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The Geochemical Characterization of Sediments from Early Cretaceous Sembar Formation

A. Nazir , T. Fazeelat & M. Asif
a a a a

Chemistry Department, University of Engineering & Technology, Lahore, Pakistan Version of record first published: 04 Oct 2012.

To cite this article: A. Nazir, T. Fazeelat & M. Asif (2012): The Geochemical Characterization of Sediments from Early Cretaceous Sembar Formation, Petroleum Science and Technology, 30:23, 2460-2470 To link to this article: http://dx.doi.org/10.1080/10916466.2010.519756

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Petroleum Science and Technology, 30:24602470, 2012 Copyright Taylor & Francis Group, LLC ISSN: 1091-6466 print/1532-2459 online DOI: 10.1080/10916466.2010.519756

The Geochemical Characterization of Sediments from Early Cretaceous Sembar Formation

A. NAZIR,1 T. FAZEELAT,1 AND M. ASIF1
1

Chemistry Department, University of Engineering & Technology, Lahore, Pakistan

Abstract The soluble organic matter (SOM) and kerogen of sediments contain organic molecules, and can be interpreted in terms of source, generative potential, thermal maturity, and depositional environment of the organic matter. Early Cretaceous sedimentary sequence of Sembar Formation comprising ve sediments samples was analyzed. Both SOM and hydrocarbons bound to the kerogen terms as pyrolyzed organic matter (POM) were characterized geochemically. Hydrous pyrolysis was carried out to release hydrocarbons from extracted sediments and fractionated by liquid chromatography. Saturated fractions from both SOM and POM were further analyzed by gas chromatography-ame ionization detector. The study suggested that Cretaceous sequence of Sembar Formation has fair to good hydrocarbon source potential. Thermal maturity parameters indicate onset of oil genesis zone. The presence of even carbon numbered n-alkenes, Pr/Ph and Pr/n-C17 versus Ph/n-C18 plots reveal marine algal source and anoxic depositional environment of organic matter from Sembar Formation. Keywords early Cretaceous, geochemical characterization, hydrous pyrolysis, kerogen, Sembar formation

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Introduction
Sediments provide a dynamic and long-term reservoir for organic species that include lipids (solvent-soluble organic matter, including hydrocarbons, fatty acids, and alcohols) and macromolecular organic matter, all derived from natural biogenic and geologic sources (Simoneit, 1978). The quantity and quality of organic matter preserved during diagenesis of sediments ultimately determine the petroleum-generative potential of the rock. The deposition of organic-rich sediments is favored by a high rate of production of organic matter and a high preservation potential. Sediments are dened as oxic, dysoxic, suboxic, and anoxic depending on the oxygen content of the overlying waters. Most petroleum is generated from source rocks deposited under anoxic to dysoxic environments because they contain more hydrogen-rich organic matter than do oxic sediments. Anoxic depositional environments are created from the lack of water circulation below the photic zone in marine or lacustrine sediments. Anaerobic degradation of organic matter is thermodynamically less efcient than aerobic degradation (Claypool and Kaplan, 1974). This observation supports the prevailing belief that anoxia is the main cause for enhanced preservation of hydrogen- and lipid-rich organic matter in petroleum source
Address correspondence to A. Nazir, Chemistry Department, University of Engineering & Technology, Lahore 54890, Pakistan. E-mail: anmalik77@gmail.com

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rocks (Demaison and Moore, 1980). Where oxic conditions exist, the organic matter is largely destroyed during sedimentation and diagenesis, even when organic productivity is high. The distribution of alkanes and alkenes in sediments is characterized by distinct carbon number ranges and has been used for the diagnosis of paleo environments (Pearson and Obaje, 1999) and organic source input (Cranwell, 1982). Potential petroleum source rocks are described in terms of the quantity, quality, and level of thermal maturity of the organic matter. A potential source rock contains adequate amounts of the proper type of dispersed kerogen to generate signicant amounts of petroleum but is not yet thermally mature. A potential source rock becomes an effective source rock only at the appropriate levels of thermal maturity (i.e., with the oil-generative window). The main objective of this work was to evaluate depositional environment, hydrocarbon-generating potential and thermal maturity of Sembar Formation from the Lower Indus Basin (Khaskheli-1). This geochemical evaluation will provide information about the source potential of Sembar Formation that subsequently helps to locate oil and gas in the area.

Experimental
Geological Description of Sembar Formation The sediment samples analyzed in this study belong to the Sembar Formation of Cretaceous age (well Khaskheli-1). The Khaskheli oileld is situated in the Badin Block, the southern central portion of the Lower Indus Basin and is about 31 km in the northwest of Badin town. The samples were provided by British Petroleum Exploration and Production Inc. (Islamabad, Pakistan). The Lower Cretaceous Sembar Formation consists mainly of shale with subordinate amount of siltstone and sandstone. Shale of Lower Cretaceous Sembar Formation is the main source rock in the Lower Indus Basin and the major component of oil discovered in Badin Platform is believed to have been sourced from Sembar shales (Kadri, 1993). Most of the Cretaceous shale contains abundant organic matter and is deposited over most of the Indus Basin in marine depositional environment and thickness varies from a few meters to 260 m (Iqbal and Shah, 1980; Kadri, 1993). Total organic carbon (TOC) values of Sembar in Badin area wells range from 0.5% to 3.5% and average about 1.4% (Wandrey et al., 2004). The Sembar Formation is thermally mature in the western deeply buried part of the shelf and becomes shallower and less mature toward the eastern edge of the Indus Basin. Geochemical analyses of rock samples and produced oil and gas in the Indus Basin have shown that the bulk of the hydrocarbons produced in the Indus Basin are derived from the Lower Cretaceous Sembar Formation (Wandrey et al., 2004). Determination of TOC The TOC was determined by wet combustion titration method (Fazeelat and Yousaf, 2004). Briey, nally grounded sediment (100 mg) was taken in a dry conical ask and solution of chromic acid (0.4 N, 10 mL) was added to it. It was placed on a sand bath for digestion at approximately 175C for 3 min. The contents of the ask were allowed to cool. The volume was then made up to 100 mL by adding distilled water and ve drops of diphenylamine indicator (0.1 g diphenylamine in 50 mL concentration H2 SO4 ) were added. The contents of the ask were titrated against ferrous ammonium sulfate (0.2 N) until endpoint green color was obtained. A blank titration was run parallel to

2462 each analysis.

A. Nazir et al.

Total Organic Carbon (wt%) D

2.16(Blank titer Sample titer) Blank titer Sample weight

Soxhlet Extraction of Organic Matter The Soxhlet extractor containing antibumping beads, thimble, and glass wool was preextracted with a mixture of solvents, CH3 OH, and CH2 Cl2 (1:1, 150 mL) for 24 hr. After pre-extraction, a known weight of grounded sediment (5 g) was taken in the thimble then covered with glass wool and placed in the extractor. Solvent mixture (CH3 OH:CH2Cl2 , 1:1; 150 mL) was taken in the round-bottom ask containing some pre-extracted boiling chips to ensure smooth boiling and extraction was performed for 72 hr. The soluble organic matter (SOM) was obtained by careful evaporation of the solvent using rotary evaporator. The extracted sediments were further used for hydrous pyrolysis. Hydrous Pyrolysis of Extracted Sediments Hydrous pyrolysis was performed on extracted sediments (Lewan et al., 1979). The stainless steel tube reactor was washed with water, alcohol, acetone, and dichloromethane successively. The extracted sediment sample (500 mg) was taken in the tube reactor (capacity 25 mL) containing 10 mL triply distilled water. It was purged with nitrogen (for removal of air and to provide inert atmosphere) and sealed. The tube reactor was heated at 330 C for 72 hr in a furnace. The expelled organic matter from extracted sediments was obtained after evaporation of water and is called pyrolysate (pyrolyzed organic matter [POM]). Organic matter thus generated (POM) was subjected to column chromatography. Fractionation of SOM and POM by Column Chromatography Both SOM and POM were fractionated into saturates; aromatics; nitrogen, sulfur, and oxygen (NSO); and asphaltene and resins fractions by column chromatography on silica gel. A glass column (40 cm 1.2 cm) was packed with slurry of activated silica gel (105C, 24 hr, 5 g) in n-hexane (25 mL). The bitumen dissolved in n-hexane (50 l) was introduced onto the column. The saturated fraction was eluted with three bed volumes of n-hexane, the aromatics with three bed volumes of 95:5 mixture of n-hexane: diethyl ether, and NSO with three bed volumes of methanol and asphaltene and resins with three bed volumes of chloroform. The fractions were recovered by careful evaporation of the solvent on a sand bath followed by the removal of residual solvent under nitrogen. The fractions were collected in pre-weighed sample vials (Fazeelat and Saleem, 2007). Gas Chromatography-Flame Ionization Detector Analysis Sample dilution for gas chromatography was made as follows: 1 mg saturated fraction D 50 L n-hexane, 10 mg saturated fraction D 500 L n-hexane (where 1 mL D 1000 L). Analysis of saturated fraction was carried using a Shimadzu GC-14B Series (Tokyo, Japan) gas chromatograph, equipped with a ame ionization detector (FID) and fused silica capillary column, coated with methyl silicone (OV-1), and 30 m 0.25 mm i.d. lm thickness was 0.25 m. The sample 1 L was injected in splitless mode at 60 C.

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Detector (FID) and injector temperatures were 300C and 280C, respectively. The oven temperature was programmed from 60C to 300C at 4 C/min. Nitrogen at a linear velocity was used as the carrier gas. The data were collected from retention time 066 min (Fazeelat and Saleem, 2007).

Results and Discussion

A total of ve sediments were analyzed and geochemically characterized from the Lower Indus Basin, Pakistan. Column chromatography and gas chromatography-ame ionization detector (GC-FID) results from both SOM and POM were used to evaluate depositional environment, generative potential, and thermal maturity of organic matter of Sembar Formation.

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Depositional Environment The Pr/Ph ratios, presence of n-alkenes, and saturates/aromatics ratios were used to classify depositional environment of the sediments. The Pr/Ph ratio can be used to determine the redox conditions of the sediments during deposition under the assumption that both pristane and phytane originate from the same source (e.g., phytol side chain of chlorophyll a). Typically Pr/Ph ratios <1 are taken to indicate an anoxic depositional environment and <2 indicates marine source input of organic matter (Peters et al., 2005). Oil from rock deposited under open water condition shows Pr/n-C17 <0.5, while those from inland peat swamps have Pr/n-C17 >1.0 (Lijmbach, 1975). Table 1 lists the calculated values of isoprenoid and n-alkanes ratios. Pr/Ph ratios (0.120.89, 0.510.68), Pr/n-C17 values (0.100.17, 0.180.24), and Ph/n-C18 values (0.280.45, 0.270.40) for SOM and POM, respectively, indicate Pr/Ph <1, Pr/n-C17 <0.5, and Ph/n-C18 >0.2 reveal reducing and hypersaline conditions of depositions of the organic matter. The values of Pr/n-C17 and Ph/n-C18 are plotted, which suggests that the source of the organic matter is mainly algal and marine and the type of kerogen is II (Figure 1). The saturate/aromatic ratios (0.490.76, 0.410.87) for SOM and POM (Table 2) indicate that organic matter is predominantly marine (Peters et al., 2005). These sediments from Sembar Formation show hypersaline and anoxic depositional conditions that most likely to preserve marine organic matter, therefore suggesting marine source of organic matter. Distribution of n-alkenes were also observed and interpreted relevant to n-alkanes (Figure 2). The predominance of n-alkane relevant to n-alk-1-ene shown by doublets (Figure 2) indicate strong contribution from either a highly aliphatic biomacromolecules (algaenan) present in outer cell wall of algae or lipids grafted to the kerogen by necondensation reactions (Derenne et al., 1997). A signicant feature displayed by GC prole of the samples is predominance of even carbon numbered n-alkenes parallel to alkanes, and n-alk-1-enes elute at retention time slightly shorter than respective n-alkanes. Furthermore, these n-alkene compounds were observed only with even carbon numbered n-alkanes. The linear increase of retention times of compounds in analogy with even carbon numbered n-alkanes shows that these compounds are members of homologous series. Figure 3 shows the plot of relative abundance (%) versus carbon number of nalkenes showing decrease in concentration of n-alkenes with increase in carbon number in POM of sediments. The presence of even carbon number compounds suggest that precursor of these compounds had been produced due to presence of unsaturated alcohol

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Table 1 n-Alkanes parameters for maturity, SOM, and depositional environment of the sediments and relative abundance (%) of even carbon numbered n-alkenes in the POM of the sediments
SOM POM, ppm CPI 0.92 0.96 0.91 0.95 0.99 0.88 0.97 0.80 0.94 0.99 0.80 0.89 0.76 0.81 1.06 0.82 0.88 0.88 0.89 0.91 0.68 0.52 0.63 0.51 BDL 0.89 0.74 0.89 0.60 0.12 0.24 0.23 0.18 0.18 BDL 0.17 0.16 0.16 0.15 0.10 0.31 0.40 0.37 0.27 BDL OEP CPI OEP POM SOM POM SOM POM 800 1,200 1,600 1,900 2,700 POM Pr/Ph Pr/n-C17 Ph/n-C18 SOM 0.45 0.36 0.37 0.30 0.28 16 9.68 26.33 25.21 23.51 15.27 Relative abundance (%) of n-alk-1-enes 18 8.57 30.48 26.78 22.3 11.87 20 9.19 28.23 30.29 22.25 10.04 22 9.41 29.53 26.03 21.96 13.07 24 9.57 29.01 27.48 21.7 12.24

Sample

Depth, m

TOC, wt%

Bit/ TOC

SOM, ppm

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A B C D E

2,55760 2,56066 2,57985 2,58591 2,59197

0.7 0.8 0.9 0.95 1.00

0.101 0.095 0.090 0.092 0.091

900 1,100 1,300 1,800 2,100

Note. CPI D (C21 C C23 C C25 C C27 C C29 ) C (C23 C C25 C C27 C C29 C C31 )/2(C22 C C24 C C26 C C28 C C30 ); OEP D (C21 C 6C23 C C25 )/4C22 C 4C24 ; relative abundance of n-alk-1-enes D peak area of C16 n-alk-1-ene/peak area of C16 -C24 n-alk-1-enes*100; SOM D weight of extract/weight of sediments taken*100; POM D weight of extract/weight of sediments taken*100; 16 D C16 , n-alk-1-ene; 18 D C18 , n-alk-1-ene; 20 D C20 , n-alk-1-ene; 22 D C22 , n-alk-1-ene; 24 D C24 , n-alk-1-ene.

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Figure 1. Pristane/n-C17 versus phytane/n-C18 (SOM and POM) to infer organic matter and depositional environment of Sembar Formation sediments (adapted from Connan and Cassou [1980]). *Isoprenoid/n-alkanes ratios of POM 2591-97 m were below detection limits.

and acids in organic matter, which had been reduced to respective olens with even number carbon chain under reducing conditions. The presence of even carbon n-alk-1enes with maxima at n-C16 and n-C18 (Figure 3) shows contribution of algal, bacterial, and fungal organic matter (Alboro, 1976).

Table 2 Column chromatography results of SOM and POM Relative percentages Saturates Sample A B C D E POM 14.00 18.64 19.60 22.50 21.43 SOM 18.20 19.42 17.86 20.71 21.66 Aromatics POM 34.00 31.82 29.40 27.50 24.29 SOM 37.45 36.00 32.14 30.71 28.33 NSOs POM 39.00 38.54 34.15 35.25 35.43 SOM 29.10 31.86 32.71 32.00 35.66 Asphaltenes POM 13.00 11.00 16.85 14.75 18.85 SOM 15.25 12.72 17.29 16.58 14.35 Saturates/ Aromatics SOM 0.49 0.54 0.55 0.67 0.76 POM 0.41 0.59 0.67 0.82 0.87

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Figure 2. Gas chromatograms showing distribution of n-alkanes and n-alk-1-enes (*) in saturated fraction of POM (Samples B and E). Number on peaks refers carbon number of n-alkanes. Pr D pristane; Ph D phytane; IS D internal standard.

Figure 3. Plot of relative abundance (%) versus carbon number of n-alkenes showing decrease in concentration of n-alkenes with both depth and carbon number in POM of sediments. (color gure available online)

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Figure 4. Classication of sediments (SOM and POM) on ternary diagram (after Tissot and Welte, 1984). Different regions of ternary plot are the following: AA D aromatic asphaltic; AI D aromatic intermediate; AN D aromatic naphthenic; N D naphthenic; PN D parafnic naphthenic; P D parafnic.

The presence of n-alk-1-enes in sediments is also an indicator of anoxicity of organic matter (Alboro, 1976) that supported earlier ndings about the depositional conditions (see previous). Table 2 suggests organic matter type from the relative amount of weight percent of compound classes supported by the ternary plot. The position of the samples of the well Khaskheli-1, on ternary plot (Figure 4) for bitumen and POM show that on going from 2,557 to 2,597 m the bitumen composition changes from aromatic naphthenic to parafnic naphthenic. It shows a gradual increase in parafnic and naphthenic character with an increase in depth. The plot also suggests that the organic matter type is marine. Generative Potential of Sediments from Sembar Formation Generative potential is the total amount of organic matter present as solvent soluble hydrocarbons and kerogen (i.e., SOM and POM). The amount of SOM illustrates the fraction of generative potential that has been effectively transformed into hydrocarbons, while the amount of POM indicates remaining hydrocarbon potential yet to generate hydrocarbons in sediments. Generative potential of the Sembar Formation sediments is determined by measuring TOC, SOM, and POM. The primary prerequisites for a potential source rock are the quantity, quality, and thermal maturity of organic matter it contained. TOC values of the analyzed sediments lie in the range of 0.71.0 wt% (Table 1). Peters and Cassa (1980) suggested TOC values as poor (TOC <0.5 wt%), fair (TOC 0.51 wt%), good (TOC 12 wt%), and very good (TOC >2 wt%). The TOC results from Sembar Formation sediments indicate that most of them have good source rock potential. The quantity of organic matter in sediments is interpreted in terms of extracted (SOM) and bound hydrocarbons (POM). Detailed compositional analysis of SOM in

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conjunction with kerogen yields the necessary information to make at least semiquantitative predictions about the amount of petroleum, which have been or will be generated by a given amount of source rock. Generally, the samples containing value of SOM less than 300 ppm are not considered for source rock potential evaluation (Wasim et al., 2004). The values of SOM for the analyzed samples range from 900 to 2,100 ppm, which shows good potential. The values of POM for the analyzed samples range from 800 to 2,700 ppm (Table 1), which is also consistent with SOM and indicates good source rock potential (Peters and Cassa, 1994).

Thermal Maturity of Sediments From Sembar Formation Thermal maturity of the samples was determined by bitumen transformation ratio (Bit/ TOC), carbon preference index (CPI), odd-even predominance (OEP), saturates/aromatics ratio, and isoprenoids to n-alkane ratios. The ratio of extractable bitumen to TOC, called the transformation ratio, ranges from near zero in shallow sediments to 0.25 (i.e., up to 250 mg/g of TOC) at peak oil generation (Peters and Cassa, 1994). Bit/TOC ratio is shown in Table 1, where the values (0.090.10) indicate thermal maturity of Sembar Formation sediments lay within the oil window (cf. Peters and Cassa, 1994). CPI and OEP are inuenced by degree of maturation and type of organic matter. CPI and OEP values are calculated by using the formula given by Bray and Evan (1961) and Scalan and Smith (1970). The CPI are calculated from n-alkanes in the range of C21 -C31 carbon numbers and OEP in the range of C21 -C25 carbon numbers (Scalan and Smith, 1970); however, the range can be adjusted to include any specied range of carbon numbers. The OEP values increase from 0.80 to 0.99 for SOM and 0.82 to 0.91 for POM as they move from top to the bottom of the sample sequence. Similarly, CPI values changes from 0.91 to 0.99 for SOM and 0.76 to 1.06 for POM as the move down to depth of the sediments samples. This increase in CPI and OEP values reveals thermal maturity of Sembar Formation sediments increases with increase in depth. The OEP and CPI signicantly above or below 1 indicate thermally immature oil or extract, whereas value of 1 indicates higher thermal maturity (Peters et al., 2005). The hydrocarbon composition of sediments was determined using capillary gas chromatography and Figure 4 shows the GC-FID chromatograms of the representative sample. Similarly each sediment sample saturated fraction exhibits unimodel n-alkanes distribution with slight even predominance in the carbon range of C20 -C30 . SOM was fractionated into saturates, aromatics, NSOs, and asphaltenes components using column chromatography on silica gel (Table 2). The column chromatographic analysis of SOM and POM reveals high proportion of aromatic hydrocarbons and polars than saturated hydrocarbons. The saturate/aromatic ratio observed for the samples increases with depth from 0.49 to 0.76 for SOM and 0.41 to 0.87 for POM. It is suggested that saturates/aromatics ratio increases with maturity that indicate maturity of the samples is increasing with depth (Peters et al., 2005). The Pr/n-C17 and Ph/n-C18 ratios decrease with increasing thermal maturity as more n-parafns are generated from kerogen by thermal cracking (Tissot et al., 1971). The ratios can be used to evaluate the thermal maturity of nonbiodegraded oils and bitumens (Peters et al., 2005). The Pr/n-C17 and Ph/n-C18 ratios for the samples are shown in Table 1 and values are in the range of 0.180.24 and 0.270.40 for POM and 0.10 0.17 and 0.280.45 for SOM, respectively (Table 2). The isoprenoids to n-alkanes ratios

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decrease with depth, which indicates a rise in thermal maturity with increasing depth of Sembar Formation (Table 1).

Conclusions
Pr/Ph ratio indicates anoxic depositional environment of sediments. Position of SOM and POM on ternary diagram shows reducing depositional conditions and marine source of organic matter. Presence of even carbon n-alkenes indicates anoxicity and low maturity of sediments, particularly in the upper part of the sedimentary column as compared with deeper samples and also probably show marine anoxic depositional environment. Pr/Ph and Pr/n-C17 versus Ph/n-C18 plots indicate source of organic matter is marine algal, deposited under reducing sedimentary environment and increasing maturity with depth. SOM, POM, and TOC reveal good source rock potential for the Sembar Formation sediments. Thermal maturity indicated by Bit/TOC ratio reveals that the organic matter of sediments is within the oil window. CPI and OEP values show increasing thermal maturity with increasing depth.

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