Geochemical Journal, Vol. 35, pp.

155 to 168, 2001

Compressively matured solid bitumen and its geochemical significance

ZHI -NONG G AO*, YUAN -YIN CHEN and FEI NIU

School of Chemistry and Molecular Science, Wuhan University, Wuhan 430072, China (Received October 21, 1999; Accepted March 15, 2001) Solid bitumens found in carbonate rocks of the Shiwan Dashan basin, south China, are suggested to have been matured under high pressure and moderate temperature conditions. These bitumens have different geochemical characteristics from thermally matured bitumen: very high bitumen reflectance (ROB) values and compact molecular structures (bigger size of crystal nucleus, more layer number of aromatic cycle, lower lamellar distance and so on) in spite of the chemical components reflecting lower thermal maturity. Therefore these are named as compressively matured bitumen. The geochemical characteristics of the compressively matured bitumens result from increase in its crystalline degree (grain size) under high pressures, not at high temperatures. The compressively matured bitumens retain chemical composition, molecular evolution parameters (associated with their chemical components) and hydrocarbon-producing potential similar to those of thermally less mature bitumens. High temperature and high pressure experiments proved that pressure and temperature have similar effect on the maturation indices, such as ROB values and molecular structures. The above contrasting geochemical characteristics can be used to distinguish the compressively matured bitumens from thermally matured bitumens.

I NTRODUCTION Reliability of natural bitumen reflectance (R OB) as a maturity index of carbonate rocks is still a controversial issue (Rogers et al., 1974; Jacob, 1985, 1989; Riediger, 1993; Landis and Castano, 1995; Parnell et al., 1996). Till now several relationships between R OB and vitrinite reflectance (RO) have been established (Jacob, 1985; Fu et al., 1989). In nature, the R OB values of primary bitumens sometimes vary considerably in spite of a same stage of maturation. The variation is caused by differences in their origin (e.g., thermal alteration, biodegradation and others) and other influence factors (e.g., tectonic activities, etc.), and different types of bitumens show different optical behaviors (Fu et al., 1989). In general, primary solid bitumens in carbonate rocks in highly mature level have the ROB values similar as or little higher than R O values of vitrinites in the same stratum (Fu et al., 1989).
*Corresponding author (e-mail: feiniu@whu.edu.cn)

However, the maturity estimated by the ROB values of primary anisotropic bitumens in the lower Triassic (T 1 ) carbonate rocks of the Shiwan Dashan basin, south China, is much higher than that estimated by RO, according to the published relationships between R OB and RO. Gao and Chen (1998) suggested that the difference in maturation pressure could have caused these different types of bitumens. This study was conducted to understand the origin of these bitumens based on the structural and optical characters and results of high pressure and high temperature experiments. TWO TYPES OF BITUMENS FROM BAXI PROFILE Geological background Shiwan Dashan basin locates in south China, close to Vietnam. It distributes in north-east orientation and its area is about 11,600 km 2 (Fig. 1). In the basin, the T 1 stratum consisting of marine

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Fig. 1. Geographic location map of the Shiwan Dashan basin. bitumen.

Place names of cities; * locations of outcropping

carbonate rocks is the main source of hydrocarbon accumulations. It is characterized by a great thickness, wide distribution and high abundance of organic matter at a level of moderate maturity. There are many oil seepages and solid bitumens in the stratum at north margin of the basin, because of tectonic activities (Gao and Chen, 1998). In the Shiwan Dashan basin, the T1 stratum consists of 61 layers of gray and oolitic limestones with 250 m thickness. Above the stratum are the middle Triassic (T 2 ) rocks consisting of green shale and shale-arenite with thickness >300 m, or in some part are the Jurassic rocks consisting of gray-green mudstone and interbeds of purplishred mudstone and siltstone (>60 m). Below the T1 stratum, there is upper Permian (P2) stratum consisting of gray mudstone, bioclastic limestone and sandy mudstone (>300 m). Analytical result of mineral inclusions indicates that the organic matter in the T 1 stratum has been exposed to the temperature of about 110C or higher, in accordance with the geothermal gradient in the basin (Gao and Chen, 1998). Sedimentation and burial history of the basin also re-

veals that the deepest T 1 carbonate hydrocarbon source rock in the basin reached the depth of 4,300 m, where temperature was about 110C. So the maximum RO value in the basin suggested by timetemperature index (TTI) is less than 1.20 (Gao and Chen, 1998). The T1 stratum in the Shiwan Dashan basin could have regionally experienced a high pressure condition, because this stratum have reached the depth of more than 4 km, with good confining condition (no fault cutting through the stratum). Soluble organic matter content in the T1 stratum is very high, especially in the middle part of the stratum. In addition, diapiric structures are found in the shale or mudstone just at the top or bottom of the stratum (Gao and Chen, 1998). These geological fectures are the macroscopic characteristics of high pressure in the strata (Hao et al., 1996). Bitumens from Baxi profile Baxi profile that contains abundant solid bitumens locates in middle part of the north margin of Shiwan Dashan basin (Fig. 1), where the thickness of T 1 carbonate rock stratum is about

Table 1. The thermal evolution characteristics of organic matter in the T 1 stratum of Shiwan Dashan basin

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The listed numbers are the averaged values. As organic matter is common at all the stratum, the averaged values for the stratum are also listed. CPI = [% C 2533 (odd number) + % C2331 (odd number)]/2[% C 2432 (even number)]. MPI = methylphenanthrene/phenanthrene. DPI = dimethylphenanthrene/phenanthrene. DNR = (2,6-dimethylnaphthene + 2,7-dimethylnaphthene)/1,5-dimethylnaphthene. Methyladamantane index = [1-MD/(1-MD + 2-MD)] 100, MD = methyladamantane. Methyldiamantane index = [4-DMD/(1-DMD + 3-DMD + 4-DMD)] 100, DMD = methyldiamantane.

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100 m. As a complete set of the T1 stratum is available as outcrops in the Baxi profile, we focused our study on this representative profile. After comprehensive study (Gao and Chen, 1998), we conclude that both bitumen and oil in the Baxi profile are derived from the same T1 carbonate stratum. The main evidence is geochemical similarity of the solid bitumen, the oil and the T1 carbonate source rocks as follows: (1) Distribution of terpenoids and steroids in the solid bitumen, the oil and the source rocks are identical. (2) Pyrolysis-gas chromatograms and infrared spectra of their asphaltene fractions are almost the same. (3) Content and composition of trace metals in the solid bitumen, the oil and the source rocks are similar. (4) The 13CPDB values of their components increase regularly in the expected order (saturated hydrocarbon aromatic hydrocarbon resin asphaltine kerogen). Analytical results of thermal evolution parameters (Table 1) show that the T 1 stratum in the Shiwan Dashan basin is in the stage of catagenesis, not in the stage of metagenesis, except the ROB values of anisotropic bitumens (Gao and Chen, 1998). All these bitumen samples were collected from the north margin of the basin (Fig. 1). The T1 carbonate organic matter in the Baxi profile is also in the thermally matured level. In the T1 carbonate hydrocarbon source rocks of the Baxi profile, however, there exist two types of primary solid bitumens, i.e., isotropic bitumen and anisotropic crystalline bitumen. These two kinds of bitumens have distinct geochemical characteristics, such as the disagreement in ROB values, although they are derived from the same T1 stratum (i.e., the same primary organic matter) and exposed to the similar temperature conditions during maturation (Gao and Chen, 1998). Isotropic bitumens are distributed only in narrow zones of about 15 m near the top and bottom of the T 1 stratum (i.e., coexistence of two bitumens), while in the middle of the stratum (about 70 m thick) only anisotropic crystalline bitumens are found. The

Fig. 2. Variation of bitumen reflectance in different layers of T1 stratum in the Baxi profile (stratum layers are numbered from bottom to top).

ROB values progressively increase from the two sides to the middle of the stratum (Fig. 2; Gao and Chen, 1998). Analytical procedure The solid natural bitumens were peeled off from rock samples and washed with dilute hydrochloric acid. Then the bitumens were analyzed with the following analytical instruments: Rigaku D/max-RA X-ray diffractometer, Leitz MPV-III microspectrophotometer, Nicolet 170SX infrared spectrometer, Perkin Elmer 240B elemental analyzer, Shimadzu DT-30B differential thermal analyzer, and Rock-Eval III (measuring Tmax values). For pyrolysis gas chromatography, a COS 820 pyrolysis analytical system was used, and temperature was increased to 550C for pyrolysis. Pyrolysis products were collected in a cold trap and then transferred to capillary gas chromatograph to identify with the mass spectrograph and their retention time (Zhou and Cao, 1991). Chloroform and acetone-methanol-benzene (1.5:1.5:7) also extracted natural bitumen samples successively. The solvent-extracted fractions were separated on a silica gel/alumina column chromatograph, and the saturated and aromatic hydrocarbons were eluted with normal heptane and benzene, respectively. Each fraction was analyzed by Shimadzu GC-9A gas chromatograph (27 m 0.23 mm i.d., OV-101 capillary column), and both hy-

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Fig. 3. A polarizing microphotograph of a compressively matured solid bitumen from the Shiwan Dashan basin (in this photograph, both the white and black bars are crystalline bitumens of random orientation).

Table 2. Geochemical characters of isotropic and anisotropic bitumen samples in the Baxi profile

drocarbon fractions were analyzed by Finnigan TSQ-70 GC/MS/MS combined equipment (30 m in length, 0.25 mm i.d., DB-5 quartz capillary column). In addition, carbon-13 NMR aromaticity measurements of bitumen using CP-MAS techniques were also performed to examine the results obtained by X-ray diffractometer, and the data were consistent. Results The analytical results of natural isotropic and anistropic bitumens from the Baxi profile are shown in Tables 1 and 2. When difference between maximum and minimum ROB values for bitumens is less than 0.1%, we classified the natural bitumen as isotropic bitumen. When the difference is larger than 0.20.3%, we classified it as the anisotropic. Crystals of the anisotropic bitumens filling cracks, vugs and cavities in microfossils are observed under microscope (Fig. 3). The crystalline bitumens show extinction phenomenon, and their values of ROB are much higher than that of isotropic bitumens and directly proportional to crystal grain size (Table 3). Therefore, the

Data for 2 anisotropic bitumen samples and 1 isotropic bitumen sample are displayed. The last 5 parameters were measured by Rigaku D/max X-ray diffractometer. d 002the lamellar distance of bitumens. f a, N c are for the aromaticity, layer number of aromatic cycle respectively. 1460 cm 1/1600 cm1 is IR intensity ratio at 1460, 1600 cm1.

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Degree of crystallization Fine-grained crystalline bitumen Medium-grained crystalline bitumen Coarse-grained crystalline bitumen ROB mean value (%) 1.52 2.29 2.55 Mean grain size (mm) 0.0045 0.007 0.010 Number of samples 10 12 8

The grain size is measured in JEOL JSM-35CF scanning electron microscope (2500 ), and more than 300 points are determined for one sample; ROB values are determined with Leitz MPV-III microspectrophotometer, and more than 30 points are measured.

Fig. 4. Gas chromatograms of saturated hydrocarbons in bitumens. a: isotropic bitumen (R OB = 1.14%), nC14 nC37, the highest peak: nC 20; b: anisotropic bitumen (R OB = 2.41%), nC 13nC 36, the highest peak: nC19.

anistoropic crystalline bitumens are likely be a cluster of small crystalline bitumens. The analysis of X-ray diffractometer also proves the result. In spite of different ROB values, Tmax values and molecular structure (d002 value, size of crystal nucleus, aromaticity and layer number of aromatic cycle), the isotropic and anisotropic crystalline bitumens have similar contents of hydrocarbons, aromatics, resin and asphaltine (about 3:1:1:1), and similar ratios of 1-methyl and

2-methyl diamondoid alkanes (two isomers related to thermal maturity; Table 1). Their chloroform and acetone-methanol-benzene solvent-extracted fractions also have similar moretane/hopane ratios (0.310.35), ratios of sterane isomers, C27 hopane T s /T m ratios, carbon preference index (CPI) values, methylphenanthrene index (MPI), dimethylphenanthrene index (DPI), dimethylnaphthene ratio (DNR), methyladamantane index and methyldiamantane

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Fig. 5. Infrared spectra of two bitumen samples. a: anisotropic bitumen (ROB = 2.41%); b: isotropic bitumen (R OB = 1.14%). Note: The intense absorption of A) 1700 cm1 (C=O), B) 1460 cm1, 1380 cm1 (>CH2, CH 3 ), C) 10001200 cm 1 (CO), D) 720 cm 1 [(CH2)n] of anisotropic bitumen is less than those of isotropic bitumen.

index (Table 1). The last two parameters are novel maturity indices for crude oils (Chen et al., 1996). Gas chromatograms of the saturated hydrocarbons in the two bitumen types are very similar to each other (Fig. 4). Although the infrared spectra of two bitumens are also similar, the spectrum of the anisotropic bitumens shows less intense absorption of some hydrocarbons (e.g., 1380 cm 1 , 1460 cm1 and 720 cm 1) and heteroatomic functional groups (e.g., 1700 cm1, 10001200 cm 1, etc.) compared with that of the isotropic bitumens (Fig. 5). Pyrolysis-gas chromatography analysis (PyGC) shows that the anisotropic crystalline bitumens contain slightly smaller amount of heteroatomic compounds and saturated and cyclic hydrocarbon components in the pyrolytic products than those in the isotropic bitumens do (Fig. 6). In Fig. 6, many alkane peaks of isotropic bitumen is higher than those of anisotropic bitumen, such

Fig. 6. Pyrograms of bitumens in the Shiwan Dashan basin (first and second peak of the paired peaks with the same carbon number in nC 8nC16 are assigned to alkenes and alkanes, respectively). a: anisotropic bitumen (R OB = 2.41%); b: isotropic bitumen (ROB = 1.14%). Note: Many alkane peaks of isotropic bitumen is higher than those of anisotropic bitumen, such as nC10, nC12, nC17, nC20, nC22, nC23, nC25 and so on. Peaks of heteroatomic and cyclic compounds between those of normal alkanes are also higher in isotropic bitumen.

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as nC10, nC 12, nC17, nC 20, nC 22, nC23, nC 25 and so on. Peaks of heteroatomic and cyclic compounds between those of normal alkanes are also higher in isotropic bitumen. The pyrograms of two bitumens are apparently similar and only after careful calculations the above difference can be obtained. In addition, their hydrocarbon-producing values in pyrolysis chromatography, total weight loss values in 700C, hydrogen index S1/(S 1 + S 2) are almost the same, and their H/C atomic ratios, IR intensity ratio 1460 cm1/1600 cm1 are also similar (Tables 1 and 2). These characteristics reveal that two bitumens possess similar hydrocarbon-producing potential. Discussion In general, sedimentary organic matter of ROB = 1.2% (corresponding to R O = 1.17%) is just in mature phase, while those of ROB = 1.9% and 2.4% (corresponding to RO = 1.65%, 2.0%) are at highly matured and overmature stages respectively (Fu et al., 1989). In this sense, the isotropic bitumens in Table 2 are in mature stage and most of the anisotropic crystalline bitumens are in overmatured phase. However, the differences in H/C atomic ratio, 1460 cm1/1600 cm1 specific value and weight loss amount at 700C are small between the two types of bitumens, compared with the large difference in ROB values and molecular structures (Tables 1 and 2). Rock-Eval Tmax value is another maturity index most in use and has a certain difference between the isotropic and anisotropic bitumens. As both bitumens are in the catagenesis stage and are derived from the same primary organic matter as stated above, these differences in the geochemical characteristics cannot be explained simply by differences in the degree of thermal maturation. Stasiuk (1997) reported that the differences in optical textures (isotropic vs. mosaic pyrobitumen) and ROB values can be related to differences in chemical compositions of precursor oil (nongraphitizing, NSO-rich petroleum vs. graphitizing, low-S petroleum). However, as was shown before, two of the bitumens in Baxi profile are derived from the same primary petroleum, and their con-

tent of S, O, and N elements is also the same (Gao and Chen, 1998). Barker and Bone (1995) discovered that high ROB (2.42.7%) zone of 6 m thickness distributes in contact aureole while ROB values are lower at out sides of this zone, and concluded that thermal stress caused the high ROB zone. However, there is not heat source igneous rocks in the Baxi profile. Curiale (1986) proposed that solid bitumens associated with oil source rocks can be classified as either pre-oil or postoil, and that the former (early-generation immature product) is much less mature than the latter (generated from a mature source rock). Following generation and expulsion, both pre-oil and post-oil solid bitumens are subject to the same modification processes, such as thermal alteration. Therefore, although there can be a large difference in their ROB values, neither pre-oil nor pastoil bitumens cannot have high ROB values if both bitumens and their source rocks experience only low thermal stress as those in T 1 carbonate rocks of Baxi profile. So the following question arises. Why did the carbonate rocks exposed to the same level of thermal stress form two types of the bitumens with different values of R OB? A sedimentary basin is actually a thermochemical reactor at low temperatures. Besides temperature, pressure is another important factor controlling maturation processes of organic matter (McTavish, 1978; Braun and Burnham, 1990; Hunt, 1990; Jiang et al., 1998). As mentioned above, the T1 stratum in Shiwan Dashan basin (including the Baxi profile) could have experienced the high pressure of 1,000 bars (4 km depth). Therefore, it is plausible that fluid pressures inside the rocks increased to a peak in the oil-generating widow and decreased below it (Hunt, 1995). As the source rocks and thermal maturation levels of these two bitumens are similar, Gao and Chen (1998) suggested that pressure difference between the middle and the margin of the stratum could be the only possible origin of two different bitumens. If formation pressure is higher at the middle than at the margins of the strata, that can cause the progressive ROB increase from its side to the middle of the strata (Fig. 2).

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In order to test the hypothesis of compressively matured solid bitumen, high pressure and high temperature simulation experiment was conducted to evaluate the effect of pressure on maturation processes. LABORATORY MATURATION E XPERIMENT Introduction for the experiment Because of the lack of practical geobarometers compared with many useful geothermometers, the influence of pressure to maturation is difficult to distinguish in the nature. Therefore, studies in this area are few and the results are not consistent (McTavish, 1978; Braun and Burnham, 1990). Most organic geochemists believe in pressure retardation of organic matter maturation (Hunt, 1990; Price and Wenger, 1992). High pressure, however, causes structural changes of organic matter, such as increase in the size of crystal nucleus and aromaticity and decrease in lamellar distance (Jiang et al., 1998). As more compact the molecular structures of bitumens are and the higher their R OB values will be, these changes should result in the increase in R OB values. To test the effect of pressure on the formation of bitumen of this type, compressively matured bitumen, a series of laboratory experiments was performed. Samples and experimental procedure Simulation experiments are conducted with the T 1 isotropic bitumens in Baxi profile, Shiwan Dashan basin, and their basic geochemical characteristics are shown in Table 2. A rock sample rich in isotropic bitumens was divided into 11 aliquots, and reacted under different experiment conditions as listed in Table 4. The high pressure experiments were performed with a specially designed piston cylinder pressure vessel, which can reach 1200 atm at 700C. The container material in the piston cylinder (19.05 mm i.d.) is platinum and medium of pressure transmission is pyrophyllite. Pressure was increased to a required value by piston-in method, and then temperature was increased. Pressure values were calibrated using lead melting point and temperatures were

Table 4. Run conditions and analytical results of simulation experiments of bitumen maturation

The analytical error of ROB measurements is about 0.01(%). f a, N c are for the aromaticity, layer number of aromatic cycle respectively.

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measured with a WRe 5-WRe 26 thermocouple. The calibrated pressure values were also compared with those produced by high-pressure liquids. The high-pressure liquids (e.g., oils) were produced and transmitted by a high-pressure pump, and the pressure values can be watched through a manometer. The pressure error of two methods is less than 2%. The temperature was controlled within 1C, and the error induced by high pressure was ignored. When the simulation experiments finished, the samples were quenched to room temperature before pressure release. During the ambient pressure experiments, the samples were held in quartz tubes filled with nitrogen. As both ends of the tubes are capillaries open to the atmosphere, the inside pressure was kept at one atmosphere during the experiment. All simulation samples were

subjected to the required temperatures and pressures for 96 hrs. After the experiments, the solid bitumens were peeled off from the rock samples and washed with dilute hydrochloric acid. Then, the bitumen samples were analyzed mainly with Rigaku D/maxRA X-ray diffractometer, Py-GC and Leitz MPVIII microspectrophotometer in addition to the ordinary analyses (e.g., elemental analysis and thermal analysis). In addition, GC, GC/MS chromatograms were also obtained for the solvent extracts from samples 10 and 11 for specific molecular distributions. Results and discussion Results of laboratory simulation are listed in Table 4. In sample 1, which reacted at 200C and

Fig. 7. Variation of a) H/C atomic ratio, b) d 002 , c) ROB and d) aromacity with temperature and pressure.

Table 5. The analytical results of saturated hydrocarbons in natural and simulation samples

Numbers 1 and 2 are for the samples of outcrop isotropic and anisotropic bitumens respectively, while numbers 3 and 4 represent simulation samples 10 and 11 respectively. Pr and Ph represent pristane, phytane respectively.

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Table 6. Pyrolytic products of natural and simulation samples

The sample numbers are consistent with Table 5. Cyclic hydrocarbon, polycyclic aromatic hydrocarbon and phenol are also counted in saturated hydrocarbon, aromatic hydrocarbon and non-hydrocarbon, respectively. Light-weight hydrocarbon ratio = light hydrocarbon ( C10)/weight hydrocarbon ( C11 ).

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1 atm, no change was observed from the starting material. While in sample 2, which reacted at 200C and 1000 atm, changes in its structure and ROB value were detected. As the temperature rises, the effect of pressure on the changes in the molecular structure (e.g., d002 value, aromaticity, size of crystal nucleus, layer number of aromatic cycle and H/C atomic ratio) and ROB value becomes more clear (Table 4, Fig. 7). The results also indicate that, at a same temperature, the change becomes more significant with increasing pressure. For example, decrease in d002 and increase in ROB values and aromaticities with pressure become more distinct at higher pressure (Fig. 7). Samples 3, 7, 10 and 1 were reacted at 1 atm with variable temperature, and the variations in the results are smaller than those observed at higher pressures. Comparing samples 9 and 10 with sample 7 or 1 respectively, we can observe that pressure mainly affects the compact degree of bitumens molecular structure, in contrast with the change in the carbon content caused by the temperature difference. Although most parameters are affected by the pressure and temperature changes, the changes of H/C atomic ratio, IR intensity ratio 1460 cm1/ 1600 cm1 and total weight loss are small compared with those of the ROB value and molecular structure (Table 4). The experimental results clearly show that not only increasing temperature but also increasing pressure can enhance solid bitumen evolution. Moreover, it seems that temperature and pressure compensate each other in bitumen evolution, but low pressures (such as 300 atm) may have little effect (comparing sample 3 with sample 4). In contrast, significant difference was observed in the results at 800 and 1000 bars, indicating that the small pressure difference at higher pressure can have the important effect on the maturation. The saturated hydrocarbon fractions extracted from samples 10 and 11 were analyzed using GC and GC/MS. The two samples reacted at the same temperature have similar values of molecular evolution parameters (Table 5), although ROB values of the bitumens increase with pressure, that is consistent with the observation in the natural bitu-

men samples (isotropic bitumen vs. anisortopic crystalline bitumen). Pyrolytic products of the simulation samples reacted at the same temperature have similar composition and the two natural bitumens in the Baxi profile also have similar composition of the pyrolytic products each other (Table 6). Although the increase of ROB values due to increase of pressure is apparently small, in particular at lower temperatures (Table 4), the pressure effect could be underestimated due to the short time duration of the laboratory experiment compared with the geological time scale. The above similarity of simulation products and natural bitumens in geochemical characteristics and chemical composition proved formation of the compressively matured bitumen in nature. O RIGIN OF THE COMPRESSIVELY M ATURED BITUMEN As the anisotropic crystalline bitumen in Baxi profile, Shiwan Dashan basin, forms under high pressures and moderate temperatures, we call it compressively matured solid bitumen. This type of pressure-induced bitumen differs in geochemical characteristics from thermally matured bitumen: high ROB values, high Tmax values and compact molecular structures vs. the chemical components reflecting lower thermal maturity. Especially, its hydrocarbon-producing potential is similar to isotropic bitumens with much lower ROB values. Sajgo et al. (1986) discovered that pressure could not only retard but also accelerate the organic matter maturation, depending on the experimental conditions. Costa Neto (1991) approved this conclusion based on theoretical considerations. Pressures can accelerate mature reactions of organic matter, as distance among reactants is smaller at higher pressure. On the other hand, McTavish (1998) discussed that high pressure causes decrease in porosity of mudstone strata resulting in decrease in heat transfer, so the cumulative heat flow in high-pressure strata is lower than that in low-pressure strata. As the result, ap-

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parent retardation of organic matter maturation can be observed due to the high pressure. As porosity is large and a number of continuous fractures exist in carbonate rocks, high pressure might not affect temperature distribution in the Baxi profile as McTavish (1998) discussed, and therefore affect only reaction processes of the organic matter as Jiang et al. (1998) suggested. Similar to thermally matured bitumens, compressively matured bitumens also increase their directional structural arrangement from no crystalline structure to crystalline-like structure, forming anisotropic bitumens with high ROB. In contrast, chemical composition of the compressively matured bitumens is relatively unchanged and their hydrocarbon-producing potential does not decrease obviously. The anisotropic crystalline bitumen in the Baxi profile, Shiwan Dashan basin, is an actual example of compressively matured bitumens. The simulation experiments also prove the pressure-induced maturation of solid bitumens. GEOCHEMICAL S IGNIFICANCE Compressively matured bitumen can be formed at moderate temperatures and high pressures in nature. It has high ROB values without having been exposed to a high level of thermal stress, therefore does not follow the usual relationships between ROB and R O which have been reported for thermally matured bitumens. As the compressively matured bitumens yield apparently higher values of R OB which overestimate the true thermal maturity of carbonate rocks, it is essential to distinguish compressively matured bitumens from thermally matured bitumens in oil and gas exploration. Geochemists classified natural bitumens based on their geochemical characteristics (Curiale, 1986; Georgy, 1992). The compressively matured solid bitumens have self-contradictory evolution parameters and geochemical characteristics. In contrast to the abnormally high ROB values, high Tmax values and compact molecular structures, the compressively matured bitumen preserves the

chemical components (including biomarkers) formed at low thermal maturity. By combining the geochemical information such as biomarkers, we might be able to use the ROB as a new maturity index to identify the compressively matured bitumen. Compressively matured solid bitumens crystallize mainly because of pressure effect. Their condensation polymerization (i.e., at the time of formation of polymers in bitumens, small molecules are released) might not be as complete as that of thermally matured bitumens, and light hydrocarbons and hydrocarbon groups might be trapped in crystal-like structures of the bitumen. As a result, hydrocarbon content and hydrocarbon-producing potential of bitumens of this type are high (e.g., high hydrogen index, high weight loss value, high H/C atomic ratio and so on), despite their high ROB values (Tables 1, 2 and 4). This phenomenon is consistent with their lower degrees of thermal evolution. CONCLUSION Field study and laboratory experiments have elucidated that pressure can accelerate evolution of natural solid bitumens. Under a high pressure and moderate temperature, solid bitumens crystallize and their reflectance increase with progress of crystallization. This pressure-induced solid bitumen (compressively matured bitumen) has self-contradictory evolution characteristics. It has high bitumen reflectance (R OB) values and compact molecular structures (lower d002 values, bigger sizes of crystal nucleus, etc.), whereas it also has a similar chemical composition and hydrocarbon-production potential to the thermally matured bitumens with lower R OB values. These geochemical characteristics can be used to distinguish the compressively matured bitumens from thermally matured bitumens.
AcknowledgmentsWe thank Professor Ming-de LU (Department of Petroleum Geology, China University of Geosciences) for his technical assistance during studying on optical characteristics of natural bitumens.

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