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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).
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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
1998). 1). bitumen. bioclastic limestone and sandy mudstone (>300 m). The T1 stratum in the Shiwan Dashan basin could have regionally experienced a high pressure condition.20 (Gao and Chen. Below the T1 stratum. N. There are many oil seepages and solid bitumens in the stratum at north margin of the basin. It is characterized by a great thickness. the T1 stratum consists of 61 layers of gray and oolitic limestones with 250 m thickness. In addition. 1. 1998). because this stratum have reached the depth of more than 4 km.. where the thickness of T 1 carbonate rock stratum is about . Analytical result of mineral inclusions indicates that the organic matter in the T 1 stratum has been exposed to the temperature of about 110°C or higher. or in some part are the Jurassic rocks consisting of gray-green mudstone and interbeds of purplishred mudstone and siltstone (>60 m). Fig. * locations of outcropping carbonate rocks is the main source of hydrocarbon accumulations. 1996). there is upper Permian (P2) stratum consisting of gray mudstone. 1998). with good confining condition (no fault cutting through the stratum). Gao et al. diapiric structures are found in the shale or mudstone just at the top or bottom of the stratum (Gao and Chen. Place names of cities. Geographic location map of the Shiwan Dashan basin. Soluble organic matter content in the T1 stratum is very high. where temperature was about 110°C. Bitumens from Baxi profile Baxi profile that contains abundant solid bitumens locates in middle part of the north margin of Shiwan Dashan basin (Fig. wide distribution and high abundance of organic matter at a level of moderate maturity. 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. Above the stratum are the middle Triassic (T 2 ) rocks consisting of green shale and shale-arenite with thickness >300 m. because of tectonic activities (Gao and Chen. These geological fectures are the macroscopic characteristics of high pressure in the strata (Hao et al.300 m. especially in the middle part of the stratum. in accordance with the geothermal gradient in the basin (Gao and Chen. In the Shiwan Dashan basin. 1998).156 Z. So the maximum RO value in the basin suggested by timetemperature index (TTI) is less than 1.
157 . the averaged values for the stratum are also listed.5-dimethylnaphthene. DNR = (2.7-dimethylnaphthene)/1. DPI = dimethylphenanthrene/phenanthrene. MD = methyladamantane. Methyldiamantane index = [4-DMD/(1-DMD + 3-DMD + 4-DMD)] × 100.Table 1.6-dimethylnaphthene + 2. MPI = methylphenanthrene/phenanthrene. The thermal evolution characteristics of organic matter in the T 1 stratum of Shiwan Dashan basin Compressively matured solid bitumen The listed numbers are the averaged values. CPI = [% C 25–33 (odd number) + % C23–31 (odd number)]/2[% C 24–32 (even number)]. Methyladamantane index = [1-MD/(1-MD + 2-MD)] × 100. As organic matter is common at all the stratum. DMD = methyldiamantane.
the oil and the T1 carbonate source rocks as follows: (1) Distribution of terpenoids and steroids in the solid bitumen. 2. ROB values progressively increase from the two sides to the middle of the stratum (Fig. a COS 820 pyrolysis analytical system was used. however. (2) Pyrolysis-gas chromatograms and infrared spectra of their asphaltene fractions are almost the same. Analytical procedure The solid natural bitumens were peeled off from rock samples and washed with dilute hydrochloric acid.d.. coexistence of two bitumens). 1991). there exist two types of primary solid bitumens.5:7) also extracted natural bitumen samples successively. and both hy- .e. 1998).e. After comprehensive study (Gao and Chen. 1998). such as the disagreement in ROB values. The main evidence is geochemical similarity of the solid bitumen.. N. the oil and the source rocks are identical. respectively. All these bitumen samples were collected from the north margin of the basin (Fig. i. the oil and the source rocks are similar. In the T1 carbonate hydrocarbon source rocks of the Baxi profile. These two kinds of bitumens have distinct geochemical characteristics. (3) Content and composition of trace metals in the solid bitumen. Gao et al. Isotropic bitumens are distributed only in narrow zones of about 15 m near the top and bottom of the T 1 stratum (i.e. Variation of bitumen reflectance in different layers of T1 stratum in the Baxi profile (stratum layers are numbered from bottom to top). we conclude that both bitumen and oil in the Baxi profile are derived from the same T1 carbonate stratum. and temperature was increased to 550°C for pyrolysis. 100 m.158 Z. 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. we focused our study on this representative profile.5:1. although they are derived from the same T1 stratum (i. Nicolet 170SX infrared spectrometer.. The solvent-extracted fractions were separated on a silica gel/alumina column chromatograph. the same primary organic matter) and exposed to the similar temperature conditions during maturation (Gao and Chen. Then the bitumens were analyzed with the following analytical instruments: Rigaku D/max-RA X-ray diffractometer. 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.. The Fig. OV-101 capillary column). 1998). Perkin Elmer 240B elemental analyzer. and the saturated and aromatic hydrocarbons were eluted with normal heptane and benzene. As a complete set of the T1 stratum is available as outcrops in the Baxi profile. Shimadzu DT-30B differential thermal analyzer. Leitz MPV-III microspectrophotometer. The T1 carbonate organic matter in the Baxi profile is also in the thermally matured level.23 mm i. except the ROB values of anisotropic bitumens (Gao and Chen. isotropic bitumen and anisotropic crystalline bitumen. while in the middle of the stratum (about 70 m thick) only anisotropic crystalline bitumens are found. Each fraction was analyzed by Shimadzu GC-9A gas chromatograph (27 m × 0. 1998). Gao and Chen. (4) The δ 13CPDB values of their components increase regularly in the expected order (saturated hydrocarbon → aromatic hydrocarbon → resin → asphaltine → kerogen). Chloroform and acetone-methanol-benzene (1. 2. For pyrolysis gas chromatography. and Rock-Eval III (measuring Tmax values). not in the stage of metagenesis. 1).
vugs and cavities in microfossils are observed under microscope (Fig.d. DB-5 quartz capillary column). 3). 1460 cm –1/1600 cm–1 is IR intensity ratio at 1460. The last 5 parameters were measured by Rigaku D/max X-ray diffractometer. Table 2. When difference between maximum and minimum ROB values for bitumens is less than 0.2–0. layer number of aromatic cycle respectively. f a.25 mm i. d 002—the lamellar distance of bitumens.3%. we classified it as the anisotropic. and the data were consistent. 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..Compressively matured solid bitumen 159 Fig.1%. N c are for the aromaticity. and their values of ROB are much higher than that of isotropic bitumens and directly proportional to crystal grain size (Table 3). Results The analytical results of natural isotropic and anistropic bitumens from the Baxi profile are shown in Tables 1 and 2. we classified the natural bitumen as isotropic bitumen. 1600 cm–1. carbon-13 NMR aromaticity measurements of bitumen using CP-MAS techniques were also performed to examine the results obtained by X-ray diffractometer. When the difference is larger than 0. . In addition. The crystalline bitumens show extinction phenomenon. 0. both the white and black bars are crystalline bitumens of random orientation). the Data for 2 anisotropic bitumen samples and 1 isotropic bitumen sample are displayed. Crystals of the anisotropic bitumens filling cracks. Therefore. A polarizing microphotograph of a “compressively matured solid bitumen” from the Shiwan Dashan basin (in this photograph. 3.
nC 13–nC 36. 4. anistoropic crystalline bitumens are likely be a cluster of small crystalline bitumens.41%).52 2. carbon preference index (CPI) values. ratios of sterane isomers.160 Z.55 Mean grain size (mm) 0. The analysis of X-ray diffractometer also proves the result. methylphenanthrene index (MPI). aromatics. size of crystal nucleus. resin and asphaltine (about 3:1:1:1). methyladamantane index and methyldiamantane . the highest peak: nC 20. N.007 0. the highest peak: nC19.14%).0045 0. nC14– nC37. In spite of different ROB values. Relationship between bitumen reflectance (R OB) and grain size Degree of crystallization Fine-grained crystalline bitumen Medium-grained crystalline bitumen Coarse-grained crystalline bitumen ROB mean value (%) 1. Gao et al. C27 hopane T s /T m ratios.010 Number of samples 10 12 8 The grain size is measured in JEOL JSM-35CF scanning electron microscope (2500 ×).31–0. and similar ratios of 1-methyl and 2-methyl diamondoid alkanes (two isomers related to thermal maturity. Table 1). and more than 300 points are determined for one sample.29 2. Their chloroform and acetone-methanol-benzene solvent-extracted fractions also have similar moretane/hopane ratios (0. dimethylphenanthrene index (DPI). b: anisotropic bitumen (R OB = 2. Tmax values and molecular structure (d002 value. aromaticity and layer number of aromatic cycle). the isotropic and anisotropic crystalline bitumens have similar contents of hydrocarbons. dimethylnaphthene ratio (DNR). Gas chromatograms of saturated hydrocarbons in bitumens.35). Table 3. Fig. a: isotropic bitumen (R OB = 1. and more than 30 points are measured. ROB values are determined with Leitz MPV-III microspectrophotometer.
5. Gas chromatograms of the saturated hydrocarbons in the two bitumen types are very similar to each other (Fig. nC12. 1380 cm–1 (>CH2. D) 720 cm –1 [(–CH2–)n] of anisotropic bitumen is less than those of isotropic bitumen. Infrared spectra of two bitumen samples. the spectrum of the anisotropic bitumens shows less intense absorption of some hydrocarbons (e. nC20. nC22. such as nC10. . 6. a: anisotropic bitumen (R OB = 2.) compared with that of the isotropic bitumens (Fig.41%). nC23. 6. In Fig. 1460 cm–1 and 720 cm –1) and heteroatomic functional groups (e.Compressively matured solid bitumen 161 Fig. B) 1460 cm–1.g. a: anisotropic bitumen (ROB = 2. etc. –CH 3 ). 1996). Pyrograms of bitumens in the Shiwan Dashan basin (first and second peak of the paired peaks with the same carbon number in nC 8–nC16 are assigned to alkenes and alkanes.14%). such Fig.14%). The last two parameters are novel maturity indices for crude oils (Chen et al.. 1700 cm–1.g.. Note: The intense absorption of A) 1700 cm–1 (C=O). nC17. 4). Peaks of heteroatomic and cyclic compounds between those of normal alkanes are also higher in isotropic bitumen. nC25 and so on. index (Table 1).. 5). 1380 cm –1 . C) 1000–1200 cm –1 (C–O). many alkane peaks of isotropic bitumen is higher than those of anisotropic bitumen. 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). b: isotropic bitumen (ROB = 1. respectively). 1000–1200 cm –1. Note: Many alkane peaks of isotropic bitumen is higher than those of anisotropic bitumen.41%). b: isotropic bitumen (R OB = 1. Although the infrared spectra of two bitumens are also similar.
their hydrocarbon-producing values in pyrolysis chromatography. nC23.17%) is just in mature phase. However. Jiang et al. mosaic pyrobitumen) and ROB values can be related to differences in chemical compositions of precursor oil (nongraphitizing. Gao et al. Braun and Burnham. as nC10.0%) are at highly matured and overmature stages respectively (Fu et al. total weight loss values in 700°C. that can cause the progressive ROB increase from its side to the middle of the strata (Fig.162 Z. O. However. and concluded that thermal stress caused the high ROB zone. compared with the large difference in ROB values and molecular structures (Tables 1 and 2). Therefore. 2).4–2. Hunt. Discussion In general. Stasiuk (1997) reported that the differences in optical textures (isotropic vs. while those of ROB = 1. 1460 cm–1/1600 cm–1 specific value and weight loss amount at 700°C are small between the two types of bitumens. 1995). As both bitumens are in the catagenesis stage and are derived from the same primary organic matter as stated above. Barker and Bone (1995) discovered that high ROB (2. 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. nC 22. The pyrograms of two bitumens are apparently similar and only after careful calculations the above difference can be obtained. the isotropic bitumens in Table 2 are in mature stage and most of the anisotropic crystalline bitumens are in overmatured phase.000 bars (4 km depth). pressure is another important factor controlling maturation processes of organic matter (McTavish. Therefore.7%) zone of 6 m thickness distributes in contact aureole while ROB values are lower at out sides of this zone. Besides temperature. If formation pressure is higher at the middle than at the margins of the strata. 1989). it is plausible that fluid pressures inside the rocks increased to a peak in the oil-generating widow and decreased below it (Hunt. 2. Peaks of heteroatomic and cyclic compounds between those of normal alkanes are also higher in isotropic bitumen. As the source rocks and thermal maturation levels of these two bitumens are similar. 1990. N. 1978. In this sense. and their con- tent of S. graphitizing. In addition. although there can be a large difference in their ROB values.65%. 1998). So the following question arises. both pre-oil and post-oil solid bitumens are subject to the same modification processes. NSO-rich petroleum vs.4% (corresponding to RO = 1. and their H/C atomic ratios. However. IR intensity ratio 1460 cm–1/1600 cm–1 are also similar (Tables 1 and 2). and that the former (early-generation immature product) is much less mature than the latter (generated from a mature source rock). nC 12. As mentioned above. such as thermal alteration. These characteristics reveal that two bitumens possess similar hydrocarbon-producing potential. hydrogen index S1/(S 1 + S 2) are almost the same.9% and 2. as was shown before. the T1 stratum in Shiwan Dashan basin (including the Baxi profile) could have experienced the high pressure of 1. low-S petroleum). . these differences in the geochemical characteristics cannot be explained simply by differences in the degree of thermal maturation. there is not heat source igneous rocks in the Baxi profile.. 1998). Following generation and expulsion. 1990. the differences in H/C atomic ratio. 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. 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. two of the bitumens in Baxi profile are derived from the same primary petroleum. nC17. nC 25 and so on.2% (corresponding to R O = 1. Curiale (1986) proposed that solid bitumens associated with oil source rocks can be classified as either pre-oil or postoil.. Rock-Eval Tmax value is another maturity index most in use and has a certain difference between the isotropic and anisotropic bitumens. nC 20. sedimentary organic matter of ROB = 1. and N elements is also the same (Gao and Chen.
“compressively matured bitumen”. To test the effect of pressure on the formation of bitumen of this type. f a. Pressure was increased to a required value by piston-in method. the influence of pressure to maturation is difficult to distinguish in the nature.. 1990).) is platinum and medium of pressure transmission is pyrophyllite. High pressure. A rock sample rich in isotropic bitumens was divided into 11 aliquots. however. N c are for the aromaticity. Pressure values were calibrated using lead melting point and temperatures were Table 4. Therefore. As more compact the molecular structures of bitumens are and the higher their R OB values will be. 1992). layer number of aromatic cycle respectively. studies in this area are few and the results are not consistent (McTavish. . Run conditions and analytical results of simulation experiments of bitumen maturation The analytical error of ROB measurements is about ±0. LABORATORY MATURATION E XPERIMENT Introduction for the experiment Because of the lack of practical geobarometers compared with many useful geothermometers. and then temperature was increased. 1998). and reacted under different experiment conditions as listed in Table 4. and their basic geochemical characteristics are shown in Table 2.05 mm i.Compressively matured solid bitumen 163 In order to test the hypothesis of “compressively matured solid bitumen”. 1990. 1978. a series of laboratory experiments was performed. which can reach 1200 atm at 700°C. 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. high pressure and high temperature simulation experiment was conducted to evaluate the effect of pressure on maturation processes. Shiwan Dashan basin.d. Braun and Burnham. The high pressure experiments were performed with a specially designed piston cylinder pressure vessel.01(%). The container material in the piston cylinder (19. Price and Wenger. Most organic geochemists believe in pressure retardation of organic matter maturation (Hunt. these changes should result in the increase in R OB values. Samples and experimental procedure Simulation experiments are conducted with the T 1 isotropic bitumens in Baxi profile.
In addition. Then. and the error induced by high pressure was ignored. and the pressure values can be watched through a manometer. The high-pressure liquids (e.. Results and discussion Results of laboratory simulation are listed in Table 4. After the experiments. In sample 1. the solid bitumens were peeled off from the rock samples and washed with dilute hydrochloric acid. .g. GC/MS chromatograms were also obtained for the solvent extracts from samples 10 and 11 for specific molecular distributions.. N. the samples were held in quartz tubes filled with nitrogen. When the simulation experiments finished. the inside pressure was kept at one atmosphere during the experiment. As both ends of the tubes are capillaries open to the atmosphere. All simulation samples were subjected to the required temperatures and pressures for 96 hrs. Variation of a) H/C atomic ratio. The temperature was controlled within ±1°C. b) d 002 . c) ROB and d) aromacity with temperature and pressure. the samples were quenched to room temperature before pressure release. Py-GC and Leitz MPVIII microspectrophotometer in addition to the ordinary analyses (e. The pressure error of two methods is less than 2%. the bitumen samples were analyzed mainly with Rigaku D/maxRA X-ray diffractometer. measured with a WRe 5-WRe 26 thermocouple. GC. During the ambient pressure experiments. The calibrated pressure values were also compared with those produced by high-pressure liquids. 7.164 Z. which reacted at 200°C and Fig. oils) were produced and transmitted by a high-pressure pump. elemental analysis and thermal analysis).g. Gao et al.
Cyclic hydrocarbon. respectively. Pyrolytic products of natural and simulation samples The sample numbers are consistent with Table 5. 165 . Light-weight hydrocarbon ratio = light hydrocarbon ( C10)/weight hydrocarbon ( C11 ). polycyclic aromatic hydrocarbon and phenol are also counted in saturated hydrocarbon. 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. Compressively matured solid bitumen Table 6. while numbers 3 and 4 represent simulation samples 10 and 11 respectively. phytane respectively. Pr and Ph represent pristane. aromatic hydrocarbon and non-hydrocarbon.Table 5.
d002 value. layer number of aromatic cycle and H/C atomic ratio) and ROB value becomes more clear (Table 4. anisortopic crystalline bitumen). The above similarity of simulation products and natural bitumens in geochemical characteristics and chemical composition proved formation of the compressively matured bitumen in nature. decrease in d002 and increase in ROB values and aromaticities with pressure become more distinct at higher pressure (Fig. 7. forms under high pressures and moderate temperatures. which reacted at 200°C and 1000 atm. This type of pressure-induced bitumen differs in geochemical characteristics from thermally matured bitumen: high ROB values. that is consistent with the observation in the natural bitu- men samples (isotropic bitumen vs. Comparing samples 9 and 10 with sample 7 or 1 respectively. The saturated hydrocarbon fractions extracted from samples 10 and 11 were analyzed using GC and GC/MS. the effect of pressure on the changes in the molecular structure (e. In contrast. N. Samples 3. Gao et al. The results also indicate that. but low pressures (such as 300 atm) may have little effect (comparing sample 3 with sample 4). the changes of H/C atomic ratio. in particular at lower temperatures (Table 4). IR intensity ratio 1460 cm–1/ 1600 cm–1 and total weight loss are small compared with those of the ROB value and molecular structure (Table 4). 1 atm. Fig. McTavish (1998) discussed that high pressure causes decrease in porosity of mudstone strata resulting in decrease in heat transfer. changes in its structure and ROB value were detected. O RIGIN OF THE COMPRESSIVELY M ATURED BITUMEN As the anisotropic crystalline bitumen in Baxi profile. Although most parameters are affected by the pressure and temperature changes. 10 and 1 were reacted at 1 atm with variable temperature. we can observe that pressure mainly affects the compact degree of bitumen’s molecular structure. Moreover. indicating that the small pressure difference at higher pressure can have the important effect on the maturation.. For example. depending on the experimental conditions. Shiwan Dashan basin. at a same temperature. Sajgo et al. significant difference was observed in the results at 800 and 1000 bars. Costa Neto (1991) approved this conclusion based on theoretical considerations. Although the increase of ROB values due to increase of pressure is apparently small.g. 7). While in sample 2.166 Z. although ROB values of the bitumens increase with pressure. On the other hand. aromaticity. and the variations in the results are smaller than those observed at higher pressures. the change becomes more significant with increasing pressure. 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). so the cumulative heat flow in high-pressure strata is lower than that in low-pressure strata. we call it “compressively matured solid bitumen”. high Tmax values and compact molecular structures vs. the pressure effect could be underestimated due to the short time duration of the laboratory experiment compared with the geological time scale. no change was observed from the starting material. size of crystal nucleus. it seems that temperature and pressure compensate each other in bitumen evolution. As the temperature rises. (1986) discovered that pressure could not only retard but also accelerate the organic matter maturation. its hydrocarbon-producing potential is similar to isotropic bitumens with much lower ROB values. Especially. ap- . as distance among reactants is smaller at higher pressure. 7). Pressures can accelerate mature reactions of organic matter. the chemical components reflecting lower thermal maturity. As the result. The two samples reacted at the same temperature have similar values of molecular evolution parameters (Table 5). The experimental results clearly show that not only increasing temperature but also increasing pressure can enhance solid bitumen evolution. in contrast with the change in the carbon content caused by the temperature difference.
These geochemical characteristics can be used to distinguish the compressively matured bitumens from thermally matured bitumens. whereas it also has a similar chemical composition and hydrocarbon-production potential to the thermally matured bitumens with lower R OB values. In contrast to the abnormally high ROB values. solid bitumens crystallize and their reflectance increase with progress of crystallization. The simulation experiments also prove the pressure-induced maturation of solid bitumens. small molecules are released) might not be as complete as that of thermally matured bitumens. is an actual example of compressively matured bitumens. Under a high pressure and moderate temperature. forming anisotropic bitumens with high ROB. 2 and 4). high Tmax values and compact molecular structures. etc. Geochemists classified natural bitumens based on their geochemical characteristics (Curiale. Georgy. As the compressively matured bitumens yield apparently higher values of R OB which overestimate the true thermal maturity of carbonate rocks. As porosity is large and a number of continuous fractures exist in carbonate rocks.g. 1986. hydrocarbon content and hydrocarbon-producing potential of bitumens of this type are high (e. bigger sizes of crystal nucleus. It has high bitumen reflectance (R OB) values and compact molecular structures (lower d002 values. The compressively matured solid bitumens have self-contradictory evolution parameters and geochemical characteristics. CONCLUSION Field study and laboratory experiments have elucidated that pressure can accelerate evolution of natural solid bitumens. therefore does not follow the usual relationships between ROB and R O which have been reported for thermally matured bitumens. the compressively matured bitumen preserves the chemical components (including biomarkers) formed at low thermal maturity. chemical composition of the compressively matured bitumens is relatively unchanged and their hydrocarbon-producing potential does not decrease obviously. This phenomenon is consistent with their lower degrees of thermal evolution. Shiwan Dashan basin. . high weight loss value.).. It has high ROB values without having been exposed to a high level of thermal stress. This pressure-induced solid bitumen (“compressively matured bitumen”) has self-contradictory evolution characteristics. high H/C atomic ratio and so on). By combining the geochemical information such as biomarkers. As a result. GEOCHEMICAL S IGNIFICANCE Compressively matured bitumen can be formed at moderate temperatures and high pressures in nature. compressively matured bitumens also increase their directional structural arrangement from no crystalline structure to crystalline-like structure. we might be able to use the ROB as a new maturity index to identify the compressively matured bitumen. Similar to thermally matured bitumens.. it is essential to distinguish compressively matured bitumens from thermally matured bitumens in oil and gas exploration. Their condensation polymerization (i. at the time of formation of polymers in bitumens. 1992). high pressure might not affect temperature distribution in the Baxi profile as McTavish (1998) discussed. Compressively matured solid bitumens crystallize mainly because of pressure effect. The anisotropic crystalline bitumen in the Baxi profile. and light hydrocarbons and hydrocarbon groups might be trapped in crystal-like structures of the bitumen. high hydrogen index. Acknowledgments—We thank Professor Ming-de LU (Department of Petroleum Geology. despite their high ROB values (Tables 1.e. China University of Geosciences) for his technical assistance during studying on optical characteristics of natural bitumens. and therefore affect only reaction processes of the organic matter as Jiang et al. (1998) suggested. In contrast.Compressively matured solid bitumen 167 parent retardation of organic matter maturation can be observed due to the high pressure.
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