PETROLEUM SCIENCE AND TECHNOLOGY, 20(5&6), 633654 (2002)

CENTRAL SAUDI ARABIAN CRUDE OILS: A GEOCHEMICAL INVESTIGATION

Mohammad Farhat Ali,1,* M. R. Al-Khadhrawi,2 H. Perzanowski,1 and H. I. Halpern2 Department of Chemistry, King Fahd University of Petroleum & Minerals, Dhahran 31261, Saudi Arabia 2 Saudi ARAMCO Research & Development Center, Dhahran 31311, Saudi Arabia
1

ABSTRACT A suite of Paleozoic oils from Central Arabia was studied in order to evaluate conventional hopane and sterane biomarkers, as well as non-conventional markers such as phenanthrene and its methylated isomers. Because it was uncertain whether conventional biomarkers would be found in these light oils, additional analyses were performed on the oils for correlation purposes. These include light-hydrocarbon and mid-range micro-scale correlation techniques. Paleozoic oils and condensates from several elds from Central Arabia as well as Paleozoic condensate and two Jurassic oils from the Eastern Province (for comparison) were studied. Bulk properties, such as API gravity, percent sulfur, and nitrogen content were determined. The oils and condensates were then fractionated into their major compound classes: saturates, aromatics, polars, and asphaltenes. The full range gas chromatographic
*Corresponding author. E-mail: mafali@kfupm.edu.sa 633
Copyright & 2002 by Marcel Dekker, Inc. www.dekker.com

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analysis of the saturate and aromatic fractions did not permit meaningful distinctions for bimodal distribution of normal alkanes or identication of aromatic compounds. Microscale correlation technique was used to correlate mid-range hydrocarbons and the mid-range star diagrams (MRSD) are drawn. The MRSD showed that all Paleozoic uids (Central Arabian oils) follow patterns that are dierent from those followed by the Eastern Province. Bulk properties, pristane/ phytane ratios, methyl penanthrene ratio (MPR), and calculated reectance (% Rc) values showed that Paleozoic oils from Central Arabia dier signicantly from Jurassic oils of the Eastern Province. Central Arabian Paleozoic oils and condensates are high-API gravity, exceedingly low sulfur, low nitrogen and low metals uids. They have pristane/phytane ratios that are greater than one indicating dysoxic conditions at the time of deposition of their source rocks. Their MPR and % Rc values are indicative of dierences in timing of generation from the source rock as well as in maturity and, perhaps most signicantly, indicative of post-generative alteration such as water washing. Eastern Province Jurassic oils are: medium-gravity, high sulfur, high nitrogen crude oils. They have pristane/phytane ratios that are less than one indicating highly reducing conditions at the time of source rock deposition. Their MPR and % Rc values are indicative of generation from a source rock that was at peak oil maturity (VRe % 0.801.0%).

1. INTRODUCTION High quality (sulfur 10%, API gravity ! 40 ) petroleum was discovered in Central Saudi Arabia in the mid-1980s. The oil in Central Arabian elds is believed to be sourced from the Paleozoic sequence of Arabia, Silurian Qusaiba member of the Qalibah Formation (1,3). Studies related to Central Arabian oils that have been undertaken to data have shown that these oils are very lean in conventional biomarkers (such as hopanes and steranes) and that the biomarker compounds, where identied, are non-specic (e.g., diasteranes and tricyclics). Furthermore, recent studies have shown that biomarkers in these Paleozoic uids are dierent from biomarkers found in Paleozoic uids of neighboring regions such as Oman (14).

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The objective of this paper is to examine a suite of Central Arabian oils so as to classify the types of biomarkers present. These include both conventional biomarkers (e.g., steranes and hopanes) and non-conventional biomarkers (e.g., bicyclics and aromatized compounds). The paper also details development of ratios of compounds useful for maturity assessment, as well as nding individual compounds potentially useful for correlation. Because of their high API gravity values (over 40 ), the Central Arabian oils are very lean in biomarkers. It was possible that meaningful biomarkers (i.e., non-routine) would not be found in these oils. In this case, detailed oil oil correlation and data synthesis are accomplished using correlation techniques employing both the light and mid-range hydrocarbons (57). Gas chromatographymass spectrometry (GCMS) is used to determine the distribution of several biomarker classes in oils as well as source rocks (812).

2. EXPERIMENTAL 2.1. Crude Oil Samples Thirteen crude oil and condensate samples were collected from seven dierent elds (A to E and G) in Central Saudi Arabia to be used in this study. Two more samples from an Eastern Province eld (H) and one condensate sample (F) were used for comparison. The samples are divided into the following sub-groups:

Area Central Arabia Central Arabia Central Arabia Central Arabia Central Arabia Eastern Province Central Arabia Eastern Province

Field I.D. Field A Field B Field C Field D Field E Field F Field G Field H

No. of Samples 3 3 3 1 1 1 1 2

The exact locations of the elds studied here and well identities were not disclosed due to reasons of condentiality on the part of Saudi Aramco. However, a general location map is presented in Figure 1.

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Figure 1.

General location map of elds studied.

2.2. Crude Oil Characterization Each crude oil and condensate sample was analyzed for its API gravity, sulfur, and nitrogen contents. ASTM methods were used for these measurements (1315).

2.3. Crude Oil Fractionation Column chromatography was used to separate the topped crude oil into saturates, aromatics, polars, and asphaltene fractions (16). HPLC grade solvents (dichloromethane, n-pentane, n-hexane, toluene and methanol) were used.

2.4. Gas Chromatography (GC) A Hewlett Packard Model 5790 gas chromatograph equipped with a ame ionization detector (FID) and a J & W Scientic DB-1 capillary column (30 m 0.25 mm) were used. The injector temperature was set at 320 C, FID temperature at 350 C. Helium was used as a carrier gas with a

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column pressure of 15 psig. The split ratio was 50 : 1. The amount injected was 1 ml. The temperature program for saturates was 80320 C, ramped at 4 C/min; and for aromatic fraction/whole crude oil was 35315 C, ramped at 3 C/min. Hold time for all samples was 20 min.

3. RESULTS AND DISCUSSION 3.1. Crude Oils: Bulk Properties and Classication The properties of the composite samples of Arab crude oils are shown in Table 1. The super light Arabian crude (ASL) has a high API gravity and very low sulfur and exceedingly low nitrogen contents. Table 2 shows the cut yield and quantity data for dierent cuts from ASL crude oil. The results show that the super light Arabian crude oil has a much higher percentage (81.9%) of low boiling materials (<343 C) and very low percentage (18.1%) of high boiling materials (heavy ends) in the crude oil. The results of the determinations of API gravity, sulfur, and nitrogen contents for the fteen oil samples are presented in Table 3. The data show that oils from Central Arabia, elds A, B, C, and E, have high API gravity values that qualify them for the super light crude oil classication. The other

Table 1.

Arabian Crude OilsWhole Crude Properties ASL AL 34.7 4.6 3 0.1 3 950 1.81 58 14 4 3.8 72.5 AM 30.4 3.9 0 0.1 3 1100 2.56 80 42 9 5.7 95.0 AH 28.0 7.8 0 0.05 4 1170 2.82 120 65 14 8.2 167.0

Sample gravity, API Ried vapor pressure, PSI Hydrogen sulde, PPM Sediment and water, vol.% Salt content, PTB, NaCl Total nitrogen, PPM Total sulfur, wt.% Ash, PPM Vanadium, PPM Nickel, PPM Carbon residue, RAMS, wt. Viscosity, SUS @ 70 F ASLArabian super light. ALArabian light. AMArabian medium. AHArabian heavy.

50.2 7.4 0 TR 1 20 0.06 27 <1 <1 0.72 32.0

638 Table 2. Data

ALI ET AL. Arabian Super Light Crude Oil-Cut Yield and Quantity

0100 F (037.8 C), pentanes and lighter Yield, vol.% 100200 F (37.893.3 C), light naphtha Yield, vol.% 200300 F (93.3148.9 C), heavy naphtha Yield, vol.% Gravity,  API Total sulfur, wt.% Mercaptan sulfur, wt.% Aromatics, cut vol.% 300450 F (148.9232.2 C), kerosene Yield, vol.% Gravity,  API Total sulfur, wt.% Mercaptan sulfur, wt.% Armoatics, cut vol.% Smoke point, MM HGT Freezing point,  F 450650 F (232.2343.0 C), diesel gas oil Yield, vol.% Gravity,  API Total sulfur, wt.% Aniline point,  F Cetane index Pour point,  F 650800 F (343427 C), residual oil Yield, vol.% Gravity,  API Total sulfur, wt.% Pour point,  F Viscosity, SSU @ 122 F 800 F (427 C), plus residuum Yield, vol.% Gravity,  API Total sulfur, wt.% Pour point,  F Viscosity, SSU @ 210 F Flash point, COC,  F
 

7.4 12.7 18.6 61.3 0.012 Nil 3.5 22.4 49.0 0.015 Nil 25.0 33.0 79.7 20.8 39.9 0.038 170.5 59.4 0.0 9.9 32.2 0.069 65 57.7 8.4 22.4 0.12 105 106.5 530

CENTRAL SAUDI ARABIAN CRUDE OILS Table 3. Sample Code A1 A2 A3 B1 B2 B3 C1 C2 C3 D1 E1 F1 G1 H1 H2 Area Central Central Central Central Central Central Central Central Central Central Central Eastern Central Eastern Eastern Bulk Properties of All Samples Used in the Study Sample Type Oil Oil Oil Oil Oil Oil Oil Oil Oil Oil Oil Condensate Oil Oil Oil Sample Age Paleozoic Paleozoic Paleozoic Paleozoic Paleozoic Paleozoic Paleozoic Paleozoic Paleozoic Paleozoic Paleozoic Paleozoic Paleozoic Jurassic Jurassic Gravity ( API) 52.60 51.00 51.90 46.80 46.40 46.20 49.40 46.10 47.70 37.10 48.40 45.80 39.90 31.30 31.40 Sulfur (Wt.%) 0.01 0.01 0.01 0.02 0.02 0.02 0.03 0.03 0.05 0.07 0.08 0.01 0.04 2.35 2.33

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Nitrogen (ppm) 22 21 16 80 82 81 82 87 87 350 100 8 210 1130 1110

two oils from Central Arabia, elds D and G may be classied as light crude oils on the basis of their API gravity values. Sample F1 is a Paleozoic condensate from Eastern Province. The other two oils (Sample H1 and H2), which are from the Eastern Province (Jurassic), may be classied as medium gravity oils, based on their API gravity values. Higher sulfur contents are related to the source rock from which these oils were generated. Carbonate source rocks generate oils with higher levels of heavy ends and sulfur (17). Central Arabian oils have been shown to be generated from the Qusaiba Member (shale) of the Silurian (440-410 MYA) Qalibah Formation and not from a carbonate source (3,7). The Central Arabian Paleozoic oils have sulfur contents that are, on average, 3080 times less than the Eastern Province Jurassic oils. These very low sulfur contents warrant the classication of these Central Arabian crude oils as very sweet oils. In most oil elds around the world, sulfur is the most abundant heteroatom (N,S,O) in crude oils. Sulfur is thought to occur naturally in early diagenesis in the form of H2S, resulting in part, from the action of sulfate-reducing anaerobic bacteria. Sulfur can be found in low, medium, and high molecular weight fractions of crude oils (7,17). Nitrogen contents of the Central Arabian Paleozoic oils are also exceedingly low compared to the Eastern Province Jurassic oils. Averages for A, B, and C elds are 20, 81, and 85 ppm, respectively. Oils from other Central Arabian elds have nitrogen levels ranging between 8 and 350 ppm.

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Nitrogen levels of the Eastern Province Jurassic oils are noticeably higher: 1130 and 1110 ppm. The average value in Central Arabian oils is between three and 140 times less than the values of the oils from the Eastern Province. Correlation studies were made of percent sulfur versus API gravity, percent nitrogen versus API gravity and percent sulfur versus percent nitrogen for all oils included in this study. The study indicated that, with the exception of the Jurassic uids from the Eastern province (low API, high %S and %N), and the oils from elds D and G, which have relatively lower API gravity, all Paleozoic uids group together very tightly. The oils from elds D and G appear either to have a closer genetic relationship, or possibly a dierent source rock organic facies than other Central Arabian oils. They may have undergone migration pathways that are similar to each other, but dierent from the other hydrocarbons.

3.2. Fractionation of Crude Oils Fourteen oils (topped) and one condensate were fractionated into their compound class fractions (saturates, aromatics, polar, and asphaltenes) using silicaalumina column chromatography. Table 4 shows the fractionation data of all uids used in the study. Samples from eld A (Paleozoic from Central Arabia) contain the highest average percentage (79.6%) of saturate compounds amongst all samples. Samples from elds B and C have average percentages of saturate compounds of 71.8 and 70.4%, respectively. Field E also has a high saturate content. The API gravity of these Paleozoic oils follows the same trend as their saturate content while the sulfur and nitrogen contents follow a trend opposite to the saturate trend (c.f. Table 3) i.e., oils with highest API gravity have the lowest sulfur and nitrogen contents. The two Jurassic oils from the Eastern Province have low saturate content and low API gravities. This trend is opposite in direction to that of the Paleozoic oils which have high saturate content and high API gravity. The sulfur and nitrogen contents of the Jurassic oils are very high when compared to Paleozoic oils.

3.3. Gas Chromatography The saturate fraction C gas chromatography showed that all 12 Paleozoic uids have similar GC proles which do not permit meaningful

CENTRAL SAUDI ARABIAN CRUDE OILS Table 4. Sample Code A1 A2 A3 B1 B2 B3 C1 C2 C3 D1 E1 F1 G1 H1 H2

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Fractionation Data of All Samples (Topped, >  C) Used in the Study 343 Area Sample Type Sample Age % % % % SATs AROs POLARs Asphaltenes 15.66 15.33 16.51 22.96 20.86 22.22 22.60 23.10 23.95 31.35 20.59 17.76 31.13 50.37 46.74 3.73 4.21 2.14 3.99 4.84 4.10 4.45 4.55 5.18 3.87 4.12 3.53 4.51 8.15 11.62 1.05 1.10 0.95 1.30 1.15 1.20 1.25 1.00 0.85 2.15 1.05 0.85 1.80 2.90 2.75

Central Oil Paleozoic 79.89 Central Oil Paleozoic 79.22 Central Oil Paleozoic 79.82 Central Oil Paleozoic 71.66 Central Oil Paleozoic 72.50 Central Oil Paleozoic 71.46 Central Oil Paleozoic 70.55 Central Oil Paleozoic 71.25 Central Oil Paleozoic 69.50 Central Oil Paleozoic 62.02 Central Oil Paleozoic 73.53 Eastern Condensate Paleozoic 77.69 Central Oil Paleozoic 62.67 Eastern Oil Jurassic 38.46 Eastern Oil Jurassic 38.90

distinctions between them. No distinctive features, such as bimodally or oddeven predominance were noticed in these chromatograms. Similarly the aromatic fraction gas chromatography did not allow identication of aromatic compounds such as naphthalenes, phenanthrenes, or benzothiophenes. Attempts to identify these compounds by concentrating on the middle range of the chromatogram were not successful. Failure to come up with any useful correlation between the uids under investigation by using gas chromatographic analyses of either the saturate or aromatic fraction led to the use of a technique known as micro-scale correlation using mid-range hydrocarbons. Micro-scale correlation techniques depend on gas chromatographic analysis of whole oils, rather than compound-class fractions of the crude such as saturates and aromatics. The mid-range hydrocarbons used for micro-scale correlation purposes represent a random selection of compounds that elute between normal alkanes n-C15 and n-C22. A whole-oil gas chromatogram of oil sample A1 is shown in Figure 2. The middle range used for correlation is expanded in Figure 3. Accurate measurement of peak heights is of major importance to the accuracy of mid-range hydrocarbons micro-scale correlation technique. The basis for correlation of compounds for this purpose is that these compounds should exhibit sample-to-sample variations that permit correlation

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Figure 2.

Whole-oil gas chromatogram of oil A1.

Figure 3.

Whole-oil gas chromatogram of the middle range (3867 min.) of oil A1.

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and/or dierentiation between uids. All compounds selected between n-C15 and n-C22 elute within the time window between 38 and 67 min (Figure 3). These compounds are usually unknown minor components which meet the criteria for selection as cited above. Among the compounds selected are some known peak such as, n-C17, pristane (i-C19 with formula C19H40) n-C18, and phytane (i-C20 with formula C20H42). The main objective here is to correlate the uids under investigation by comparing ratios of compounds. To put these comparison in a pictorial form, multivariate plots (star diagrams) are used. These star diagrams make correlating and/or dierentiating uids easier. Star diagrams are multivariate plots in polar coordinates. Each star diagram can have as many axes as one needs to use. However, the more axes a star diagram has, the more complicated the picture becomes. Thus, for clarity, star diagrams that will be used in this study will have eight axes per plot, i.e., the 24 sequential ratios will be plotted on three star diagrams. These star diagrams will be referred to hereafter as mid-range star diagrams (MRSD). Star diagrams have been used to represent chemical compositions of water and oil samples. Studies of oils that employ star diagrams include: evaluation of reservoir lateral and vertical continuity, assigning relative contributions in multizone producing reservoirs and monitoring contribution changes with time, and identication of production problems such as casing leakage (5). In the present study, 24 compounds were selected for mid-range microscale correlation. These compounds are labeled C through Z as can be seen in Figure 3. Sequential ratios of these twenty-four compounds are used to construct mid-range star diagrams (MRSD). The 24 sequential ratios are calculated based on peak heights of the compounds selected. The rst ratio is calculated by dividing height of peak C by height of peak D; the second ratio is calculated by dividing height of peak D by height of peak E; the third ratio is calculated by dividing of peak E by that of peak F, and so on until the last ratio which is the only nonsequential one. This ratio is calculated by dividing height of peak C by height of peak Z. The 24 ratios are normalized and then represented by 24 axes that are divided into three groups each of which consists of eight axes. The rst eight ratios, C/D through J/K, constitute the eight axes for the rst mid-range-star-diagram (MRSD-1). The second eight ratios, K/L through R/S, constitute the eight axes for the second mid-rangestar-diagram (MRSD-2). The third eight ratios, S/T through C/Z, constitute the eight axes for third mid-range-star-diagram (MRSD-3). The maxima of the axes of the MRSDs vary and are printed in parentheses next to the axis endpoints.

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Figure 4.

MRSD-1 of all oils included in the study.

Figures 46 depict MRSD-1, MRSD-2, and MRSD-3, respectively, for all oils. Since it is somewhat hard to distinguish individual oils from these gures, the star diagrams were further subdivided. Figure 7 depicts MRSD-1 of eld A oils and shows the close grouping among eld A oils, and their extreme dierences from eld H oils. This dierentiation is in line with the dierences in source rock between the two elds (source rock of eld A is Paleozoic shale while that of eld H is Jurassic carbonate). Similar MRSDs were plotted for all Paleozoic uids and oils from the Eastern Province. The star diagram showed that all Paleozoic uids follow patterns that are dierent from those followed by oils from Eastern Province. Field B and C follow fairly similar pattern on the MRSDs. Gross dierences were observed among the remaining oils from eld D, E, F, and G. However, oils from eld D and G do follow similar paths on the three MRSDs suggesting a strong similarity between these two oils.

3.4. Gas ChromatographMass Spectrometry (GC/MS) GCMS fragmentograms of saturate fractions showed that Central Arabian oils are exceedingly lean in conventional biomarkers (e.g., hopanes

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Figure 5.

MRSD-2 of all oils included in the study.

Figure 6.

MRSD-3 of all oils included in the study.

and steranes). These biomarkers were not present in high enough concentrations and the compounds that are present were not diagnostic enough to permit using them for correlation purposes. Due to the lack of the conventionally applied biomarkers (hopanes and steranes) in the Central Arabian oils and condensate, it was decided to

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Figure 7.

MRSD-1 of eld A oils contrasted with eld H oils.

look for unconventional markers in the aromatic fractions. Phenanthrene and its four methylated isomers (MP) are amongst the promising compounds that one may nd in the aromatic fraction of crude oils. The diagnostic ion for phenanthrene is m/z 178 and that for the methylated isomers is m/z 192. GCMS fragmentogram for the aromatic fraction of oil A-1 for m/z 178 shows a single peak (Figure 8) which is that of phenanthrene. The fragmentogram for m/z 192 (Figure 9) shows four major peaks which are, in order of increasing elution time, those of 3 MP, 2 MP, 9 MP and 1 MP. Table 5 lists the abundances of phenanthrene and its methylated isomers in all oils calculated from their GCMS chromatograms. The values in the table are based on area integration of each peak. These abundances are then used to calculate various parameters that are reported in the literature, such as the maturity-sensitive Methylphenanthrene Index (MPI-1), which is used in the calculation of the calculated reectance, % Rc. The Methylphenanthrene Ratio (MPR) is calculated from the ratio of the abundances of 2-MP to 1-MP and provides the criterion as to whether Eq. I or II should be used in calculating % Rc. The criterion is that Eq. I should be used for samples with MPR values of less than 2.24 and Eq. II should be used for samples with MPR values of higher than 2.24 (1822).

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Figure 8.

GCMS chromatogram (m/z 178) of the aromatic fraction of oil A1.

Figure 9.

GCMS chromatogram (m/z 192) of the aromatic fraction of oil A1.

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Table 5.

Abundances of Phenanthrene and Its Methylated Isomers in All Oils Included in the Study

Sample Code Phen* 1.65E 09 1.34E 08 2.38E 08 1.69E 07 2.61E 08 3.32E 07 8.30E 07 4.44E 07 2.48E 07 5.57E 06 2.98E 07 2.58E 08 1.71E 07 1.73E 06 7.27E 05 1.18E 09 1.58E 08 3.26E 08 2.32E 07 3.75E 08 4.43E 07 9.51E 07 6.01E 07 3.27E 07 8.54E 06 4.06E 07 3.79E 08 2.40E 07 2.99E 06 1.11E 06 3.10E 08 3.70E 07 5.77E 07 1.09E 07 1.59E 08 2.11E 07 9.29E 07 3.24E 07 1.66E 07 1.10E 07 1.43E 07 7.27E 07 2.37E 07 5.88E 06 2.74E 06 2.24E 08 2.73E 07 6.11E 07 1.17E 07 1.85E 08 2.28E 07 5.24E 07 3.35E 07 1.73E 07 1.05E 07 1.43E 07 9.80E 07 2.33E 07 3.94E 06 1.54E 06 1.57 1.49 1.71 1.31 1.32 1.45 0.77 1.09 1.11 0.65 1.42 1.59 0.83 0.46 0.45 5.25 5.79 5.33 1.99 2.03 1.94 1.82 1.79 1.89 0.81 2.84 3.87 1.03 0.76 0.72 N.A. N.A. N.A. 1.19 1.19 1.27 0.86 1.06 1.07 0.79 N.A. N.A. 0.90 0.68 0.67 3-MePhen* 2-MePhen* 9-MePhen* 1-MePhen* MPI-1 MPR 1.36 1.41 1.28 N.A. N.A. N.A. N.A. N.A. N.A. N.A. 1.45 1.35 N.A. N.A. N.A.

Rc (for 0.65% Rm 1.35%)

Rc (for 1.35% <Rm 2.00%)

Oil-A1 Oil-A2 Oil-A3 Oil-B1 Oil-B2 Oil-B3 Oil-C1 Oil-C2 Oil-C3 Oil-D1 Oil-E1 Oil-F1 Oil-G1 Oil-H1 Oil-H2

2.17E 09 2.29E 08 3.77E 08 2.32E 07 3.82E 08 3.62E 07 2.03E 08 7.74E 07 4.39E 07 1.11E 07 4.57E 07 4.31E 08 2.72E 07 5.57E 06 1.91E 06

*Data is based on absolute areas from the GCMS results. N.A. not applicable. MPI 1 {1.5*[2 MP] [3 MP]}/{[P] [1 MP] [9 MP]}. MPI 2 {3*[2 MP]}/{[P] [1 MP] [9 MP]}. Rc (for 0.65% Rm 1.35%) 0.60 MPI 1 0.40. Rc (for 1.35%<Rm 2.00%) 0.60 MPI 1 2.30. MPR [2 MP]/[1 MP].

ALI ET AL.

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These two equations are reprinted here: Rc for 0:65 Rc for 1:35 Rm Rm 1:35 0:60 MPI-1 0:40 2:00 0:60 MPI-1 2:30 Eq: I Eq: II

Oils from eld A (Central Arabian) have low gas/oil ratios (GOR) and MPR values that are greater than 2.24 (average 5.46), thus Eq. II was used to determine their calculated vitrinite reectance values (% Rc). The % Rc values (average 1.35%) of the three oils from eld A indicate the %Rm value of the source rock at the time of generation, i.e., the source rock was at the late-post mature stage of oil generation. Low GOR for such high gravity oils may be taken as an indication of water-washing since waterwashing results in depleting the gas in the oil phase and, in turn, depleting the gas cap present over the oil via a dissolution phenomenon (5). The % Rc of these oils are on the high ends of oil generation; this may be an articial elevation resulting from water-washing, not true maturity. Water-washing may deplete phenanthrene concentration to a greater extent than it depletes the concentration of methylphenanthrenes, thus altering the outcome of the equation (18). Since aqueous solubility data for phenanthrene and methylphenanthrenes are not available, the above conclusions (about increased solubility of phenanthrene relative to methylphenanthrenes) were reached from solubility trends of benzene, toluene, and dimethylbenzene, which decrease by about an order of magnitude with each addition of a methyl group (17). Oils from eld B (Central Arabia) have low GOR and MPR values that are less than 2.24 (average 1.99) meaning that equation I should be used for the calculations of % Rc. The calculated % Rc values have an average of 1.22%. Taking these values to correspond to the % Rm values of the source rock at the time of generation, means that the source stock was in the late mature stage of oil generation. Since that is also a low GOR eld, the % Rc values obtained may again be an artifact of water-washing rather than real maturity. Field C (Central Arabia) oils have MPR values that are less than 2.24 (average 1.83), thus equation I was used in calculating the % Rc values of these oils. The calculated % Rc show an average of 0.99%. These % Rc values suggest that the source rock was at the late mature stage of oil generation. Field C has a slightly higher GOR than elds A and B. Thus, it may be as heavily water-washed as those two elds. However, the % Rc is more reasonable than that for elds A and B. Oils D1 and G1 (Central Arabia) have GOR values that are considerably higher than all the above eld, and MPR values that are less than 2.24.

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The % Rc values (using Eq. I) are 0.79 and 0.90%, respectively, suggesting that they were generated from source rocks that were at the peak time stage of oil generation, with oil G1 generated at a stage bordering on the late mature stage. Maturity seen here may be closer to reality than at elds, A, B, or C. The oil from eld E (Central Arabia) has a low GOR and MPR value that is greater than 2.24 and corresponding % Rc value (using Eq. II) of 1.45%. The same reasoning as given for eld A oils is also applicable here. F1 (Paleozoic condensate from the Eastern Province) has the highest GOR of all the Paleozoic uids considered in this study. It has an MPR value that is greater than 2.24 and corresponding % Rc value (using Eq. II) of 1.35%. This suggests that it was generated from a source rock at the post mature stage of oil generation and is in agreement with its believed true maturity. Field H oils (Jurassic, Eastern Province) have MPR values that are less than 2.24 and % Rc values (using Eq. II) of 0.68% (Oil-H1) and 0.67% (OilH2). These % Rc values indicate that these oils were generated from a source rock that was at the early peak mature stage of oil generation. Calculated reectance values (% Rc) for Paleozoic oils and condensate show that oils from elds A, B, and E (low GOR, high API) were generated when the source rock was at the late-post mature stage. These % Rc values, however, are unlikely in view of the fact that at such values of % Rc, only gas should be produced by the source rock. However, we nd black oils. Because of the low GOR of the eld, water-washing may be causing preferential depletion of phenanthrene relative to methylphenanthrenes, thus aecting (raising) the MPI-1 values and resulting in an articially high % Rc. The % Rc values for oils from eld C (higher GOR than A and B, high API) show that they were generated when the source rock was at the latemature stage or that they have been aected by water-washing though not as heavily as eld A and B. % Rc values for this eld are more reliable than those of eld A and B. The % Rc values for oils from elds D and G indicate that these oils were generated when the source rock was at the peak mature and bordering on the late mature stage. These two elds have considerably higher GORs. Thus, maturity at these elds assessed on the basis of % Rc is closer to reality than at elds A and B. These % Rc values show that the condensate from eld F was generated when the source rock was at the post mature stage. Calculated % Rc values for the Eastern Province Jurassic oils suggest that they were generated from source rock which was at the peak mature stage.

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CONCLUSIONS The following conclusions are drawn from the previously described results and discussions: (1) Bulk properties: API gravity values of Paleozoic Central Arabian oils (Fields A to G) are much higher than Jurassic oils from the Eastern Province (Field H). Percent sulfur and nitrogen contents of Paleozoic oils are exceedingly low, and especially so when compared with Jurassic oils from the Eastern Province. Bulk properties reveal similarities between Fields B and C, D and G, as well as E and F. Pristane/phytane ratios indicate that source rocks of the Central Arabian oils were deposited under dysoxic conditions and that source rocks of the Eastern Province oils were deposited under highly reducing conditions. The mid-range star diagrams (MRSD) show that all Paleozoic uids (Central Arabian oils and the condensate from Eastern Province) follow patterns that are dierent from those followed by oils from the Eastern Province. Fields B and C follow fairly similar patterns on the MRSDs. MRSDs also show that the two oils from eld D and G have, for the most part, similar patterns, which is in agreement with their similar bulk properties. Central Arabian oils are exceedingly lean in conventional biomarkers (e.g., hopanes and steranes). These biomarkers are not present in high enough concentrations and the compounds that are present are not diagnostic enough to permit using them for correlation purposes. The methylphenanthrene ratio (MPR) values of the oils from Central Arabia are all higher than those of Jurassic oils from the Eastern Province, with the exception of the oils from elds D and G. These exceptions may result from the eects of water-washing on all Central Arabian elds except D and G. The latter two elds exhibit MPR values that are closer to the Eastern Province Jurassic oils than to Central Arabian oils. Calculated reectance values (% Rc) for Paleozoic oils and condensate indicate the following: Oils from elds A, B and E [low gas/oil ratio (GOR), high API gravity] were generated when the source rock was at the latepost mature stage. Their % Rc values, however, are unrealistic in view of the fact that at such values of % Rc, only gas should be produced by the source rock. However, we nd black oils. (b) Because of low GOR of the eld, water-washing may be causing preferential depletion of phenanthrene relative to (a)

(2)

(3)

(4)

(5)

(6)

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methylphenanthrenes, thus aecting (raising) the MPI-1 values and resulting in an articially high % Rc. (c) Oils from eld C (higher GOR than A and B, high API gravity) were generated when the source rock was at the late mature stage or they have been aected by water-washing though not as greatly as elds A and B. Calculated reectance (% Rc) values for this eld are more reliable than those of eld A and B. (d) Oils from eld D and G were generated when the source rock was at the peak mature and bordering on the late mature stage. These two elds have considerably higher GORs. Thus, maturity at these elds assessed on the basis of % Rc is closer to reality than at elds A and B. (e) Condensate from eld F was generated when the source rock was at the post mature stage. (7) Calculated % Rc values for the Eastern Province jurassic oils suggest that they were generated from source rock which was at the peak mature stage.

ACKNOWLEDGMENT The facilities and support provided by King Fahd University of Petroleum & Minerals and Saudi ARAMCO are gratefully acknowledged.

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5. Halpern, H.I. Development and Applications of Light Hydrocarbon Based Star Diagrams. AAPG Bulletin 1995, 76(6), 801. 6. Kaufman, R.L.; Ahmed, A.S.; Hempkins, W.B. A New Technique for the Analysis of Comingled Oils and Its Application to Production Allocation Calculations. Proceedings Indonesian Petroleum Association, 8723/21, 1987, pp. 24268. 7. Cole, G.A.; Carrigan, W.J.; Colling, E.L.; Halpern, H.I.; Al-Khadrawi, M.R.; Jones, P.J. The Organic Geochemistry of the Jurassic Petroleum System in Eastern Saudi Arabia, Pangea: Global Environments and Resources. Canadian Society of Petroleum Geologists, Memoir 1994, 17, 413. 8. Zhilin, C.Z.; Guangja, R.; Alexander, R. A Biomarker Study of Immature Crude Oils from the Shengli Oil Field, Peoples Republic of China. Chemical Geology 1994, 113, 117. 9. Peters, K.E.; Moldowan, J.M. The Biomarker Guide. Prentice-Hall, Inc.: Englewood Clis, New Jersey, 1993. 10. Moldowan, J.M.; Peters, K.E.; Carlson, R.M.K.; Schoel, M.; Abu-Ali, M.A. Diverse Applications of Petroleum Biomarker Maturity Parameters. Arabian J. Sc. and Engg. 1994, 19(2B), 272. 11. Peters, K.E.; Kontorovich, A.Eh.; Huizinga, B.J.; Moldowan, J.M.; Lee, C.Y. Multiple Oil Families in the West Siberian Basin. AAPG Bulletin 1994, 78(6), 893. 12. Warburton, G.A.; Zumberge, J.E. Determination of Petroleum Sterane Distribution by Mass Spectrometry with Selective Metstable Ion Monitoring. Analytical Chemistry 1983, 55, 123. 13. Annual Book of ASTM Standards, Part 05.03, D405296. Standard Test Method for Density and Relative Density of Liquids by Digital Density Meter, 1999. 14. Annual Book of ASTM Standards, Part 05.02, D462996. Standard Test Method for Trace Nitrogen in Liquid Hydrocarbons by Syringe/ Inlet Oxidative and Chemiluminscence Detection, 1999. 15. Annual Book of ASTM Standards, Part 05.03, D545393. Standard Test Method for Determination of Total Sulfur in Liquid Hydrocarbon, Motor Fuels, and Oils by UV Flourescence, 1997. 16. Lancas, F.M.; Carrilho, E.; Deane, G.H.N.; Camilo, M.C.F. Group-Type Fractionation of Petroleum and Alternative Fuels by Column Liquid Chromatography. Journal of High Resolution Chromatography 1989, 12, 368. 17. Tissot, B.P.; Welte, D.H. Petroleum Formation and Occurrence, 2nd Ed.; Springer-Verlag: Berlin Heidelberg, Germany, 1984; 699 p. 18. Radke, M.; Welte, D.H. The Methylphenanthrene Index (MPI): A Maturity Parameter Based on Aromatic Hydrocarbons.

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Advances in Organic Geochemistry. John Wiley & Sons Limited, 1981; 504512. 19. Radke, M.; Welte, D.H.; Willsch, H. Geochemical Study on a Well in the Western Canada Basin: Relation of the Aromatic Distribution Pattern to Maturity of Organic Mater, Geochim, et Comochim. Acta 1982, 46(3), 1. 20. Radke, M. Organic Geochemistry of Aromatic Hydrocarbons. Advances in Chemistry. Academic Press: New York, 1987, 2, 140. 21. Radke, M. Application of Aromatic Compounds as Maturity Indicators in Source Rocks and Crude Oils. Marine Petroleum Geology 1988, 5, 224. Received June 9, 2001 Accepted September 30, 2001