinger, C.T., Watt, D.S., 1991. Rearranged hopanes in sediments and petroleum. Geochimica et Cosmochimica Acta 55, 33333353. Murphy, M.T.J., 1969. Analytical methods. In: Eglinton, G., Murphy, M.T.J. (Eds.), Organic Geochemistry. Springer, Berlin, pp. 7488. Murray, A.P., Boreham, C.J., 1992. Organic Geochemistry in Petroleum Exploration. Australian Geological Survey Organization, Canberra, 230pp. Nabbefeld, B., Grice, K., Twitchett, R.J., Summons, R.E., Hays, L., Bttcher, M.E., Asif, M., 2010a. An integrated biomarker, isotopic and palaeoenvironmental study

1239

through the Late Permian event at Lusitaniadalen, Spitsbergen. Earth and Planetary Science Letters 291, 8496. Nabbefeld, B., Grice, K., Summons, R.E., Hays, L., 2010b. Signicance of polycyclic aromatic hydrocarbons (PAHs) in Permian/Triassic boundary sections. Applied Geochemistry 25, 13741382. Obermajer, M., Osadetz, K.G., Fowler, M.G., Silliman, J., Hansen, W.B., Clark, M., 2002. Delineating compositional variabilities among crude oils from central Montana, USA, using light hydrocarbon and biomarker characteristics. Organic Geochemistry 33, 13431359. Obermajer, M., Osadetz, K.G., Fowler, M.G., Li, M., Snowdon, L.R., 2004. Variable alteration in heavy crude oils of west-central Saskatchewan, Canada. Organic Geochemistry 35, 469491. Ourisson, G., Albrecht, P., Rohmer, M., 1982. Predictive microbial biochemistry from molecular fossils to prokaryotic membranes. Trends in Biochemical Science 7, 236239. Pasadakis, N., Obermajer, M., Osadetz, K.G., 2004. Denition and characterization of petroleum compositional families in Williston Basin, North America using principal component analysis. Organic Geochemistry 35, 453468. Peters, K.E., Moldowan, J.M., 1993. The Biomarker Guide: Interpreting Molecular Fossils in Petroleum and Ancient Sediments. Prentice-Hall, Englewood Cliffs, New Jersey. Peters, K.E., Walters, C.C., Moldowan, J.M., 2005. The Biomarker Guide, second ed. Cambridge University Press. Philp, R.P., Gilbert, T.D., 1986. Biomarker distributions in oils predominantly derived from terrigenous source material. In: Leythaeuser, D., Rullktter, J. (Eds.), Advances in Organic Geochemistry 1985, Organic Geochemistry 10. Pergamon, Oxford, pp. 7384. Philp, R.P., Li, J., Lewis, C.A., 1989. An organic geochemical investigation of crude oils from shanganning, Jianghan, Chaidamu and Zhungeer basins, China. Organic Geochemistry 14, 447460. Quadri, V.N., Quadri, S.M.J.G., 1997. Indus Basin of Pakistan contains few wells. Oil and Gas Journal Archives 95, i. 24. Radke, M., 1987. Organic geochemistry of aromatic hydrocarbons. In: Brooks, J., Welte, D. (Eds.), Advances in Petroleum Geochemistry. Academic Press, London. Radke, M., 1988. Application of aromatic compounds as maturity indicators in source rocks and crude oils. Marine and Petroleum Geology 5, 224236. Radke, M., Welte, D.H., 1983. The methylphenanthrene index (MPI): a maturity parameter based on aromatic hydrocarbons. In: Bjory, M. et al. (Eds.), Advances in Organic Geochemistry 1981. Wiley, Chichester, pp. 504512. Radke, M., Welte, D.H., Willsch, H., 1982. Geochemical study on a well in the Western Canada Basin: relation of the aromatic distribution pattern to maturity of organic matter. Geochimica et Cosmochimica Acta 46, 110. Radke, M., Welte, D.H., Willsch, H., 1986. Maturity parameters based on aromatic hydrocarbons: inuence of the organic matter type. In: Leythaeuser, D., Rullktter, J. (Eds.), Advances in Organic Geochemistry 1985. Organic Geochemistry, vol. 10. Pergamon, Oxford, pp. 5163. Rullktter, J., Marzi, R., 1988. Natural and articial maturation of biological markers in a Toarcian shale from northern Germany. Organic Geochemistry 13, 639 645. Schoell, M., 1984. Stable isotopes in petroleum research. In: Brooks, J., Welte, D.H. (Eds.), Advances in Petroleum Geochemistry, vol. 1. Academic Press, London, pp. 215245. Seifert, W.K., Moldowan, J.M., 1980. The effect of thermal stress on source rock quality as measured by hopane stereochemistry. In: Douglas, A.G., Maxwell, J.R. (Eds.), Advances in Organic Geochemistry 1979. Pergamon, Oxford, pp. 229 237. Seifert, W.K., Moldowan, J.M., 1986. Use of biological markers in petroleum exploration. In: Johns, R.B. (Ed.), Methods in Geochemistry and Geophysics 24, 261290. Simoneit, B.R.T., Schoell, M., Dias, R.F., Aquino Neto, F.R., 1993. Unusual carbon isotope compositions of biomarker hydrocarbons in a Permian tasmanite. Geochimica et Cosmochimica Acta 57, 42054211. Sofer, Z., 1984. Stable carbon isotope compositions of crude oils: applications to source depositional environments and petroleum alteration. American Association of Petroleum Geologist Bulletin 68, 3149. Trolio, R., Grice, K., Fisher, S.J., Alexander, R., Kagi, R.I., 1999. Alkylbiphenyls and alkyldiphenylmethanes as indicators of petroleum biodegradation. Organic Geochemistry 30, 12411253. van Aarssen, B.G.K., Bastow, T.P., Alexander, R., Kagi, R.I., 1999. Distributions of methylated naphthalenes in crude oils: indicators of maturity, biodegradation and mixing. Organic Geochemistry 30, 12131227. van Graas, G.W., 1990. Biomarker maturity parameters for high maturities: calibration of the working range up to the oil/condensate threshold. Organic Geochemistry 16, 10251032. Volk, H., George, C.S., Middleton, H., Schoeld, S., 2005. Geochemical comparison of uid inclusion and present-day oil accumulations in the Papuan Foreland evidence for previously unrecognised petroleum source rocks. Organic Geochemistry 36, 2951. Volkman, J.K., Banks, M.R., Denwer, K., Aquino Neto, F.R., 1989. Biomarker composition and depositional setting of tasmanite oil shale from northern Tasmania, Australia [C]. In: 14th International Conference on Organic Geochemistry, Paris, September 1822, Abstract, p. 168. Wandrey, C.J., Law, B.E., Shah, H.A., 2004. Patala-Nammal composite total petroleum system, Kohat-Potwar geologic province, Pakistan. US Geological Survey Bulletin 2208-B. <http://pubs.usgs.gov/bul/b2208-b/>.

Author's personal copy

1240

M. Asif et al. / Organic Geochemistry 42 (2011) 12261240 Zhang, S., Huang, H., 2005. Geochemistry of Palaeozoic marine petroleum from the Tarim Basin, NW China: Part 1. Oil family classication. Organic Geochemistry 36, 12041214.

Wenger, L.M., Davis, C.L., Isaksen, G.H., 2001. Multiple controls on petroleum biodegradation and impact on oil quality. SPE Reservoir Evaluation Engineering 5, 375383. Winters, J.C., Williams, J.A., 1968. Microbiological alteration of crude oil. I. The reservoir. Preprints. ACS Division of Fuel Chemistry, Paper PETR 86; E22E31.