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1.
Hydrous pyrolysis (HP) experiments were used to investigate the petroleum composition and quality of petroleum generated from a Brazilian lacustrine source rock containing Type I kerogen with increasing thermal maturity. The tested sample was of Aptian age from the Araripe Basin (NE-Brazil). The temperatures (280–360 °C) and times (12–132 h) employed in the experiments simulated petroleum generation and expulsion (i.e., oil window) prior to secondary gas generation from the cracking of oil. Results show that similar to other oil prone source rocks, kerogen initially decomposes in part to a polar rich bitumen, which decomposes in part to hydrocarbon rich oil. These two overall reactions overlap with one another and have been recognized in oil shale retorting and natural petroleum generation. During bitumen decomposition to oil, some of the bitumen is converted to pyrobitumen, which results in an increase in the apparent kerogen (i.e., insoluble carbon) content with increasing maturation.The petroleum composition and its quality (i.e., API gravity, gas/oil ratio, C15+ fractions, alkane distribution, and sulfur content) are affected by thermal maturation within the oil window. API gravity, C15+ fractions and gas/oil ratios generated by HP are similar to those of natural petroleum considered to be sourced from similar Brazilian lacustrine source rocks with Type I kerogen of Lower Cretaceous age. API gravity of the HP expelled oils shows a complex relationship with increasing thermal maturation that is most influenced by the expulsion of asphaltenes. C15+ fractions (i.e., saturates, aromatics, resins and asphaltenes) show that expelled oils and bitumen are compositionally separate organic phases with no overlap in composition. Gas/oil ratios (GOR) initially decrease from 508–131 m3/m3 during bitumen generation and remain essentially constant (81–84 m3/m3) to the end of oil generation. This constancy in GOR is different from the continuous increase through the oil window observed in anhydrous pyrolysis experiments. Alkane distributions of the HP expelled oils are similar to those of natural crude oils considered to be sourced from similar Brazilian lacustrine source rocks with Type I kerogen of Lower Cretaceous age. Isoprenoid and n-alkane ratios (i.e., pristane/n-C17 and phytane/n-C18) decrease with increasing thermal maturity as observed in natural crude oils. Pristane/phytane ratios remain constant with increasing thermal maturity through the oil window, with ratios being slightly higher in the expelled oils relative to those in the bitumen. Generated hydrocarbon gases are similar to natural gases associated with crude oils considered to be sourced from similar Brazilian lacustrine source rocks with Type I kerogen of Lower Cretaceous, with the exception of elevated ethane contents. The general overall agreement in composition of natural and hydrous pyrolysis petroleum of lacustrine source rocks observed in this study supports the utility of HP to better characterize petroleum systems and the effects of maturation and expulsion on petroleum composition and quality.  相似文献   

2.
High maturity oil and gas are usually generated after primary oil expulsion from source rocks, especially from oil prone type I/II kerogen. However, the detailed impacts of oil expulsion, or retention in source rock on further thermal degradation of kerogen at the high maturity stage remain unknown. In the present study, we collected an Ordovician Pingliang shale sample containing type II kerogen. The kerogens, which had previously generated and expelled oil and those which had not, were prepared and pyrolyzed in a closed system, to observe oil expulsion or oil retention effects on later oil and gas generation from kerogen. The results show that oil expulsion and retention strongly impacts on further oil and gas generation in terms of both the amount and composition in the high maturity stage. Gas production will be reduced by 50% when the expulsion coefficient reaches 58%, and gas from oil-expelled kerogen (less oil retained) is much drier than that from fresh kerogen. The oil expulsion also causes n-alkanes and gas compounds to have heavier carbon isotopic compositions at high maturity stages. The enrichment of 13C in n-alkanes and gas hydrocarbons are 1‰ and 4–6‰ respectively, compared to fresh kerogen. Oil expulsion may act as open system opposite to the oil retention that influences the data pattern in crossplots of δ13C2–δ13C3 versus C2/C3, δ13C2–δ13C3 versus δ13C1 and δ13C1–δ13C2 versus ln(C1/C2), which are widely used for identification of gas from kerogen cracking or oil cracking. These results suggest that the reserve estimation and gas/source correlation in deep burial basins should consider the proportion of oil retention to oil expulsion the source rocks have experienced.  相似文献   

3.
《Applied Geochemistry》1993,8(4):317-324
Two crude oils with relatively high (0.60 wt%) and low (0.18 wt%) oxygen contents were heated in the presence of water in gold-plated reactors at 300°C for 2348 h. The high-oxygen oil was also heated at 200°C for 5711 h. The compositions of aqueous organic acid anions of the oils and of the headspace gases were monitored inn order to investigate the distribution of organic acids that can be generated from liquid petroleum.The oil with higher oxygen content generated about five times as much organic anions as the other oil. The dominant organic anions produced were acetate, propionate and butyrate. Small amounts of formate, succinate, methyl succinate and oxalate were also produced. The dominant oxygen-containing product was CO2, as has been observed in similar studies on the hydrous pyrolysis of kerogen. These results indicate that a significant portion (10–30%) of organic acid anions reported i be generated by thermal alteration of oils in reservoir rocks. The bulk of organic acid anions present in formation waters, however, is most likely generated by thermal alteration of kerogen in source rocks. Kerogen is more abundant than oil in sedimentary basins and the relative yields of organic acid anions reported from the hydrous pyrolysis of kerogen are much higher than the yields obtained for the two oils.  相似文献   

4.
Unlike long-term heating in subsiding sedimentary basins, the near-instantaneous thermal maturation of sedimentary organic matter near magmatic intrusions is comparable to artificial thermal maturation in the laboratory in terms of short duration and limited extent. This study investigates chemical and H, C, N, O isotopic changes in high volatile bituminous coal near two Illinois dike contacts and compares observed patterns and trends with data from other published studies and from artificial maturation experiments. Our study pioneers in quantifying isotopically exchangeable hydrogen and measuring the D/H (i.e., 2H/1H) ratio of isotopically non-exchangeable organic hydrogen in kerogen near magmatic contacts. Thermal stress in coal caused a reduction of isotopically exchangeable hydrogen in kerogen from 5% to 6% in unaltered coal to 2-3% at contacts, mostly due to elimination of functional groups (e.g., OH, COOH, NH2). In contrast to all previously published data on D/H in thermally matured organic matter, the more mature kerogen near the two dike contacts is D-depleted, which is attributed to (i) thermal elimination of D-enriched functional groups, and (ii) thermal drying of hydrologically isolated coal prior to the onset of cracking reactions, thereby precluding D-transfer from relatively D-enriched water into kerogen. Maxima in organic nitrogen concentration and in the atomic N/C ratio of kerogen at a distance of ∼2.5 to ∼3.5 m from the thicker dike indicate that reactive N-compounds had been pyrolytically liberated at high temperature closer to the contact, migrated through the coal seam, and recombined with coal kerogen in a zone of lower temperature. The same principle extends to organic carbon, because a strong δ13Ckerogen vs. δ15Nkerogen correlation across 5.5 m of coal adjacent to the thicker dike indicates that coal was functioning as a flow-through reactor along a dynamic thermal gradient facilitating back-reactions between mobile pyrolysis products from the hot zone as they encounter less hot kerogen. Vein and cell filling carbonate is most abundant in highest rank coals where carbonate δ13CVPDB and δ18OVSMOW values are consistent with thermal generation of 13C-depleted and 18O-enriched CO2 from decarboxylation and pyrolysis of organic matter. Lower background concentrations of 13C-enriched carbonate in thermally unaffected coal may be linked to 13C-enrichment in residual CO2 in the process of CO2 reduction via microbial methanogenesis.Our compilation and comparison of available organic H, C, N isotopic findings on magmatic intrusions result in re-assessments of majors factors influencing isotopic shifts in kerogen during magmatic heating. (i) Thermally induced shifts in organic δD values of kerogen are primarily driven by the availability of water or steam. Hydrologic isolation (e.g., near Illinois dikes) results in organic D-depletion in kerogen, whereas more common hydrologic connectivity results in organic D-enrichment. (ii) Shifts in kerogen (or coal) δ13C and δ15N values are typically small and may follow sinusoidal patterns over short distances from magmatic contacts. Laterally limited sampling strategies may thus result in misleading and non-representative data. (iii) Fluid transport of chemically active, mobile carbon and nitrogen species and recombination reactions with kerogen result in isotopic changes in kerogen that are unrelated to the original, autochthonous part of kerogen.  相似文献   

5.
The presence of partially oxidized algal organic matter in oil-prone marine source rocks, is the rule rather than the exception. Partially oxidized, algal kerogen can still act as a significant source of liquid hydrocarbons. However, the corresponding peak of C12 + hydrocarbon generation is shifted to a considerably lower maturity level compared with that of the classical Type II kerogen. The extent of primary alteration-oxidation of marine algal kerogen is monitored by means of solid state microfluorescence spectroscopy. A new parameter, the Primary Alteration Factor (PAF) is established, and the relationships between PAF and H/C, O/C, HI, TOC and between PAF and %0δ13C are determined. The present data show large variations in the bulk chemistry of immature marine algal kerogens, and reveal evidence for gradational dehydrogenation/oxidation of the source organic matter. This contrasts with the recently proposed mechanism for kerogen formation. SEM analysis reveals a relationship between the physical breakdown of algal organic matter and the formation of liptodetrinite. FTIR analysis shows that the incorporation of primary oxygen in the kerogen macromolecules is not in the form of carbonyl or carboxyl functionalities. The presence of highly unreactive, stable oxygen, associated with aromatic structures in partially oxidized algal kerogen, is suggested by resistance of the kerogen to graphitization. The FTIR data also suggest the presence of aryl ether oxygen. The present findings raise fundamental questions regarding the mechanisms of kerogen cracking and kerogen formation, and have important implications for petroleum exploration.  相似文献   

6.
Asphaltenes extracted from crude oils are proposed to possess structural features of the related source rock kerogen. For the present study micro-scale sealed vessel pyrolysis (MSSV) and combustion isotope ratio mass spectrometry (GC–C–IRMS) were used to compare gas generation from a whole rock (type II-S kerogen) from southern Italy with that from related sulfur rich asphaltenes isolated from a low maturity heavy crude oil. The purpose of was to determine whether experimental pyrolysis of oil asphaltenes can be used to predict the timing and the chemical and isotopic composition of hydrocarbon gases generated from genetically related kerogen in the source rock during burial maturation. The results show that parameters such as (gas to oil ratio) GOR and oil and gas formation timing are very similar for these two sample types, whereas gas composition, product aromaticity and sulfur content are remarkably different. Slight differences in GOR are mainly due to differences in gas formation characteristics at very high levels of thermal alteration. Secondary gas formation from the whole rock covers a much broader temperature range under geological conditions than that from the asphaltene products. However, it is remarkable that both the onset and the maximum temperature are nearly identical under geological conditions. The observed differences in gas generation characteristics are supported by discrepancies in the carbon isotopic characteristics of the gas range compounds and indicate different precursors and/or mechanisms for gas generated from whole rock and asphaltenes.  相似文献   

7.
《International Geology Review》2012,54(14):1792-1812
Abundant crude oil and CO2 gas coexist in the fourth member of the Upper Cretaceous Quantou reservoir in the Huazijing Step of the southern Songliao Basin, China. Here, we present results of a petrographic characterization of this reservoir based on polarizing microscope, X-ray diffraction, fluid inclusion, and carbon–oxygen isotopic data. These data were used to identify whether CO2 might be trapped in minerals after the termination of a CO2-enhanced oil recovery (EOR) project, and to determine what effects might the presence of CO2 have on the properties of crude oil in the reservoir. The crude oil reservoir in the study area, which coexists with mantle-derived CO2, is hosted by dawsonite-bearing lithic arkoses and feldspathic litharenites. These sediments are characterized by a paragenetic sequence of clay, quartz overgrowth, first-generation calcite, dawsonite, second-generation calcite, and ankerite. The dawsonite analysed during this study exhibits δ13 C (Peedee Belemnite, PDB) values of ?4.97‰ to 0.67‰, which is indicative for the formation of magmatic–mantle CO2. The paragenesis and compositions of fluid inclusions in the dawsonite-bearing sandstones record a sequence of two separate filling events, the first involving crude oil and the second involving magmatic–mantle CO2. The presence of prolate primary hydrocarbon inclusions within the dawsonite indicates that these minerals precipitated from oil-bearing pore fluids at temperatures of 94–97°C, in turn suggesting that CO2 could be stored as carbonate minerals after the termination of a CO2-EOR project. In addition, the crude oil in the basin would become less dense after deposition of bitumen by deasphalting the injection of CO2 gas into the oil pool.  相似文献   

8.
随着色谱-质谱联用技术的引用,对原油及岩石抽提有机质开展了生物标志物的研究,使我们对陆相沉积岩中有机质的认识,深入到单烃化合物及其分子结构中了。这将使我们准确地鉴别出陆相沉积中特征有机化合物,对探讨石油起源、演化、运移等较复杂的地球化学问题,提供了可靠的信息,更好的为石油地质勘探服务。  相似文献   

9.
Fixed-ammonium in clays associated with crude oils   总被引：3，自引：0，他引：3  
The association of ammonium (NH4+) silicates with organic-rich sedimentary environments has stimulated interest in the chemical cycle of N, and its possible application as an indicator of in situ organic maturation reactions or crude oil migration. Fixed-NH4 in clay minerals was determined from three hydrocarbon occurrences of similar depositional environment but different ages, depth and thermal maturity, to determine whether anomalously high NH4-substitution occurs near mature hydrocarbons. Results show higher fixed-NH4 concentrations in marginally mature mudstones than in immature sediments. The highest fixed-NH4 concentrations were found in clays from sandstone reservoirs containing migrated crude oil.Fixed-NH4 in clays from Holocene oil seep sediments in the Gulf of Mexico continental slope, offshore Louisiana, averages 0.08 wt % and increases with depth in shallow cores (420 cm), reflecting an early diagenetic trend that is apparently not influenced by migrating crude oil. Programmed pyrolysis shows that the sediments are thermally immature (av.Tmax = 419°C). High Hydrogen Index values (av.= 359mg/g) are the result of biodegraded crude oil, and a high Oxygen Index (av.= 182mg/g) reflects the presence of authigenic carbonate.Fixed-NH4 averages 0.16 wt % in Wilcox Group (Eocene) mudstones enclosing two sandstone reservoirs at Fordoche Field, onshore Louisiana. In comparison to these mudstones, anomalously high NH4-fixation appears to occur in reservoir clay minerals. Pyrolysis shows that the sediments are marginally mature for crude oil generation (av.Tmax = 432°C). Average Hydrogen Index (187 mg/g) and Oxygen Index values (75 mg/g) are consistent with oil-prone Type II and Type III kerogen. Increased pyrolysis Production Index values and solvent extraction shows the presence of migrated crude oil. This suggests that a reaction which releases NH3 during crude oil generation or migration is recorded byNH4+ substitution in clays.Fixed-NH4 and total organic carbon (TOC) at Fordoche Field show no statistically significant correlation, suggesting that NH4+ substitution in clay minerals is not simply related to the amount of organic matter in the section, but is also influenced by the presence of crude oil. Once NH4+ has been fixed in clays, it is a more stable hydrocarbon proximity indicator than pore fluid tracers, because it is less influenced by later chemical or geological changes.  相似文献   

10.
This study examined the molecular and isotopic compositions of gases generated from different kerogen types (i.e., Types I/II, II, IIS and III) in Menilite Shales by sequential hydrous pyrolysis experiments. The experiments were designed to simulate gas generation from source rocks at pre-oil-cracking thermal maturities. Initially, rock samples were heated in the presence of liquid water at 330 °C for 72 h to simulate early gas generation dominated by the overall reaction of kerogen decomposition to bitumen. Generated gas and oil were quantitatively collected at the completion of the experiments and the reactor with its rock and water was resealed and heated at 355 °C for 72 h. This condition simulates late petroleum generation in which the dominant overall reaction is bitumen decomposition to oil. This final heating equates to a cumulative thermal maturity of 1.6% Rr, which represents pre-oil-cracking conditions. In addition to the generated gases from these two experiments being characterized individually, they are also summed to characterize a cumulative gas product. These results are compared with natural gases produced from sandstone reservoirs within or directly overlying the Menilite Shales. The experimentally generated gases show no molecular compositions that are distinct for the different kerogen types, but on a total organic carbon (TOC) basis, oil prone kerogens (i.e., Types I/II, II and IIS) generate more hydrocarbon gas than gas prone Type III kerogen. Although the proportionality of methane to ethane in the experimental gases is lower than that observed in the natural gases, the proportionality of ethane to propane and i-butane to n-butane are similar to those observed for the natural gases. δ13C values of the experimentally generated methane, ethane and propane show distinctions among the kerogen types. This distinction is related to the δ13C of the original kerogen, with 13C enriched kerogen generating more 13C enriched hydrocarbon gases than kerogen less enriched in 13C. The typically assumed linear trend for δ13C of methane, ethane and propane versus their reciprocal carbon number for a single sourced natural gas is not observed in the experimental gases. Instead, the so-called “dogleg” trend, exemplified by relatively 13C depleted methane and enriched propane as compared to ethane, is observed for all the kerogen types and at both experimental conditions. Three of the natural gases from the same thrust unit had similar “dogleg” trends indicative of Menilite source rocks with Type III kerogen. These natural gases also contained varying amounts of a microbial gas component that was approximated using the Δδ13C for methane and propane determined from the experiments. These approximations gave microbial methane components that ranged from 13–84%. The high input of microbial gas was reflected in the higher gas:oil ratios for Outer Carpathian production (115–1568 Nm3/t) compared with those determined from the experiments (65–302 Nm3/t). Two natural gas samples in the far western part of the study area had more linear trends that suggest a different organic facies of the Menilite Shales or a completely different source. This situation emphasizes the importance of conducting hydrous pyrolysis on samples representing the complete stratigraphic and lateral extent of potential source rocks in determining specific genetic gas correlations.  相似文献   

11.
The Rock-Eval pyrolysis and TOC analysis have been widely used to evaluate the source rock quality. The atomic H/C ratio of kerogen, however, has been overlooked in source rock evaluation. In this study, coal and carbonaceous samples, including 26 from northwestern Taiwan, 12 from China, and 4 from the United States were analyzed, and integrated with 157 published data, to explore the significance of atomic H/C ratio as a parameter of source rock evaluation. Two different linear trends were observed in the cross-plot of S 1 versus S 2. Field outcropped shale or C-shale exhibits a steeper slope compared to that of coal samples which can be attributed to the compositional difference in their organic material. A rather strong positive correlation for H% versus S 2 illustrates the contribution of H-containing macerals, especially exinite. Organic matters in the samples studied are of type II/III kerogen based on the relationship between HI and T max. The H/C ratio, as well as the HI, S 1, and S 2, generally decreases with the maturity increasing. The H/C ratio decreases slightly from 1.1 to 0.7 with the maturity increasing from R o 0.55 to 0.85%. Samples with H/C ratio in this range show significant change in certain other geochemical parameters (e.g. HI, S 1, S 2, S 1 + S 2, S 1/(S 1 + S 2), S 1/TOC, (S 1 + S 2)/TOC, T max). The (S 1 + S 2)/TOC ratio (defined as QI) was used as an indicator of the hydrocarbon potential. The QI, HI, and H/C ratio show a certain correlation, all increasing accordingly. The QI of the samples analyzed in this study is approximately 100–380 (mgHC/gTOC), similar to that of most humic coals for oil and gas generation. Samples with R o value lower than 0.55% always show significant variation in their HI, ranging from 80 to 520 mgHC/gTOC. It is inferred that hydrocarbon potential started from R o 0.55% and atomic H/C ratio 1.1 in this study.  相似文献   

12.
Bicyclic sesquiterpenoids are mostly used to illustrate the origins of organic matter and genetic types of crude oil presently.In this paper,the relationship between distributions and compositions of C16 homodrimane in immature to mature source rocks and evolution of organic matter was studied,and the correlation between C16 homodrimane at immature to low mature stages and thermal evolution of organic matter was analyzed.The results show that in terrestrial facies depositional system,the ratio of 8α(H)-homodrimane to 8β(H)-homodrimane has a high sensitivity about the maturity’s minor changes at immature to low mature stages.It is found that when the vitrinite reflectance R0<0.7%,the ratio significantly decreases with increasing burial depth or maturity.This kind of phenomenon reveals that these parameters may be the useful maturity indicators for determining the relative maturation of organic matter at immature to low mature stages,and have certain practical value in biogeochemical and en- vironmental geochemical research on low mature oil and gas.  相似文献   

13.
Hydrous pyrolysis experiments at 200 to 365°C were carried out on a thermally immature organic-rich limestone containing Type-IIS kerogen from the Ghareb Limestone in North Negev, Israel. This work focuses on the thermal behavior of both organic and inorganic sulfur species and the partitioning of their stable sulfur isotopes among organic and inorganic phases generated during hydrous pyrolyses. Most of the sulfur in the rock (85%) is organic sulfur. The most dominant sulfur transformation is cleavage of organic-bound sulfur to form H2S(gas). Up to 70% of this organic sulfur is released as H2S(gas) that is isotopically lighter than the sulfur in the kerogen. Organic sulfur is enriched by up to 2‰ in 34S during thermal maturation compared with the initial δ34S values. The δ34S values of the three main organic fractions (kerogen, bitumen and expelled oil) are within 1‰ of one another. No thermochemical sulfate reduction or sulfate formation was observed during the experiments. The early released sulfur reacted with available iron to form secondary pyrite and is the most 34S depleted phase, which is 21‰ lighter than the bulk organic sulfur. The large isotopic fractionation for the early formed H2S is a result of the system not being in equilibrium. As partial pressure of H2S(gas) increases, retro reactions with the organic sulfur in the closed system may cause isotope exchange and isotopic homogenization. Part of the δ34S-enriched secondary pyrite decomposes above 300°C resulting in a corresponding decrease in the δ34S of the remaining pyrite. These results are relevant to interpreting thermal maturation processes and their effect on kerogen-oil-H2S-pyrite correlations. In particular, the use of pyrite-kerogen δ34S relations in reconstructing diagenetic conditions of thermally mature rocks is questionable because formation of secondary pyrite during thermal maturation can mask the isotopic signature and quantity of the original diagenetic pyrite. The main transformations of kerogen to bitumen and bitumen to oil can be recorded by using both sulfur content and δ34S of each phase including the H2S(gas). H2S generated in association with oil should be isotopically lighter or similar to oil. It is concluded that small isotopic differentiation obtained between organic and inorganic sulfur species suggests closed-system conditions. Conversely, open-system conditions may cause significant isotopic discrimination between the oil and its source kerogen. The magnitude of this discrimination is suggested to be highly dependent on the availability of iron in a source rock resulting in secondary formation of pyrite.  相似文献   

14.
Basalts interbedded with oil source rocks are discovered frequently in rift basins of eastern China, where CO2 is found in reservoirs around or within basalts, for example in the Binnan reservoir of the Dongying Depression. In the reservoirs, CO2 with heavy carbon isotopic composition (δ13C>-10‰ PDB) is in most cases accounts for 40% of the total gas reserve, and is believed to have resulted from degassing of basaltic magma from the mantle. In their investigations of the Binnan reservoir, the authors suggested that the CO2 would result from interactions between the source rocks and basalts. As the source rocks around basalts are rich in carbonate minerals, volcanic minerals, transition metals and organic matter, during their burial history some of the transition metals were catalyzed on the thermal degradation of organic matter into hydrocarbons and on the decomposition of carbonate minerals into CO2, which was reproduced in thermal simulations of the source rocks with the transition metals (Ni and Co). This kind of CO2 accounts for 55%-85% of the total gas reserve generated in the process of thermal simulation, and its δ13C values range from -11‰- -7.2‰ PDB, which are very similar to those of CO2 found in the Binnan reservoir. The co-generation of CO2 and hydrocarbon gases makes it possible their accumulation together in one trap. In other words, if the CO2 resulted directly from degassing of basaltic magma or was derived from the mantle, it could not be accumulated with hydrocarbon gases because it came into the basin much earlier than hydrocarbon generation and much earlier than trap formation. Therefore, the source rocks around basalts generated hydrocarbons and CO2 simultaneously through catalysis of Co and Ni transition metals, which is useful for the explanation of co-accumulation of hydrocarbon gases and CO2 in rift basins in eastern China.  相似文献   

15.
《Applied Geochemistry》2005,20(11):2097-2107
The main purpose of the present study is to evaluate the nature and amount of gaseous compounds that would be generated from the Boom Clay kerogen due to the foreseen thermal stress associated with the geological disposal of high activity nuclear waste. To this end, pyrolysis experiments were carried out on this low maturity, O-rich kerogen with focus on mild conditions, including Rock–Eval and closed pyrolyses using a wide range of temperature/time conditions. The residual kerogen recovered after the closed pyrolyses was re-examined by Rock–Eval and elemental analyses and the components of the gas fractions were identified and quantified by gas chromatography. These experiments showed substantial production of CO2 (corresponding to ca. 1/5 of the total O content of the kerogen) under mild thermal stress. The kinetic parameters (frequency factor and distribution of activation energy) of this early production of CO2 were determined and used to simulate the possible consequences for the deep disposal of highly radioactive waste. Extrapolation to thermal stresses, corresponding to 80 and 100 °C over 1 ka, indicated that this production of CO2 might influence the geochemistry and perhaps therefore the effectiveness of the geological barrier. For example, unless diffusion out of the heated zone counterbalances the effect of CO2 generation, significant acidification and large changes in bicarbonate concentration may take place, in the interstitial water of the clay, at a time scale of only tens to a few hundred years.  相似文献   

16.
The extent of sterane isomerisation reactions and the moretane/hopane ratios of 234 crude oils, taken world wide, from a wide variety of source rocks of differing geological ages, have been measured.This data indicates that in 78 crude oils derived from Tertiary source rocks, sterane isomerisation reactions as determined by the 20S/(20S + 20R) ration of the C29 5α(H), 14α(H), 17α(H) normal-steranes and the C29 iso/(iso + normal) ratio [iso = 5α (H), 14β(H), 17β(H)] are mainly incomplete and sometimes considerably so. In addition, the same crude oils have 17β(H), 21α(H)-moretane/17α(H), 21β(H)-hopane ratios which are significantly greater (predominantly in the range 0.10–0.30) than those of crude oils derived from older, mature source rocks (mainly less than 0.1).This data, for crude oils, lends support to the hypothesis, proposed by Mackenzie and McKenzie (1983) for source rock extracts, that the time/temperature constraints of sterane isomerisation reactions are such that the time available for isomerisation in Tertiary sediments is generally insufficient, despite generation of crude oil at relatively high temperatures.An alternative hypothesis is that the incomplete sterane isomerisation of Tertiary crude oils may be due to generation of these crude oils from their deltaic, land plant-containing source rocks under low heating conditions.A third hypothesis proposes that the Tertiary crude oils may have picked up the incompletely isomerised steranes from immature sediments during migration. Although possible in particular instances, such a mechanism does not appear to be generally applicable since, in that case, the phenomenon would then appear to be restricted to the Tertiary.The higher moretane/hopane ratios of the Tertiary crude oils could suggest that constraints, similar to those applying in sterane isomerisation, also operate in the conversion of moretane to 17α(H)-hopane.  相似文献   

17.
The Menilite Shales (Oligocene) of the Polish Carpathians are the source of low-sulfur oils in the thrust belt and some high-sulfur oils in the Carpathian Foredeep. These oil occurrences indicate that the high-sulfur oils in the Foredeep were generated and expelled before major thrusting and the low-sulfur oils in the thrust belt were generated and expelled during or after major thrusting. Two distinct organic facies have been observed in the Menilite Shales. One organic facies has a high clastic sediment input and contains Type-II kerogen. The other organic facies has a lower clastic sediment input and contains Type-IIS kerogen. Representative samples of both organic facies were used to determine kinetic parameters for immiscible oil generation by isothermal hydrous pyrolysis and S2 generation by non-isothermal open-system pyrolysis. The derived kinetic parameters showed that timing of S2 generation was not as different between the Type-IIS and -II kerogen based on open-system pyrolysis as compared with immiscible oil generation based on hydrous pyrolysis. Applying these kinetic parameters to a burial history in the Skole unit showed that some expelled oil would have been generated from the organic facies with Type-IIS kerogen before major thrusting with the hydrous-pyrolysis kinetic parameters but not with the open-system pyrolysis kinetic parameters. The inability of open-system pyrolysis to determine earlier petroleum generation from Type-IIS kerogen is attributed to the large polar-rich bitumen component in S2 generation, rapid loss of sulfur free-radical initiators in the open system, and diminished radical selectivity and rate constant differences at higher temperatures. Hydrous-pyrolysis kinetic parameters are determined in the presence of water at lower temperatures in a closed system, which allows differentiation of bitumen and oil generation, interaction of free-radical initiators, greater radical selectivity, and more distinguishable rate constants as would occur during natural maturation. Kinetic parameters derived from hydrous pyrolysis show good correlations with one another (compensation effect) and kerogen organic-sulfur contents. These correlations allow for indirect determination of hydrous-pyrolysis kinetic parameters on the basis of the organic-sulfur mole fraction of an immature Type-II or -IIS kerogen.  相似文献   

18.
Molecular data from a large set of source rock, crude oil and oil-containing reservoir rock samples from the Tarim Basin demonstrate multiple sources for the marine oils in the studied areas of this basin. Based on gammacerane/C31 hopane and C28/(C27 + C28 + C29) sterane ratios, three of the fifteen crude oils from the Tazhong Uplift correlate with Cambrian-Lower Ordovician source rocks, while the other crude oils from the Tazhong Uplift and all 39 crude oils from the Tahe oilfield in the Tabei Uplift correlate with Middle-Upper Ordovician source rocks. These two ratios further demonstrate that most of the free oils and nearly all of the adsorbed and inclusion oils in oil-containing reservoir rocks from the Tazhong Uplift correlate with Cambrian-Lower Ordovician source rocks, while the free and inclusion oils in oil-containing carbonates from the Tahe oilfield correlate mainly with Middle-Upper Ordovician source rocks. This result suggests that crude oils in the Tazhong Uplift are partly derived from the Cambrian-Lower Ordovician source rocks while those in the Ordovician carbonate reservoirs of Tahe oilfield are overwhelmingly derived from the Middle-Upper Ordovician source rocks.The scatter of C23 tricyclic terpane/(C23 tricyclic terpane + C30 17α,21β(H)-hopane) and C21/(C21 + ΣC29) sterane ratios for the free and inclusion oils from oil-containing carbonates in the Tahe oilfield possibly reflects the subtle organofacies variations in the source rocks, implying that the Ordovician reservoirs in this oilfield are near the major source kitchen. In contrast, the close and positive relationship between these two ratios for oil components in the oil-containing reservoir rocks from the Tazhong Uplift implies that they are far from the major source kitchen.  相似文献   

19.
The origin, depositional environment and maturity of petroleum source rocks were determined via conventional whole rock and biomarker analysis of samples from wells in the Banat Depression, where the most important Serbian oil and gas fields are located. The organic matter (OM) in organic-rich upper Tertiary siltstones and marls consists predominantly of Type II kerogen. Numerous biomarker parameters indicated mixed algal-terrestrial OM, related to a brackish or freshwater environment, whose salinity decreased from Middle to Upper Miocene. The OM was deposited under variable redox conditions, reducing to sub-oxic.The wells in the Banat Depression experienced variable high rates of rapid heating, providing an opportunity for examining the applicability of different thermal indicators in a hyperthermal basin. Rock-Eval and numerous biomarker parameters indicate that the main stage of oil generation begins at ca.130 °C and vitrinite reflectance (Rc) ca. 0.63% and reaches a maximum at ca.145-150 °C and Rc ca. 0.72-0.75%, while the late stage of oil generation starts at ca.155 °C and ca. Rc 0.78%, which corresponds, depending on geothermal gradient, to relative depths of 2100-2300 m, 2600-2900 m and 3050-3100 m, respectively. The naphthalene and phenanthrene maturity parameters proved to be less applicable than the biomarker ratios, particularly in the early to moderate maturation range. The newly proposed parameter C(14a)-homo-26-nor-17α(H)-hopane/C30hopane (C30HH/C30H) proved applicable to a wide range of maturity.  相似文献   

20.
A scientific exploration well(CK1) was drilled to expand the oil/gas production in the western Sichuan depression, SW, China. Seventy-three core samples and four natural gas samples from the Middle–Late Triassic strata were analyzed to determine the paleo-depositional setting and the abundance of organic matter(OM) and to evaluate the hydrocarbon-generation process and potential. This information was then used to identify the origin of the natural gas. The OM is characterized by medium n-alkanes(n C_(15)–n C_(19)), low pristane/phytane and terrigenous aquatic ratios(TAR), a carbon preference index(CPI) of ～1, regular steranes with C_(29) C_(27) C_(28), gammacerane/C_(30) hopane ratios of 0.15–0.32, and δD_(org) of-132‰ to-58‰, suggesting a marine algal/phytoplankton source with terrestrial input deposited in a reducing–transitional saline/marine sedimentary environment. Based on the TOC, HI index, and chloroform bitumen "A" the algalrich dolomites of the Leikoupo Formation are fair–good source rocks; the grey limestones of the Maantang Formation are fair source rocks; and the shales of the Xiaotangzi Formation are moderately good source rocks. In addition, maceral and carbon isotopes indicate that the kerogen of the Leikoupo and Maantang formations is type Ⅱ and that of the Xiaotangzi Formation is type Ⅱ–Ⅲ. The maturity parameters and the hopane and sterane isomerization suggest that the OM was advanced mature and produced wet–dry gases. One-dimensional modeling of the thermal-burial history suggests that hydrocarbon-generation occurred at 220–60 Ma. The gas components and C–H–He–Ar–Ne isotopes indicate that the oilassociated gases were generated in the Leikoupo and Maantang formations, and then, they mixed with gases from the Xiaotangzi Formation, which were probably contributed by the underlying Permian marine source rocks. Therefore, the deeply-buried Middle–Late Triassic marine source rocks in the western Sichuan depression and in similar basins have a great significant hydrocarbon potential.  相似文献   

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