Carbonates Evaporites (2011) 26:155165 DOI 10.

1007/s13146-011-0042-9

ORIGINAL ARTICLE

Diamondoids and biomarkers: as a tool to better dene the effects of thermal cracking and microbial oxidation on oils/condensates from reservoirs of the Upper Indus Basin, Pakistan
Muhammad Irfan Jalees Thomas S. Bianchi Roger Sassen Fazeelat Tahira

Accepted: 10 February 2011 / Published online: 18 March 2011 Springer-Verlag 2011

Abstract The present study examined crude oils and condensates from 12 productive oil eld zones present in the Upper Indus Basin, Pakistan, located at 33110 0000 N to 33560 0000 N and 73100 0000 to 73560 0000 E. These crude oils and condensates belonged to Eocene, Paleocene, and Jurassic ages. GC and GCMS parameters revealed that these samples were mature and contained marine and algal/ bacterial organic matter sources from an oxidizing environmental/dysoxic environment. The total methyladamantanes/admantane ratio varied from 4.05 to 15.25 and showed increasing levels of microbial oxidation. The diamantane/adamantane ratio varied from 1.14 to 3.06, and total methyldiamantanes/diamantane ratio also supports the results. The degree and classication of microbial oxidation in different crude oils and condensates were best dened by plotting American Petroleum Institute gravity versus diamondoid concentrations. Diamondoid parameters indicated a maturity of samples but the levels of maturity were different based on the particular diamondoid maturity parameter used, which varied considerably. This study further demonstrated that utilization of both biomarkers

and diamondoids provided the best approach for determining the maturity level of crude oils and condensates. Keywords Diamondoids Biomarker Microbial oxidation Thermal maturity Upper Indus Basin Pakistan

Introduction In petroleum, compounds exhibit differences in their resistance to microbial oxidation. More specically, it is the relative susceptibility of different compound classes (e.g., n-alkanes, branched alkanes, alkylated monocyclic alkanes, bicyclic terpanes, steranes, diasteranes, hopanes, alkylated benzenes, alkylated biphenyls, polycyclic aromatic hydrocarbons) to microbial oxidation that in part, collectively determines such differences in bulk petroleum stability (Illich et al. 1977; Seifert and Moldowan 1979; Alexander et al. 1983; Connan 1984; Gough and Rowland 1990; Peters and Moldowan 1991; Armanios et al. 1992; Bennett et al. 2006; Trolio et al. 1999). Diamondoids are of particular importance in petroleum geochemistry since they can provide valuable information toward achieving a better understanding of petroleum systems in sedimentary basins. Unfortunately, little information is available about the implications of diamondoid signatures in petroleum reservoirs (Williams et al. 1986; Trolio et al. 1999; Grice et al. 2000, Zhibin et al. 2007). Diamondoids are cage hydrocarbons occurring naturally in petroleum in varying abundance with a substituted and unsubstituted homologous series of lower diamondoids, including adamantanes, diamantanes and triamantanes (Grice et al. 2000). They are rigid, fused-ring alkanes with diamond-like structures and unique thermal stabilities

M. I. Jalees (&) T. S. Bianchi (&) R. Sassen Department of Oceanography, College of Geosciences Texas A & M University, College Station, TX 3146-77843, USA e-mail: Jalees@uet.edu.pk T. S. Bianchi e-mail: tbianchi@tamu.edu M. I. Jalees F. Tahira Chemistry Department, University of Engineering and Technology, Lahore 54890, Pakistan M. I. Jalees Institute of Environment Engineering and Research, University of Engineering and Technology, Lahore 54890, Pakistan

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(Zhibin et al. 2007). Diamondoids are more stable than most hydrocarbons and once formed, are resistant to thermal and biological destruction (Wingert 1992). Their formation from polycyclic hydrocarbon precursors, probably catalyzed by a strong Lewis acid catalyst, is driven by accompanying increases in their thermodynamic stability (Wingert 1992). Although the concentrations of these compounds are often very low, they are widely distributed in crude oils and source rocks. Diamondoid concentrations increase under conditions that cause thermal degradation of most other compounds in crude oil; or chemical oxidation, such as thermochemical sulphate reduction, is also responsible for losses of these non-diamondoid compounds (Dahl et al. 1999). However, some work has suggested that some diamondoids, such as adamantane (A), is also subject to microbial oxidation (Dahl et al. 1999; Grice et al. 2000). Nevertheless, most normal oils with low maturity and no cracking typically have high concentrations of biomarkers and extremely low concentrations of diamondoids (Zhibin et al. 2007). Conversely, in highly cracked oils, concentrations of diamondoids are generally very high and biomarkers are extremely low or in some cases totally absent (Trolio et al. 1999). This suggests that any oil with high abundances of both diamondoids and biomarkers should reect a mixture of low maturity oil and highly cracked sources (Zhibin et al. 2007). However, alteration of diamondoid moieties in advanced stages of oil microbial oxidation in some reservoirs have been reported (Grice et al. 2000). Thus, microbial oxidation could eventually reduce diamondoid concentrations in highly biodegraded oils, while selective microbial oxidation of biomarkers could increase their concentrations. Variations in the thermal stability of methyl-substituted diamondoids have lead to the use of certain isomer ratios as maturity parameters for crude oils and source rocks, especially at high overmature stages of hydrocarbon generation (Chen et al. 1996). For example, 1-methyl-adamantane (1-MA) is more stable than 2-methyl-adamantane (2-MA) and 4-methyldiamantane (4-MD) is more stable than 1-methyldiamantane (1-MD) and 3-methyl-diamantane (3-MD). Hence, the ratios 1-MA/(1-MA ? 2-MA) and 4-MD/(1-MD ? 3-MD ? 4-MD) should increase with increasing thermal stress (or depth). In other words, the higher the ratio, the higher the maturity of the oils and source rocks. Consequently, it has been proposed that diamondoid hydrocarbon ratios can be used as maturity indices for overmature crude oils and source rocks (Chen et al. 1996). Based on the aforementioned chemical indices, the primary goal of this study was for the rst time to use diamondoids and biomarkers to examine crude oils and condensates, collected from 12 productive oil eld zones in the Upper Indus Basin, Pakistan.

Geology and study area The study area is located to the southeast of Islamabad in Potwar Plateau, Upper Indus Basin, Pakistan. The oil elds are located between latitude 33110 0000 N to 33560 0000 N and longitude 73100 0000 to 73560 000 E (Fig. 1; Table 1). This depression has several features that make it a favorable site for hydrocarbon accumulations. Located on a continental margin, the depression is lled with thick deposits of sedimentary rocks, including potential source reservoir and cap rock. It contains a thick overburden (about 3,000 m) of uvial sediments, which provides the burial depth and optimum geothermal gradient for seeps found in this area (Khan et al. 1986). The details on the geology of this area have been reported in other studies (e.g. Fazeelat et al. 1994, 1995, 1999, 2010; Robison et al. 1999; Lakhdar et al. 2002, 2002; Sylvian et al. 2002; Ahmed et al. 2003; Wasim 2004; Wandrey et al. 2004). More specically, further details on these particular study sites along with the geological setting can be found in Fazeelat et al. (2010) and Muhammad et al. (2010).

Experimental Twelve different samples of crude oils and condensates were selected for chemical analyses. These oils are from Eocene, Paleocene and Jurassic reservoirs; details about geological ages and formation are provided in Table 1. Column chromatography Elemental sulphur was removed (Blumer 1957) before fractionating samples. Sulphur free samples were dissolved in n-hexane and fractionated into saturates (alkanes), aromatics, and NSO (nitrogen, sulphur, and oxygen) fractions, using a glass column (40 9 0.9 cm i.d.) with activated silica gel (Fazeelat and Yousaf 2004). The fractions were recovered by careful evaporation of the solvent on a sand bath, followed by removal of residual solvent with nitrogen gas. The samples were collected in pre-weighed vials and quantied; the results are shown in Table 1. Gas chromatography The saturated fractions (mg of sample/10 lL of solvent) obtained by liquid chromatography were then analyzed using capillary gas chromatography (GC) with a ame ionization detector (FID). GC-FID analyses of the saturated fractions were carried out using a Shimadzu 14B series Gas Chromatograph, equipped with FID, and a 30 m 9 0.25 mm (i.d.) lm thickness 0.25 lm fused silica capillary column, coated with methyl silicone (OV-1).

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33.3

Murree Thrust Fault

Dhakni Ratana Pariwali

NORTHERN FOLDED ZONE

Dhurnal Pindori

33.2

Meyal Khaur Dhulian

Fimkasar

33.1

POTOWAR PLATEAU
SOAN RIVER
Karsal Balkasar

Thrust Fault Anticline Oil Well

0 10 20

Soan Syncline
Balkasar Oxy

Miles

33 72 72.1 72.2 72.3 72.4 72.5 72.6 72.7 72.8

Fig. 1 Map of Pakistan showing the location of the oil wells in Upper Indus Basin Pakistan

Table 1 Location and general information of the sample wells Well name Balkasar Balkasar Oxy Dhakni Dhulian Dhurnal Fimkasar Karsal Khaur Meyal Pariwali Pindori Ratana Total depth (m) 2,528.92 2,520 4,591.07 2,738.15 5,039.69 3,244.61 3,896.92 1,673.84 4,130.15 5,024.30 4,275.38 4,516.92 Location of wells 33 50 23 13 N, 72 35 22 33E 33 55 60 N,72 30 0E 33 25 04 49 N, 72 10 22 39E 33 12 9 N, 72 20 41E 33 20 N, 72 33E 33 12 16 68 N, 72 58 05 57 E 33 11 21 68 N, 72 33 28 82 E 33 14 59 N,72 27 19E 33 18 11 81 N, 72 17 25 71E 33 19 02 N, 72 28 37 E 33 14 28 04 N, 72 56 01 42E 33 22 34 58 N, 72 18 07 88E Reservoir Chorgali/Sakesar Chorgali/Sakesar Lockhart Lockhart Chorgali/Sakesar/ Patala Chorgali/Sakesar Chorgali/Sakesar/ Lockhart Sakesar Datta Dhak pass Chorgali/Sakesar Chorgali/Sakesar Age Eocene Eocene Paleocene Paleocene Eocene/ Paleocene Eocene Eocene/ Paleocene Eocene Jurassic Paleocene Eocene Eocene API 19.91 19.37 35.83 37.12 35.63 21.34 20.12 35.23 39.91 39.81 36.39 35.21 SATS (%) 37 35 59 63 63 41 34 63 67 68 63 63 AROS (%) 42 41 30 28 28 36 40 25 23 21 25 26 NSO (%) 11 13 6 5 5 10 15 6 5 7 7 6 ASPH (%) 10 11 5 4 4 13 11 6 5 4 5 4 S (%) 0.1 0.1 0.1 0.01 0.01 0.1 0.01 0.01 0.01 0.01 0.01 0.01

Each sample (1 lL) was injected in splitless mode using a glass syringe through a rubber septum into the column. The FID detector and injector temperatures were maintained at 300 and 280C, respectively. The oven temperature was programmed to ramp from 60 to 300C at 4C/min, with a 5 min hold time. Nitrogen was used as carrier gas with a linear velocity of 2 mL/min. Further details on data collection, where peak retention times occurred between 0 and 66 min are provided by Muhammad et al. (2010). Gas chromatographymass spectrometry GCMS analysis was performed using a HewlettPackard (HP) 5973 mass selective detector (MSD) interfaced to a HP 6890 N gas chromatograph. The column used was a 30 m 9 0.25 mm ID capillary column coated with a

0.25 lm 5% phenyl 95% methyl polysiloxane stationary phase (DB-5 MS, J & W scientic). One microliter sample of the saturated fraction (1 mg/mL in n-hexane) was introduced into the split/splitless injector using the HP 6890 N autosampler. The injector was operated at 280 in pulsed splitless mode. Helium maintained at a constant ow rate of 1.1 mL/ min was used as carrier gas. The GC oven was programmed from 40 to 310C at 3C/min with an initial and nal hold time of 1 and 30 min, respectively. The transfer line between the GC and the MSD was held at 310C. The MS source and quadrupole temperatures were at 230 and 106C, respectively. Data were acquired in full scan mode from 50 to 550 amu, with the MS ionization energy 70 eV and the electron multiplier voltage 1,800 V. The identication of compounds peaks are shown in Fig. 2. The details of method can be found in Muhammad et al. (2008) .

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158 Fig. 2 TIC of Balkasar, Balkasar Oxy and Dhakni oil well sample

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Isolation of branched and cyclic alkanes A saturated fraction obtained by liquid chromatography separation was used to isolate branched and cyclic alkanes from straight chain alkanes. The saturated fraction (up to 15 mg) in cyclohexane (12 mL) was added to a 2-mL auto-sampler vial quarter lled (2 g) with activated 5A molecular sieves. The auto-sampler vial was capped and placed into pre-heated aluminum block (85C) for at least 8 h. The resulting mixture was ltered through a small column of silica (5.5 9 0.5 i.d.) and rinsed thoroughly with cyclohexane. The cyclohexane containing branched/cyclic alkanes were collected in pre-weighed vials. The removal of excess cyclohexane under a slow stream of nitrogen yielded the branched and cyclic fractions, according to Muhammad et al. (2008). Recovery of straight chain alkanes from molecular sieves The molecular sieve containing n-alkanes were air-dried and transferred to a 20 mL Teon tube. n-Hexane (23 mL) was then added to cover the sieves along with 1 mL of milli-Q water. The mixture was homogenized with a magnetic stirrer while being placed in an ice bath. Hydrouoric acid (50%, 2030 drops) was added drop wise while stirring until the sieve had dissolved (4550 min). The excess HF

was neutralized by adding saturated solution of sodium bicarbonate while stirring. The n-alkanes from sieves were dissolved in n-hexane and separated by passing through a small column of anhydrous magnesium sulfate. The aqueous mixture was further extracted with pentane (ca. 3 9 1 mL). Excess pentane was removed carefully using sand bath (50C), according to Muhammad et al. (2010). Diamondoid analyses using selected ion monitoring mode Diamondoid analyses were carried out using a HewlettPackard (HP) 5973 mass selective detector (MSD) interfaced to a HP 6890 N gas chromatograph (GC). A 30 m 9 0.25 mm ID capillary column coated with a 0.25 lm 5% phenyl 95% methyl polysiloxane stationary phase (DB-5 MS, J & W scientic) was used for the analysis. One microliter of the saturated fraction (1 mg/mL in n-hexane) was introduced into the split/splitless injector using the HP 6890 N auto-sampler. The oven temperature was programmed to increase from 20 to 294C at a rate of 4C/min and was held at the nal temperature for about 30 min. The mass spectrometer generated positive ions by electron impact at 70 eV. The ion source was maintained at 200C. Ion chromatograms were obtained by selective ion monitoring (SIM), using 20 masses and a 70 ms dwell time for each mass. The transfer line between the GC and the

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MSD was held at 294C. The MS source and quadrupole temperatures were at 210 and 106C, respectively. Mass spectra were obtained by scanning from 30 to 450 amu at a rate of about 1.2 s per scan. Identication of different derivatives of diamondoids is provided in Fig. 3 and Table 2.

Results and discussion The samples represent a suite of different types of oils and condensates with different levels of biodegradation. The general characterizations of these crude oils from the Indus Basin Pakistan are shown in Table 1. These assigned categories were made on the basis of API gravity, GC-FID analysis and UCM (unresolved complex mixture) of aliphatic hydrocarbon fractions along with diamondoid and biomarker analysis. Depositional environment and organic matter The major factors largely responsible for the alteration of petroleum composition are source, maturation, migration and microbial oxidation. The ratios of iso-prenoids to

n-parafns are often used to determine oil-to-source correlation, maturation, and levels of microbial oxidation (Connan et al. 1980). Pristane (Pr)/n-C17 and phytane (Ph)/ n-C18 ratios were used for analyzing organic matter, depositional environment and maturation. Values less than 1.0 are an indication of non-biodegraded oils (Connan et al. 1980). Both Pr/n-C17 and Ph/n-C18 decrease with maturation due to the increasing prevalence of n-parafns (Hunt 1979). The ratios of the sample for all the oils/condensates were less than 1.0 and which revealed a generally mature character (Table 3). Pr/Ph ratios used to assess paleoredox conditions of this depositional environment (Connan et al. 1980) indicated ratios greater than 1.0 for all crude oils/ condensates indicative of oxidizing conditions for this depositional environment. A plot of Pr/n-C17 versus Ph/n-C18 provided further information about past organic matter inputs to this system, which appeared to be mainly derived from aquatic algal and bacterial sources in a marine environment/dysoxic conditions (Figs. 4, 5). The ratio of 30-nor-hopane/hopane (30Nor-Hop/Hop) (Peters et al. 2004) also supported that organic matter inputs were dominated from inputs from algal and bacterial sources (Table 3). Figure 2 shows representative total ion chromatogram (TIC) of three samples; total abundance of the

m/z 136 18

m/z 188

27

m/z 240

2 3 4 5

m/z 135 19 20 6 7 9 8 10 24 23 12 13 14 11 15 m/z 163 22 m/z 253 m/z 215 17 m/z 177 26 25 m/z 201 28 m/z 149 21 m/z 187

m/z 239

29 16

Adamantanes

Diamantanes

Triamantanes

Fig. 3 The base ion peak chromatogram of the adamantanes (m/z 136 and CnH2n-5 series), diamantanes (m/z 188 and CnH2n-9 series) and triamantanes (m/z 240 and CnH2n-13 series). The peaks are identied in Table 3

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160 Table 2 Diamondoids identied in crude oil samples

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Peak no. 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29

Tentative assignment of peaks Adamantane 1-Methyladamantane 2-Methyladamantane 1-Ethyladamantane 2-Ethyladamantane 1,3-Dimethyladamantane 1,4-Dimethyladamantane, cis 1,4-Dimethyladamantane, trans 1,2-Dimethyladamantane 1-Ethyl-3-methyladamantane 1,3,5 Trimethyladamantane 1,3,6-Trimethyladamantane 1,3,4-Trimethyladamantane, cis 1,3,4-Trimethyladamantane, trans 1-Ethyl-3,5-dimethyladamantane 1,3,5,7-Tetramethyladamantane 1,2,5,7-Tetramethyladamantane Diamantane 4-Methyldiamantane 1-Methyldiamantane 3-Methyldiamantane 4,9-Dimethyldiamantane 1,4 and 2,4-Dimethyldiamantane 4,8-Dimethyldiamantane 3,4-Dimethyldiamantane Trimethyldiamantane Triamantane 9-Methyltriamantane Dimethyltriamantane

Abbreviations AD 1, MA 2, MA 1 EA 2 EA 1,3 DMA 1,4 DMA (cis) 1,4 DMA (trans) 1,2 DEA 1E, 3, MA 1,3,5 TMA 1,3,6, TEA 1,3,4, TEA (cis) 1,3,4, TEA (trans) 1E, 3,5, DMA 1,3,5,7 TtMA 1,2,5,7 TtMA D 4 MD 1, MD 3, MD 4,9 DMD 1,4 and 2,4 DMD 4,8 DED 3,4 DMD TED T 9, MT DMT

M? 136 150 150 164 164 164 164 164 164 178 178 178 178 178 192 192 192 188 202 202 202 216 216 216 216 230 240 254 268

Base peak 136 135 135 135 135 149 149 149 149 149 163 163 163 163 163 177 177 188 187 187 187 201 201 201 201 215 240 239 253

diamondoids in each sample is shown in Table 3. Unresolved complex mixtures (UCM) were present in all oils and condensates; low molecular weight alkanes were absent. Diamondoids Diamondoids were analyzed and identied by GCMS. All diamondoids were identied by comparison of their mass spectra and relative retention time with reported literature values (Wingert 1992; Chen et al. 1996). Adamantanes, diamantanes, and triamantanes, which were present in all the crude oils, were examined using m/z 135, 136, 149, 163, and 177 ions (adamantanes); m/z 187, 188, and 201 ions (diamantanes); m/z 240, 239, and 253 ions (triamantantes) (Fig. 3 and Table 3). The plot between diamondoids versus API gravity (Fig. 6) showed that the Balkasar Oxy, Balkasar and Fimkasar sites had high concentrations of diamondoids, likely due to cracking of high molecular compounds (HMC) and decreases in API gravity. In the Ratana, Khaur, Karsal

and Dhulian sites, the reverse trend was observed with less cracking which resulted in fewer diamondoids and a higher API gravity. Finally, the Meyal, Pariwali, Pindori and Dhurnal sites showed a different trend with high API values and diamondoid concentrations which suggested that these samples were mixed. Diamondoids are some of the most abundant resolved components present in the saturated hydrocarbon fraction in biodegraded oils and heavy oils (Grice et al. 2000). However, diamondoids are also formed by the cracking of polycyclic compounds present in the crude oils/condensates (Zhibin et al. 2007). This cracking generally decreases the American Petroleum Institute (API) gravity of the oils and increases the diamondoid concentrations. Therefore, it seems that any normal oils with high API gravity and no cracking have a low abundance of diamondoids and those with low API gravity and high cracking have a high abundance of diamondoids (Zhibin et al. 2007). The situation becomes complex when considering maturity, which is also based on cracking (e.g., cracking of kerogen and HMC).

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Table 3 Abundance and different ratios of n-alkanes, iso-prenoids, diamondoids and biomarkers in crude oils/condensates from Upper Indus basin Pakistan GC parameters Pr/Ph (ppm) Pr/n-C17 Ph/n-C18 Diamondoids parameters Adamantane (ppm) Diamantane (ppm) Triamantane (ppm) MA/n-C11a MAD/ADb MDAD/DADc 1-MAD/(1-,?2-MAD) MADI (%)d MDADI (%)e 1,2-?1,3-?1,4 DMAD/ADf 33.08 37.17 47.89 49.9 13.26 20.13 9.36 1.64 25.62 49.64 28.91 7.48 1.14 40.76 12.07 0.47 0.93 1.56 1.10 33.21 36.48 45.89 6.14 1.51 59.36 10.35 0.51 0.97 1.79 1.00 28.88 68.19 6.63 2.90 1.31 17 5.88 0.52 0.97 1.72 0.99 57.02 34.24 4.89 5.12 1.12 11.29 9.25 0.47 0.93 1.56 1.10 6.00 13.53 43.04 9.05 41.5 18.12 0.51 0.97 1.79 1.00 84.78 28.88 36.88 39.67 12.09 6.63 3.89 3.06 2.90 1.31 5.86 35.11 19.75 1.71 14.55 70.34 5.91 0.51 0.97 1.79 1.00 NA 68.80 NA 6.5 NA NA 13.91 0.52 0.97 1.72 0.99 7.83 14.02 15.97 10.51 14.37 42.72 18.68 0.47 0.93 1.57 1.10 Meyal Pariwali Pindori Dhurnal Fimkasar Balkasar Ratana Khaur Karsal Dhulian Dhakni Balkasar Oxy 1.76 0.72 1.75 0.66 1.65 0.68 0.44 428 52.91 488 17.86 707 2.05 0.22 6.06 3.70 1.63 0.79 0.48 207 57.14 313 15.07 388 1.50 0.16 5.48 3.23 1.62 0.66 0.45 240 36.92 315 16.77 390 3.30 0.15 5.09 2.14 1.43 0.69 0.48 144 28.41 162 26.20 253 6.63 0.47 4.05 3.15 1.79 0.43 0.25 2.3 9.25 95.6 39.50 99.9 28.31 0.38 84.65 8.34 1.67 0.70 0.58 113 346 332 9.03 0.14 7.44 2.41 1.62 0.66 0.45 168 220.5 273 3.30 0.14 5.09 3.68 1.46 0.57 0.39 5.8 20.4 84.4 24.96 124 15.55 0.37 27.65 2.90 6.42 36 47.66 57 11.03 0.31 NA 6.5 1.65 0.75 0.31 1.36 0.58 0.38 3.13 8.95 45 56.34 65 10.24 0.12 15.25 7.28

0.427 0.40 353 594 1011 277 456 673

Alkyl adamantanes (relative %) 38.11 43.24 Alkyl diamantanes (relative %) 25.07 24.34 Alkyl triamantanes (relative %) 4.466 3.52 0.458 0.24 8.53 3.47 12.22 3.28

25.98 36.92 22.53 21.17

3,4-?4,8-?4,9-DMDAD/DADg 7.13 DAD/ADh 1.68 Alkyl diamantane/diamantanej Biomarkers Ts/Ts ? Tmk 30 Nor/Hopl C31 Hop/C30 Hopm C32 (S/S ? R)
a b c d e f g h i j k l m n n

Alkyl adamantane/adamantanei 29.20 39.30 11.41 13.44 0.51 0.97 1.79 1.00 0.52 0.97 1.72 0.99

176.56 24.84 17 7.037 7.42 0.52 0.97 1.72 0.99 0.47 0.93 1.56 1.10

1-, ?2-, Methyladamantane/n-C11 1-, ?2-, Methyladamantane/adamantane (relative %) 1-, ?2-, ?4-, Methyldiamantane/diamantane (relative %) 4-Methyladamantane/(1-, ?3-, ?4-, Methyladamantane) 9 100 4-Methyldiamantane/(1-, ?3-, ?4-Methyldiamantane) 9 100 1,2-, ?1,3-, ?1,4-Dimethyladamantane/adamantane 3,4- ?4,8-, ?4,9-Dimethyldiamantane/diamantane Diamantane/adamantane Alkyl adamantanes including 1-methyl, 2-methyl, 1-ethyl, 2-ethyl, 1,3-dimethyl, 1,4-dimethyl and 1,2 dimethyladamantane Alkyl diamantanes including 1-methyl, 3-methyl, 4-methyl, 4,9-dimethyl, 4,8-dimethyl, 3,4-dimethyl diamantine Ts = 18a 22,29,30-tris nor-hopane, Tm = 17a 22,29,30-tris nor-hopane 30 Nor = 17a,21b-30 nor-hopane, Hop = 17a-hopane C31 Hop = 22(R ? S) 17a, 21b homohopane C32 = 22R 17a,21b bishomohopane, 22S 17a,21b bishomohopane

Maturity The thermal maturity of the admantane (A) is different from its methyl derivatives, methyladamantane (1-MA) and 2-methyladamantane (2-MA) (Grice et al. 2000). Since the

thermal stability of 1-MA is greater than 2-MA, the ratio of 1-MA/(1-MA ? 2-MA) increases with maturity (Grice et al. 2000). A similar trend is observed with diamantane and its methyl derivatives, 1-methyldiamantane (1-MD), 3-methyldiamantane (3-MD) and 4-methyldiamantane (4-MD),

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162 Fig. 4 Base ion chromatogram of hopanes (m/z 191 and CnH2n-8 series)

Carbonates Evaporites (2011) 26:155165

C30-Hop

m/z 191

C29-Hop

C31-Hop S C32-Hop S R R C33-Hop S C34-Hop R S R C35-Hop S R

Tm

Ts

Fig. 5 Organic matter classication of sample analyzed (modied after Hunt 1979)

where 4-MD is more stable than the other two derivatives (Grice et al. 2000). A plot between 1-MA/(1-MA ? 2-MA) versus 4-MD/(1-, ?2-, ?3- MD), showed that most samples had a high maturity level (Fig. 7). The Balkasr Oxy, Ratana and Dhulian sites showed minimum levels of maturity, while Khaur, Balkasar were at the highest level of maturity. Dhurnal, Karsal, Meyal,

Pindori, Fimkasar and Dhakni showed very complex trends and maturity levels could not be determined. All are formations considered to be mature show values of 4-MD/ (1-, ?3-, ?4-MD) that ranged from 38 to 75%, with 1-MA(1-, ?2-MA) values similar, but generally less than 40%. This suggested that while the 1-MA and 4-MD were thermally stable, their relative stabilities were different.

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Such a comparison between two maturity indices is complex and requires the use of biomarkers for a valid interpretation. Ts and Tm are tris-norhopanes whereby, Ts is more thermally stable than Tm; this allows the Ts/(Ts ? Tm) ratio to be used as another index of maturity. The maturity range for this index starts from about 0.5, which is very close to 1-MA/(1-, ?2-MA) maturity value of 40%. A plot between Ts/(Ts ? Tm) versus 1-MA/(1-, ?2-MA) provided a more clear picture of the maturity level. The Ratana, Dhulian, Khaur, Dhurna, Pariwali, Meyal, Fimkasar, Dhakni sites were all mature oils, while Balkasar Oxy, Balkasar, Karsal and Pindori were only near the mature oil window (Fig. 8). These results suggested that the 1-MA/ (1-, ?2-MA) ratio alone should not be used as a maturity parameter in the absence of additional biomarker information. For example, the 22S/(22S ? 22R) values ranged from 0.49 to 0.52 indicative of a moderate maturity level, while the 30 Nor-hopane/hop and 31 homohopane/hopane both indicated the same level of maturity and showed a range of 1.571.79 and 0.930.97, respectively (Table 3).

Microbial oxidation Methyl derivatives of diamondoids showed more resistance microbial oxidation than the diamondoids (Grice et al. 2000). This was evidenced by the ratio of methyladamantanes (MA) (relatively low susceptibility) to the n-C11 alkane (relatively high susceptibility) (Table 3). Increasing microbial oxidation was reected by increases in the ratio of MA/n-C11 alkanes. For example, the range of ratios increased from 0.12 (Balkasar Oxy) to 0.47 (Balkasar). As might be expected, mixed oils, multiple oil accumulations, and microbial oxidation events were probably components of this ratio. Also, changes in relative abundances of MA to adamantine (A) and methyldiamantanes (MD) to diamantine (D) occurred with microbial oxidation; the MA/A ratios of samples are shown in Table 3. This ratio varied from 4.05 to 15.25, with two exceptions for Ratana and Dhulian which had values of 84.65 and 27.65, respectively. This exception in Ratana and Dhulian was likely due to removal of adamantane from oil and condensates. Many factors were associated with the removal of the admantane

Fig. 6 Plot between API gravity and total diamondoids concentration showing effect of cracking

Fig. 7 Plot between maturity parameters i.e. 1-4MD/(1-, ?3-, ?4MD) 9 100 versus 1-MA/ (1-, ?2-MA) 9 100, showing relative thermal stability of the methylated diamondoid derivatives

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164 Fig. 8 Plot between biomarker parameters and diamondoid maturity parameter index for the relative thermal stability of the sample analyzed

Carbonates Evaporites (2011) 26:155165

but the most important were biodegradation and oxidation. Adamantane is easily oxidized and biodegraded, while its derivatives are much stable (Grice et al. 2000; Chen et al. 1996). Diamantanes and triamantanes were also more stable than adamantane due to an increase in the number of carbon rings. Therefore, here we suggest that variations in MA/A ratios were directly affected by changes in the concentrations of the adamantane. Since adamantanes were most susceptible to microbial oxidation in all diamondoids, only a minor amount of microbial oxidation can result in signicant variation in the MA/A ratios. The ratio of MA/A clearly increased with microbial oxidation, while the ratio between diamantane and its methyl derivative did not vary much (from 2.14 to 8.34). Since diamantane is more stable than adamantine, even Ratana showed a value of 8.34 which was more biodegraded with a MA/A value of 84.65. Diamantane/adamantane ratio can also be used as an index of microbial oxidation (Zhibin et al. 2007). As adamantane is more susceptible than diamantine, so their ratio increases with increasing levels of microbial oxidation. These oils and condensates in this study varied from 1.14 to 3.06 with exception for Ratana with 41.5, Dhulian with 14.55 and Balkasar Oxy with 14.37. Dhulian and Balkasar Oxy values were not as high as compared with Ratana, but microbial oxidation levels were higher than in other samples; Ratana had the highest level of microbial oxidation. Alkyladamantane and alkyldiamantane were more stable than the adamantane and diamantane, respectively. The ratio between adamantane and its methyl derivatives indicated the extent of the microbial oxidation. In these samples, this ratio ranged from 17 to 40.76, with exception for Ratana (176.56) and Dhulian (70.34), which likely had high levels of microbial oxidation. The ratio between diamantane and its methyl derivatives in these samples did

not vary much (5.8818.68) due to the stability of diamantane.

Conclusions Iso-prenoids and iso-prenoids to n-alkane ratios showed that all the samples were mature and have oxidizing depositional environment. Marine organic matter, under marine/dysoxic conditions, was the major source. UCM was present in all the samples and low molecular weight alkanes were also absent. Cracking of high molecular weight compounds and high concentration of diamondoids were present in Balkasar Oxy, Balkasar and Fimkasar. Conversely, Ratana, Khaur, Karsal and Dhulian had the reverse trend. Balkasr Oxy, Ratana and Dhulian had minimum levels of maturity, while Khaur, Balkasar were at high level of maturity. A plot between Ts/(Ts ? Tm) versus 1-MA/ (1-, ?2-MA) showed that Ratana, Dhulian, Khaur, Dhurna, Pariwali, Meyal, Fimkasar, Dhakni were all in mature oil window, while Balkasar Oxy, Balkasar, Karsal and Pindori were only near the mature oil window. With increasing microbial oxidation, the ratio of MA/ n-C11 alkane increases from 0.12 (Balkasar Oxy) to 0.47 (Balkasar). The lower the ratio, the lower will be microbial oxidation and vice versa. Removal of adamantine from samples made MA/A ratio of samples highly variable so need of alternative parameter is required. The results suggest that cracked, uncracked and mixed oils and condensates are present in this region of Pakistan.
Acknowledgments Authors are thankful to OGDCL, Pakistan and POL Pakistan for providing samples and necessary data. Authors are also thankful to Higher Education Commission of Pakistan for providing grant under IRSIP 8 Ps 23 and under PIN-202451-C-019 for the study.

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