PII:

Org. Geochem. Vol. 29, No. 57, pp. 11391147, 1998 # 1998 Published by Elsevier Science Ltd. All rights reserved Printed in Great Britain S0146-6380(98)00134-X 0146-6380/98 $ - see front matter

Geochemical eects of asphaltene separation procedures: changes in sterane, terpane, and methylalkane distributions in maltenes and asphaltene co-precipitates
RGEY KADIR GU
Turkish Petroleum Corporation (TPAO) Research Center, Mustafa Kemal Mah. 2. Cad. No. 86 06520, Ankara, Turkey AbstractAsphaltene precipitation, either natural or articial, may be an important cause of observed compositional dierences in oils of identical source and maturity. We studied variations in both the bulk and molecular compositions of maltenes (and asphaltene co-precipitates) prepared from six dierent oils using dierent procedures. The rst procedure used a single treatment with n-pentane (1PTC) to separate asphaltenes from maltenes. The second procedure applied four sequential n-pentane extractions of the 1PTC asphaltenes (four times-4PTC). Analyses of resulting fractions included thin layer chromatography (TLC), gas chromatography (GC), and gas chromatographymass spectrometry (GC MS). These asphaltene separation processes resulted in changes in geochemical parameters previously considered to be inuenced solely by source or thermal maturity. Maltene geochemical parameters not signicantly aected by multiple n-pentane extractions of the n-pentane-precipitated asphaltenes were the C15C35 n-paran distributions (except for a small increase in higher n-alkanes), hopane and homohopane distributions, Tm/Ts ratios, and C27:C28:C29 sterane distributions. Maltene geochemical parameters which were aected by multiple n-pentane washes of the n-pentane-precipitated asphaltenes, were increases in the C21 and C22 sterane (pregnane) to C27, C28, C29, and C30 sterane and C20 to C24 tricyclic terpane to C29 to C35 hopane ratios. The n-pentane-precipitated asphaltene co-precipitates showed an increasing ratio of methylalkanes to n-alkanes in the range from C25 to C36 following multiple extractions with n-pentane. These results suggest mechanisms of molecular interactions between maltenes and asphaltenes. # 1998 Published by Elsevier Science Ltd. All rights reserved Key wordsasphaltene, maltene, co-precipitates, n-alkane, methylalkanes, sterane, terpane, hopane, biomarker, biological marker, chemical fossils

INTRODUCTION

Petroleum consists of saturated hydrocarbons (HC), aromatic HC, and resins, the so-called ``maltene'' fraction, and an asphaltene fraction which is, by denition, a solubility class (Speight, 1980). In petroleum analyses for exploration purposes, organic geochemical processing usually begins with the separation of uid maltenes from the asphaltene solids by a solvent precipitation step. However, due to their colloidal and polar nature, asphaltenes can absorb/adsorb some of the maltene molecules forming associated co-precipitates. Therefore, separation is not complete which, in turn, has the potential to distort information obtained from saturated and aromatic HC including biomarkers (i.e., n-alkanes, isoprenoids, steranes, terpanes, etc.). If biomarker proles can be altered by asphaltene precipitation procedures, then correlation studies, and assessments of paleodepositional environments, maturity, biodegradation, and other geochemical parameters important to exploration (Seifert and Moldowan, 1981; Mackenzie, 1984; Moldowan et al., 1985) can be compromised. Asphaltene precipitation has been investigated by numerous researchers. Mitchell and Speight (1973)

demonstrated that Athabasca bitumen contains two types of asphaltenes whose solubilities dier in various organic solvents. Long (1979) has shown, for a given solvent, that the precipitation limit of an asphaltene depends upon its molecular weight and mean polarity. Schultz and Mima (1980) reported the signicance of operating conditions related to solvent to sample ratio, temperature, rinsing, and contact times on asphaltene isolations. Others have washed the asphaltenes for a single (Selucky et al., 1977) or multiple times (Jones et al., 1988; Philp et al., 1988). Still others have tried to ``purify'' precipitated asphaltenes using a soxhlet extractor (Rubinstein et al., 1979; Myhr et al., 1990). Regardless of the solvent type and operating conditions, there is a tendency for non-asphaltic n-pentane soluble and insoluble materials to be coprecipitated with asphaltenes. Only a few researchers have mentioned the co-precipitation phenomenon. Rubinstein et al. (1979) noted the coprecipitation of high molecular weight n-alkanes in the range from C30 to C40 and certain aromatic HC with asphaltenes during an asphaltene pyrolysis study. Ignaisak et al. (1977), Jones et al. (1988) and

1139

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K. Gu rgey
Table 1. Some geochemical information related to the oil samples used in this study Oil sample Basin Thrace Thrace Thrace Thrace Pre-caspian SE Turkey Source rock Tertiary-clastic Tertiary-clastic Tertiary-clastic Tertiary-clastic Permian-clastic Cretaceous-carbonate API gravity 33 34 34 35 26 15 Sulfur wt% 0.08 0.05 0.07 0.05 0.50 4.18 Pour point (8C) 40 41 36 49 45 2 Wax 32 32 32 52 33 25

A B C D E F

Osmanc|k-2 Osmanc|k-8 |-9 Devec atag lu Alacaog Daryinskaya Yananko y

Myhr et al. (1990) also noticed signicant co-precipitated material during asphaltene separations. In this study, the inuence of repeated washings on the yields and compositions of material co-precipitated with asphaltenes and maltenes was examined. Our objective was to investigate the eects on the bulk composition as well as C15+ molecular distribution of the n-alkanes, acylic isoprenoids, sterane and terpane biomarkers in the various maltene and co-precipitate fractions for one versus four npentane treatments. In the following, ``co-precipitated material-1 and co-precipitated material-4'' refer to dichloromethane soluble material removed from the precipitated asphaltenes present in the 1PTC and 4PTC fractions, respectively. Maltene-1 and maltene-4 refer to the n-pentane soluble portion of the oil obtained from 1PTC and 4PTC, respectively.
EXPERIMENTAL

eld in the Pre-caspian Basin of Kazakhstan, and the carbonate Cretaceous-sourced non-biodegraded Yananko y (F) eld in southeastern Turkey were analyzed. Geochemical information including API gravity, wax content, pour point, and sulfur content of the oil samples is given in Table 1. For comparison purposes, the wax content of the oil sample C was also determined at the University of Oklahoma and found to be 25 wt% compared to our result of 32 wt%. Analytical procedures Asphaltene separation. 0.5 g of oil was added to 20 ml n-pentane in a tared centrifuge tube. After the contact time of 30 min, the tube was stoppered, shaken vigorously, centrifuged at 2000 rpm for 5 min, and the supernatant solution (maltenes) decanted. This single precipitation is termed 1PTC. Next, the 1PTC process was repeated and a fresh 20 ml of n-pentane was added to the asphaltene precipitate remaining in the tube that was again stoppered and shaken vigorously until all the precipitate was broken up and re-suspended. The tube was again centrifuged and the supernatant solution decanted and combined with the previous one. This process (Fig. 1) was repeated four times (4PTC) to

Samples Six crude oils from the clastic Oligo-Miocenesourced Osmanc|k (A and B), Devec atag i (C), and lu (D) elds in the Thrace Basin of Turkey, Alacaog the clastic (likely) Permian sourced Daryinskaya (E)

Fig. 1. Asphaltene/maltene separation and analysis scheme with single asphaltene precipitation yielding 1PTC fractions and multiple precipitations/washings yielding 4PTC fractions. (A) TLC analysis of compound classes, (B) GC analysis of n-alkanes and isoprenoids, (C) GCMS analysis of steranes and terpanes.

Asphaltene separation procedures

1141

more thoroughly remove maltenes. Co-precipitated material was released from the asphaltenes using dicholoromethane. Thin layer chromatography. The relative percentages of saturated HC, aromatic HC, and resins of the deasphaltened oils were determined using IatroscanThio Model thin layer chromatography. Prior to sample spotting, the chromarods (quartz SIII, silica gel powder coated) were rst activated by passing through the FID ame. 1 ml deasphalted sample was then spotted. The following elution procedure was used: n-hexane to separate saturated HC, n-hexane:toluene 25:75 v/v to separate aromatic HC, and nally dichloromethane:methanol, 95:5 v/v to separate resins. Accuracy of measurements was within the 21.07% limit. Wax content. 5 ml of oil were treated with 80 ml water free acetone. After vigorous agitation, the solution was diluted to 100 ml with acetone in a 100 ml preweighed centrifuge tube. In order to reprecipitate the dissolved paran wax, the tube was cooled to 08C or less. The tube was quickly centrifuged and the clear supernatant solution was decanted and discarded. Another portion of waterfree acetone was added; the resulting solution was cooled, centrifuged, and decanted as before. The tube was then air dried and the precipitate weight reported as paran wax. Gas chromatography. Maltene fractions were analyzed on a Varian 3700 FID capillary gas chromatograph using a 25 m WCOT/OV-101 (0.22 mm i.d.) column. Asphaltene fractions (1PTC and 4PTC) were dissolved in dichloromethane prior to gas chromatography to release the co-precipitated materials. Gas chromatography/mass spectrometry. Branched/cyclic fractions were isolated from the saturated HC and analyzed on a HewlettPackard (HP) Model 5980 gas chromatograph directly connected to a HP Model 5988 A Mass spectrometer operating at 70 eV under the control of a HP Chem-Station Series 300 Data System. Selected ion monitoring was set at m/z 191 (terpanes) and m/z 217 (steranes). GCMS analysis were conducted only on the maltene fractions of the oil samples A, B, and C. Details of the analyses are described in Gu rgey (1991). Normalized distribution of C15+ alkanes, acyclic isoprenoids, methylalkanes, and biomarker ratios were calculated from the measured peak heights.

saturated HC increases for 4PTC compared to 1PTC. In contrast, asphaltenes exhibit a dramatic decrease from 1029% for 1PTC down to 28% for 4PTC. Aromatic HC and resins remain fairly constant except for sample C in which aromatic HC changes signicantly from 3% for 1PTC to 29% for 4PTC. The relative percentages of the saturates in oils have been reported to increase with the increasing maturity and migration distances, but decrease with increasing biodegradation, while asphaltenes decrease with increasing maturity and migration distance, and increase with increasing biodegradation (Connan, 1984; Williams and Winters, 1969). For unaltered oils with similar maturity, ternary diagrams of saturates, aromatics and resins + asphaltenes have even been used for correlation purposes (Bockmeulen et al., 1983). However, the bulk composition of 1PTC maltenes would cause misleading geologic interpretations if compared with bulk compositions of maltenes obtained using the 4PTC procedure. In general, as the relative saturated HC percentages of the waxy oils A, B, D, and E increase, the relative asphaltene percentage decreases from 1PTC to 4PTC. These changes are minimal for the asphaltic Yananko y oil (F) (Fig. 2). This indicates that waxy material, probably consisting of high molecular weight n-alkanes, is co-precipitated with the 1PTC asphaltenes of the waxy crudes. The co-precipitation mechanism of the waxy material could be absorption on asphaltene particles or limited solubility in n-pentane.

RESULTS AND DISCUSSION

Bulk composition There are signicant dierences in the bulk composition of the six oils analyzed by the 1PTC and 4PTC procedures (Fig. 2). For each oil, the

Fig. 2. A ternary diagram depicting saturated HC, aromatic HC, and resins + asphaltene distributions in the maltenes for the 1PTC vs. 4PTC fractions. (A) Osmanc|k lu, (E) 2, (B) Osmanc|k-8, (C) Devecatag|-9, (D) Alacaog Daryinskaya, and (F) Yananko y oils.

1142

Table 2. Normalized n-alkane distribution of the oil samples (AF). The data obtained from the gas chromatogram of the saturate fraction isolated from the maltene-1 (1PTC) and maltene-4 (4PTC) fractions C19 8.11 6.99 8.33 6.89 7.04 7 6.66 6.62 8.3 7.41 8.91 8.64 7.3 6.7 8.1 5.9 7.2 6.6 7.1 6.8 6.3 7.3 7.6 8.9 8.1 6.1 7.5 6 6.2 6.4 7.2 7 5.3 6.9 6.9 7.2 6.87 6.49 6.37 5.82 5.9 5.85 7.15 6.92 5.53 5.77 7.25 7.28 6.87 6.7 6.37 5.82 5.81 5.58 7.27 7.07 5.34 5.11 5.88 6.18 5.06 6.07 5.34 5.44 5.1 5.76 6.9 6.77 5.04 4.37 5.88 6.1 4.68 6.07 4.31 5.82 4.93 4.96 6.66 6.09 3.75 4.94 4.32 4.06 3.24 5.01 3.37 5.44 4.14 4.87 6.12 6.32 4.35 4.7 3.49 3.56 2.58 4.66 2.81 4.98 3.96 3.9 5.94 5.79 3.46 3.79 2.85 2.54 1.8 3.7 1.9 3.8 3 3.4 4.3 4.4 3 3.4 2.5 2.5 1.1 3 1.4 3.1 2.6 2.7 3.1 3.8 2.5 2.7 1.7 1.4 0.57 1.91 0.84 2.37 1.76 1.95 2.06 2.63 2.17 2.39 1.38 1.27 0.4 1.5 0.6 1.7 1.2 1.4 1.2 1.7 1.2 2.1 0.8 0.6 0.19 0.85 0.37 1.15 0.7 0.89 0.67 1.13 1.58 1.65 0.55 0.34 0.19 0.56 0.19 0.77 0.44 0.62 0.3 0.68 1.38 1.4 0.37 0.17 C20 C21 C22 C23 C24 C25 C26 C27 C28 C29 C30 C31 C32 C33 C34 0.1 0.28 0.09 0.46 0.22 0.31 0.18 0.45 0.99 1.07 0.28 0.08 C35 0.1 0.14 0.09 0.23 0.18 0.18 0.06 0.19 0.79 0.82 0.09 0.01

Oil-number of PTC

C15

C16

C17

C18

A-1PTC A-4PTC B-1PTC B-4PTC C-1PTC C-4PTC D-1PTC D-4PTC E-1PTC E-4PTC F-1PTC F-4PTC

10.7 9.39 12.4 10.6 11.9 10.7 7.09 6.39 11.6 8.15 9.64 8.89

12.2 8.61 10 8.88 10.8 9.04 6.36 6.39 10.9 9.39 11 9.99

11 8.61 10.7 7.81 8.97 9.75 6.66 6.47 7.91 7.66 9 9.65

8.78 6.7 9.08 7.04 7.92 8.24 6.97 6.39 8.7 8.98 9.64 10.7

K. Gu rgey

Table 3. Comparison of some geochemically signicant n-alkane and acyclic isoprenoid ratios for the oil samples (AF) which are obtained from the maltene-1 (1PTC) and maltene-4 (4PTC) fractions (C21+C22)/(C28+C29) 1PTC 5.16 4.20 2.16 1.94 1.97 3.37 1.88 1.71 2.00 1.70 2.07 3.71 3.59 3.08 2.38 1.80 0.81 0.52 2.92 2.85 2.75 2.13 0.83 0.46 0.04 0.07 0.17 0.18 0.14 0.09 4PTC 1PTC 4PTC 1PTC Pr/Ph C31/C19 4PTC 0.21 0.25 0.20 0.26 0.28 0.07 1PTC 1.13 1.07 1.05 1.02 0.97 0.89 OEP* 4PTC 1.04 1.04 1.97 1.01 1.05 0.90 (ak)/(C21C36)** 100 1PTC 9.8 n.d. n.d. 0.01 56 35 4PTC 65 n.d. n.d. 227 118 281

Oils

(C16+C17)/(C28+C29)

1PTC

4PTC

A B C D E F

8.00 6.27 3.53 1.76 3.42 4.76

2.57 2.42 3.08 1.57 2.80 5.04

*OEP (oddeven predominance) = (C21+6C23+C25)/(4C22+4C24). **ak and C21 C36 are the methylalkane and n-alkanes in Fig. 3C and D. The ratio belongs to the material coprecipitated with asphaltenes.

Asphaltene separation procedures 1143

Fig. 3. Gas chromatograms of the oil sample C. The maltene-1 and maltene-4 fractions are shown as A and B, respectively. C and D belong to the material from the CH2Cl2-dissolved coprecipitate-1 and coprecipitate-4 fractions, respectively. Numbers refer to carbon number of n-alkanes; Pr = pristane; Ph = phytane and the letters a k refer to methylalkanes.

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K. Gu rgey

Table 4. Normalized terpane (m/z 191) compound distribution and some geochemical ratios for the saturate fraction isolated from the maltene-1 (1PTC) and maltene-4 (4PTC) fractions Oilnumber of PTC A-1PTC A-4PTC B-1PTC B-4PTC C-1PTC C-4PTC

T20 2.9 3.99 1.63 4.75 2 6.35

T21 5.43 13.83 2.86 14.25 4 10.66

T23 5.8 11.17 4.08 8.38 3.6 13.38

T24 5.07 11.97 2.86 9.78 3.2 10.38

Tm 8.7 9.04 7.76 6.42 6 4.76

Ts 6.16 6.65 7.35 6.15 8 7.03

H29 21.74 13.3 24.49 16.76 26 19.05

H30 38.41 27.13 43.27 29.33 41.2 23.81

M30 5.8 2.93 5.71 4.19 6 4.08

T23/H30 Tm/Ts 0.15 0.41 0.09 0.28 0.09 0.56 1.41 1.36 1.06 1.04 0.75 0.68

H29/H30 0.57 0.49 0.57 0.57 0.63 0.8

M30/H30 0.15 0.11 0.13 0.14 0.15 0.17

*Numbers refer to carbon number of terpanes; T = tricyclic terpane; H = hopane; M = moretane; Tm = 17a(H)-22,29,30- trisnorhopane; Ts = 18a(H)-22,29,30-trisnorneohopane.

Molecular composition Comparison of n-alkanes and acyclic isoprenoids present in the maltene-1 and maltene-4 fractions. Oils AE are waxy (Table 1) and show low maturity with respect to biomarker signatures (Gu rgey and Yu kler, 1996). Waxy oils of this nature usually contain large proportion of terrestrially sourced nalkanes with carbon numbers in the C23C33 range (Philp and Gilbert, 1986) and show C31/C19 nalkane ratio greater than 0.4 (Saikia and Dutta, 1978) but none of the oils examined show these characteristics (Tables 2 and 3). Decreases in the C16+C17 to C28+C29 and C21+C22 to C28+C29 ratios for the maltene-4 compared to maltene-1 fractions indicate a the greater removal of C28+C29 n-alkanes from the 4PTC asphaltenes compared to the 1PTC asphaltenes (Table 3). These observations imply that some of the C23C33 n-alkanes are coprecipitated with the asphaltenes possibly by absorption of these compounds on the asphaltene particles. Similar results have been also reported by Rubinstein et al. (1979). Pristane to phytane ratio, which is a sensitive indicator of paleodepositional environmental conditions (Didky et al., 1978) does not change signicantly, except for oil sample A. This implies that asphaltene separation, which can also occur in natural settings (Wilhelms and Larter, 1994), could in some cases aect Pr/Ph ratios and associated geochemical interpretations. Oddeven predominance (OEP) stays relatively constant (Table 3). Comparison of the n-alkanes and acylic isoprenoids present in the co-precipitated material-1 and co-precipitated material-4. Representative C15+ gas chromatograms of the maltenes obtained from the co-

precipitate-1 and 4 for the oil sample C are given in Fig. 3 on which peaks from a to k appear to be methylalkanes (Philp, P. R., 1998, personal communication). All oils show an appreciable amount of n-alkanes and methylalkanes in the gas chromatograms of the co-precipitated material-1. However, n-alkanes decrease, but do not completely disappear in the co-precipitated material-4 (Fig. 3). In fact, methylalkane to n-alkane ratios increase regularly from 1PTC to 4PTC (Table 3) suggesting that removal of methylalkanes from asphaltenes is more dicult than the n-alkanes. Methylalkanes have been reported to be plant wax markers (Czochanska et al., 1986). A pronounced naphthenic hump consisting of an unresolved complex mixture (UCM) in co-precipitate-4 compared to co-precipitate-1 may be due to a decrease in the co-precipitated maltene content with repeated washings (Fig. 3). More interestingly, detectable pristane + n-C17 and phytane + n-C18 peaks are also present in the gas chromatograms of the co-precipitate-4 (Fig. 3). Comparison of the biological markers present in the maltene-1 and maltene-4 fractions. Biological marker (sterane and terpanes) variations in 1PTC compared to 4PTC, both as classes and as individual compounds, are apparent in the chromatograms of oil samples A and B (Tables 4 and 5), and C (Fig. 4). Dierences in biomarker distributions for 1PTC and 4PTC are particularly striking for oil sample C. For example, a clear relative enrichment of the C20C29 range tricyclic terpanes over the range from C29 to C35 pentacyclic terpanes is evident in the maltene-4 fraction relative to the maltene-1 fraction. This phenomenon is exemplied by

Table 5. Normalized sterane (m/z 217) compound distribution and some geochemical ratios for the selected oil samples A, B, and C. The data obtained from the mass chromatograms of the saturate fraction isolated from the maltene-1 (1PTC) and maltene-4 (4PTC) Oil-number of PTC A-1PTC A-4PTC B-1PTC B-4PTC C-1PTC C-4PTC C21 6.28 13.56 2.61 7.32 0.40 5.20 C22 2.24 3.95 1.30 1.95 0.40 16.36 C22* 0.45 1.13 0.87 2.93 0.40 50.19 C27 20R 35.5, 43.1, 39.3, 43.3, 37.2, 38.2, 32.29 35.03 37.39 38.05 36.80 10.78 C28 20R 26.1, 23.77 28.5, 23.16 26.9, 25.65 27.8, 24.39 28.7, 28.40 31.6, 8.92 C29 20R 38.4, 34.98 28.5, 23.16 33.8, 32.17 28.9, 25.37 34.0, 33.60 30.3, 8.55 (C21+C22+C22*)/ (C27+C28+C29) 0.1 0.23 0.05 0.14 0.01 2.54

*Homopregnane. **C27 20R = 14a(H) 17a(H) cholestane, C28 20R = 14a(H) 17a(H) methylcholestane; C29 20R = 14a(H) 17a(H) methyl cholestane.

Asphaltene separation procedures 1145

Fig. 4. Sterane and terpane chromatograms of saturated hydrocarbon fractions isolated from the maltene-1 and maltene-4 fractions of the oil sample C (Devecatag|-9). The terpane (m/z 191) ion chromatograms for the maltene-1 and maltene-4 fractions are shown as A and B, respectively. The sterane (m/z 217) ion chromatograms for the maltene-1 and maltene-4 fractions are shown as C and D, respectively. Numbers refer to carbon number of terpanes and steranes; T = tricyclic terpanes; H = hopane; M = moretane; Tm = 17a(H)-22, 29, 30-trisnorhopane; Ts = 18a(H)-22,29,30-trisnorneohopane.

1146

K. Gu rgey

the T23 to H30 (C23 tricyclic to C30 pentacyclic ratio) ratio that increases in maltene-4 compared to maltene-1 (Table 4). For the steranes, the C21+C22 pregnanes to C27+C28+C29 sterane (low molecular weight steranes to regular steranes) ratio again show striking increases (Fig. 4; Table 5). The presence of higher concentration of lower molecular weight biomarkers (both terpanes and steranes) in the 4PTC maltenes compared to the 1PTC maltenes suggests a possible size exclusion mechanism for ``coprecipitation'' or binding of the pregnane/homopregnane and tricyclic hydrocarbons by the asphaltenes. That is, the pregnanes and tricyclics may be small enough to t into a pore structure in asphaltene molecules but the C27C29 steranes and hopanes may be too large and are excluded. It appears that multiple washing is a way of removal of lower molecular weight molecules from the asphaltene pores. As well known in the literature, biomarkers often comprise less than 1% of an oil but are, nonetheless, key factors in oil to oil and oil to source rock correlation studies for interpreting the paleodepositional environment, age, maturation, biodegradation, and migration (Mackenzie, 1984; Grantham and Wakeeld, 1988; Peters and Moldowan, 1993). For example, signicant concentrations of pregnane and homopregnane have been linked to hypersaline paleodepositional environments (ten Haven et al., 1985): source interpretations based on biomarker analyses of 1PTC and 4PTC would dier. Also, the ratio of tricyclics to hopanes has been used as a measure of thermal maturity (Seifert and Moldowan, 1978; Aquino Neto et al., 1983) as well as a source parameter: thermal maturity interpretations for 1PTC (Fig. 4A) and 4PTC (Fig. 4B) would also dier. The apparent close associations of tricyclic terpanes with asphaltenes may help explain the tricyclic's apparent resistance to biodegradation. The dierences between 1PTC and 4PTC appear to be indicating something fundamental about the interactions of lower and higher molecular weight steranes, terpanes and methylalkane molecules and asphaltene molecules. Because asphaltene precipitation also naturally exists in reservoirs (Lomando, 1992), these results may help explain certain observations of biomarker behavior in natural settings.
CONCLUSIONS

and C20 to C24 tricyclic terpane to C29 to C35 hopane ratios. Major change in n-pentane-precipitated asphaltene co-precipitate compositions were the increasing in the ratio of methylalkanes to n-alkanes in the C25 to C36 range.
Acknowledgements The author thanks Turkish Petroleum Corporation (TPAO) for permission to publish. Sema Say|l|, Ays e Harput, Fahri Dikmen, and Tahir Can of TPAO Researh Center are acknowledged for their analytical support. The author is also grateful to Haki Naz and Oguz Ertu rk for their help in English language. I particularly appreciate the constructive review of R. M. K. Carlson as a referee; his review helped us to rene our understanding of the data and improve the manuscript.
REFERENCES

Based on the six oil samples analyzed, separation of asphaltenes with one versus four n-pentane treatments has revealed pronounced dierences in certain geochemical correlation parameters previously considered to be inuenced solely by source or thermal maturity. Major dierences from maltene-1 to maltene-4 fractions were an increase in the C21 and C22 sterane (pregnane) to C27, C28, C29, and C30 sterane

Aquino Neto, F. R., Trendel, J. M., Restle, A., Connan, J. and Albrecht, P. A. (1983) Occurrence and formation of tricyclic and tetracyclic terpanes in sediments and petroleums. In Advances in Organic Geochemistry 1981, eds. M. Bjoroy et al. Wiley, Chichester, pp. 659667. Bockmeulen, H., Barker, C. and Dickey, P. A. (1983) Geology and geochemistry of crude oils, Boliviar coastal Fields, Venezuela. Bulletin of the American Association of Petroleum Geologists 67, 242260. Connan, J. (1984) Biodegradation of crude oil in reservoirs. In Advances in Petroleum Geochemistry, eds. J. Brooks and D. H. Welte, Vol. 1. Academic Press, London, pp. 299335. Czochanska, Z., Sheppard, C. M., Weston, R. J. and Woolhouse, A. D. (1986) Organic geochemistry of sediments in New Zealand. Part I. A biomarker study of the petroleum seepage at the geothermal region of Waiotapu. Geochimica et Cosmochimica Acta 50, 507 515. Didky, B. M., Simoneit, B. R. T., Brasell, S. C. and Eglinton, G. (1978) Organic geochemical indicators of paleoenvironmental conditions of sedimentation. Nature 272, 216222. Grantham, P. J. and Wakeeld, L. L. (1988) Variations in the sterane carbon number distributions of marine source rock derived oils through geological time. Organic Geochemistry 12, 6173. Gu rgey, K. (1991) Genetic classication of the SE Turkey oils and delineation of source rock types with the use of biological markers. Ph.D. Thesis, Middle East Technical University, Ankara, 317 pp. Gu rgey, K. and Yu kler, M. A. (1996) Generation and geochemical characterization of oils in rapidly subsiding Tertiary basins A quantitative approach. In EAGE 58th Conference, Extended Abstracts, Vol. 2, LOO5. ten Haven, H. L., de Leeuw, J. W. and Schenk, P. A. (1985) Organic geochemical studies of a Messinian evaporitic basin, northern Apennines (Italy) I: Hydrocarbon biological markers for a hypersaline environments. Geochimica et Cosmochimica Acta 49, 2181 2191. Ignaisak, T., Kemp-Jones, A. V. and Strausz, O. P. (1977) The molecular structure of Athabasca asphaltene. Cleavage of the carbon sulphur bonds by radical ion electron transfer reactions. Journal of Organic Chemistry 42, 312320. Jones, M. D., Douglas, G. A. and Connan, J. (1988) Hydrous pyrolysis of asphaltenes and polar fractions of biodegraded oils. In Advances in Organic Geochemistry 1987, eds M. Mattevelli and L. Novelli, Organic Geochemistry 13, 9951001. Pergamon Press, London.

Asphaltene separation procedures Lomando, A. J. (1992) The inuence of solid reservoir bitumen on reservoir quality. Bulletin of the American Association of Petroleum Geologists 76, 11371152. Long, R. B. (1979) The concept of asphaltenes. American Chemical Society Petroleum Chemistry Division Preprints 24, 891900. Mackenzie, A. S. (1984) Application of biological markers in petroleum geochemistry. In Advances in Petroleum Geochemistry, eds J. Brooks and D. Welte, Vol. 1. Academic Press, London. Mitchell, D. L. and Speight, J. G. (1973) The solubility of asphaltenes in hydrocarbon solvents. Fuel 52, 149152. Moldowan, J. M., Seifert, W. K. and Gallegos, E. J. (1985) Relationship between petroleum composition and depositional environment of petroleum source rocks. Bulletin of the American Association of Petroleum Geologist 69, 12551268. Myhr, M. B., Schou, L., Skjetne, T. and Krane, J. (1990) Characterization of asphaltenes and co-precipitated material from a Californian oil. In Advances in Organic Geochemistry 1989, eds B. Durand and F. Behar, Organic Geochemistry 16, 931941. Pergamon Press, London. Peters, K. E. and Moldowan, J. M. (1993) The Biomarker Guide: Interpreting Molecular fossils in Petroleum and Ancient Sediments. Prentice Hall, Englewood Clis, NJ, 363 pp. Philp, R. P. and Gilbert, T. D. (1986) Biomarker distribution in Australian oils predominantly derived from terrigenous source materials. In Advances in Geochemistry 1985, eds D. Leythaeuser and J. Rullkotter, Pergamon Press, London, pp. 7384. Philp, R. P., Bakel, A., Galveez-Sinibaldi, A. and Lin, H. L. (1988) A comparison of organosulphur compunds produced by pyrolysis of asphaltenes and those present

1147

in related crude oils and tar sands. In Advances in Organic Geochemistry 1987, eds L. Mattevelli and L. Novelli, Organic Geochemistry 13, 915926. Pergamon Press. Rubinstein, I., Spyckerelle, C. and Strausz, P. O. (1979) Pyrolysis of asphaltenes: a source of geochemical information. Geochimica et Cosmochimica Acta 43, 16. Saikia, M. M. and Dutta, T. K. (1978) Depositional environment of source beds of high-wax oils in Assam Basin, India. Bulletin of the American Association of Petroleum Geologist 64, 427430. Schultz, H. and Mima, M. J. (1980) Comparison of methods for the determination of asphaltenes, oil and insolubles. Part II. American Chemical Society Fuel Chemistry Division Preprints 25, 1824. Seifert, W. K. and Moldowan, J. M. (1978) Applications of steranes, terpanes and monoaromatics to the maturation, migration and source of crude oils. Geochimica et Cosmochimica Acta 42, 7795. Seifert, W. K. and Moldowan, J. M. (1981) Paleoenvironmental reconstruction by biological markers. Geochimica et Cosmochimica Acta 45, 783794. Selucky, M. L., Chu, Y., Ruo, T. and Strausz, D. P. (1977) Chemical composition of Athabasca bitumen. Fuel 56, 369381. Speight, J. G. (1980) The Chemistry and Technology of Petroleum. Marcel Dekker, Inc., 497 pp. Wilhelms, A. and Larter, S. R. (1994) Origin of tar mats in petroleum reservoirs: Part I. Introduction and case studies. Marine and Petroleum Geology 11, 418441. Williams, J. A. and Winters, J. C. (1969) Microbial alteration of crude oil in reservoir. In Symp. Pet. Transformations in geology, American Chemical Society Division of Petroleum Chemistry, New York Meeting, Preprints 14, 22-31.