Hydrous pyrolysis: a tool for the study of organic acid synthesis

Hydrous pyrolysis, commonly used for the simulation of liquid hydrocarbon generation, is a potentially useful technique for the study of dissolved organic acid synthesis if modifications to conventional methods are made. Simple experiments demonstrate the thermal origin of formic, acetic, proprionic, and butyric acids. The use of stainless steel reactors at high temperatures ( ca. 300°C), however, results in short chain aliphatic acid yields and distributions that are a function of experimental conditions. Once generated, propionate is destroyed more rapidly than acetate during the experiments. Experimental artifacts can be reduced by using lower temperatures and less catalytically active reactor materials.With present methodology, hydrous pyrolysis provides a useful semi-quantitative method for assessing the organic acid generating capacities of different rocks and organic matter types. As much as 1.2 wt% of the organic C in low thermal rank kerogen can be converted to short chain aliphatic acids. However, carbon dioxide is the dominant oxygen-containing product, exceeding organic acid yields by roughly 10 times. Relative organic acid generating capacities can vary by a factor of two or more in narrow stratigraphic intervals (<3 m). Bulk geochemical parameters, like oxygen indices, and gross organic petrography (organic matter type) only partly explain the observed variations in organic acid yields between samples.     

烃源岩生成有机酸过程的高分辨质谱研究

研究石油中有机酸的生成过程对研究储层改造、石油润湿性及页岩油可动性评价具有重要意义。在热压生烃模拟实验基础上,对Ⅲ型烃源岩不同演化阶段生成油中的非烃馏分进行了负离子电喷雾傅立叶变换离子回旋共振质谱分析,研究了烃源岩生成有机酸过程。对样品生成有机酸分析表明,在整个演化过程烃源岩都能生成有机酸,在低演化阶段主要生成脂肪酸,随演化程度的升高,脂肪酸丰度快速减少,芳环酸开始大量生成。随演化程度的增加,芳环上短链取代基发生断裂,并促进了有机酸的缩合,使得生成的有机酸缩合度逐渐提高,高碳数有机酸逐渐减少;烃源岩生成脂肪酸系列中存在偶奇优势,生成的C16、C18脂肪酸存在异常高丰度, C16、C18脂肪酸异常丰度现象可能是污染造成的,是否与烃源岩类型及成熟度有关尚需进一步研究。     

Oil-generation kinetics for organic facies with Type-II and -IIS kerogen in the Menilite Shales of the Polish Carpathians

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.     

Evaluation of the petroleum composition and quality with increasing thermal maturity as simulated by hydrous pyrolysis: A case study using a Brazilian source rock with Type I kerogen

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.     

Comparison of natural gases accumulated in Oligocene strata with hydrous pyrolysis gases from Menilite Shales of the Polish Outer Carpathians

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% R_r, 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.     

Thermal alteration experiments on organic matter from recent marine sediments in relation to petroleum genesis

Three fractions of organic matter: lipid (benzene:methanol-extractable), humic acid (alkali-extractable) and kerogen (residue) were extracted from a young marine sediment (Tanner Basin, offshore southern California) and heated for different times (5–116 hr) and temperatures (150°–410°C). The volatile (gases) and liquid products, as well as residual material, were then analyzed. On a weight basis, the lipid fraction produced 58% of the total identified n-alkanes, the kerogen fraction 41%, and the humic acid <1%. Whereas n-alkanes produced from lipid show a CPI > 1.0, those produced by thermal alteration of kerogen display a CPI < 1.0. The volatiles produced by heating the lipid and humic acid fractions were largely CO₂ and water, whereas those produced from heated kerogen also included methane, hydrogen gas and small amounts of C₂–C₄ hydrocarbons. A mechanism for hydrocarbon production due to the thermal alteration of organic constituents of marine sediment is discussed.     

Vanadyl porphyrins in exploration: maturity indicators for source rocks and oils

The Porphyrin Maturity Parameter (PMP), which is derived from the vanadyl porphyrin distribution, is an excellent parameter for: (1) identifying the zone of hydrocarbon generation from marine source rock extracts; and (2) determining from oils the thermal maturity of their source rocks at expulsion.The PMP is measured using a methodology which is inexpensive, reliable and faster than earlier methods, allowing it to be used as a routine exploration tool. The PMP may be a more reliable maturity indicator for marine organic matter than some conventional methods such as vitrinite reflectance. Unlike most conventional maturity parameters guided by processes other than kerogen conversion, the reactions causing PMP evolution directly monitor the generation of bitumen and the concurrent thermal degradation of kerogen.Measurements on hydrous pyrolyzates from the Monterey Formation (offshore California), source rock bitumens from the Devonian-Mississippian Bakken Shale (Williston Basin), and Miocene Monterey equivalent source strata (San Joaquin Basin, California) illustrate the method. In all cases reviewed so far, PMP begins increasing at the onset of hydrocarbon generation and increases systematically and predictably as kerogen decomposition proceeds.In oils generated from high-S marine kerogens, PMP reflects the maturity of the source rock at the time of oil expulsion, provided that the oil does not undergo subsequent reservoior maturation or mixing with in-situ bitumen.     

北黄海盆地LV井侏罗系烃源岩特征及油源对比

对北黄海盆地LV井中、上侏罗统烃源岩及上侏罗统原油（油砂抽提物）进行常规有机地球化学分析和碳同位素测试,分析研究烃源岩和原油的地球化学特征并探讨原油的来源问题。测试结果显示,侏罗系烃源岩达成熟-高熟阶段,有机质类型以Ⅲ型为主。中侏罗统烃源岩有机碳含量较高,但生烃潜能、氯仿沥青“A”及总烃含量低值,属于差的烃源岩。干酪根碳同位素总体偏重（-24.4‰～-23.5‰）,与原油碳同位素特征（-29‰左右）差异显著,排除与原油的母岩关系。上侏罗统烃源岩有机碳含量较中侏罗统低,但生烃潜能、氯仿沥青“A”及总烃含量高值。上侏罗统烃源岩抽提氯仿沥青“A”碳同位素（-26‰～-21.5‰）特征、单体烃碳同位素分布模式及甾萜烷生物标志物特征都与原油相似,综合分析认为原油应该来源于上侏罗统中干酪根类型较好、母质为混源的成熟烃源岩。     

Source rock potential of selected Cretaceous shales,Orange Basin,South Africa

Twenty Cretaceous shale samples from two wells in the Orange Basin of South Africa were evaluated for their source rock potential. They were sampled from within a 1400 m-thick sequence in boreholes drilled through Lower to Upper Cretaceous sediments. The samples exhibit total organic carbon (TOC) content of 1.06–2.17%; Rock-Eval S2 values of 0.08–2.27 mg HC/g; and petroleum source potential (SP), which is the sum of S1 and S2, of 0.10–2.61 mg HC/g, all indicating the presence of poor to fair hydrocarbon generative potential. Hydrogen index (HI) values vary from 7 to 128 mg HC/g organic carbon and oxygen index (OI) ranges from 37 to 195 mg CO₂/g organic carbon, indicating predominantly Type III kerogen with perhaps minor amounts of Type IV kerogen. The maturity of the samples, as indicated by T _max values of 428–446°C, ranges from immature to thermally mature with respect to oil generation. Measured vitrinite reflectance values (%Ro) of representative samples indicate that these samples vary from immature to mature, consistent with the thermal alteration index (TAI) (spore colour) and fluorescence data for these samples. Organic petrographic analysis also shows that amorphous organic matter is dominant in these samples. Framboidal pyrite is abundant and may be indicative of a marine influence during deposition. Although our Rock-Eval pyrolysis data indicate that gas-prone source rocks are prevalent in this part of the Orange Basin, the geochemical characteristics of samples from an Aptian unit at 3318 m in one of the wells suggest that better quality source rocks may exist deeper, in more distal depositional parts of the basin.     

Generation of unsaturated and aromatic hydrocarbons by thermal alteration of young kerogen

Monounsaturated, monoaromatic and polyaromatic hydrocarbons generated by artificial thermal alteration of young marine (Tanner basin, offshore California) kerogen were studied by computerized GC-MS. Their relative amounts changed with temperature (150–410°C) and time (5–120 hr) of heating as follows: Monounsaturates → Monoaromatics → Polyaromatics. Distribution of alkyl homologs of phenanthrene also changed with increasing degree of thermal alteration. These results are in agreement with those observed for crude oils and shales.     

陆相烃源岩凝析油形成演化实验模拟特征

为了解陆相烃源岩在深埋过程中凝析油形成与演化特征,利用高温高压生烃模拟仪对辽河盆地西部凹陷曙13 井、马南603 井和东部凹陷桃10 井烃源岩样品进行了半封闭体系生烃模拟实验。实验结果显示,I 型有机质（曙13 井烃源岩样品） 总凝析油产率峰值为2.32 mg/g TOC,出现在镜质体反射率（VR） 1.76 %Ro,并以低分子量烃类物质为主要成分,可能表明I 型有机质凝析油主要通过液态烃二次裂解形成。II 型有机质（马南603 井烃源岩样品） 总凝析油产率峰值为2.28 mg/g TOC,该峰值出现在VR 为2.42 %Ro,明显晚于I 型有机质凝析油产率峰值,其成分以相对高分子量的烃类物质为主,其次为低分子量烃类物质。III 型有机质（桃10 井烃源岩样品） 凝析油总产率最低,产率峰值仅为0.92 mg/g TOC,可能表明III型有机质生成凝析油潜力较差。     

陆相烃源岩凝析油形成演化实验模拟特征

为了解陆相烃源岩在深埋过程中凝析油形成与演化特征，利用高温高压生烃模拟仪对辽河盆地西部凹陷曙13 井、马南603 井和东部凹陷桃10 井烃源岩样品进行了半封闭体系生烃模拟实验。实验结果显示，I 型有机质（曙13 井烃源岩样品） 总凝析油产率峰值为2.32 mg/g TOC，出现在镜质体反射率（VR） 1.76 %Ro，并以低分子量烃类物质为主要成分，可能表明I 型有机质凝析油主要通过液态烃二次裂解形成。II 型有机质（马南603 井烃源岩样品） 总凝析油产率峰值为2.28 mg/g TOC，该峰值出现在VR 为2.42 %Ro，明显晚于I 型有机质凝析油产率峰值，其成分以相对高分子量的烃类物质为主，其次为低分子量烃类物质。III 型有机质（桃10 井烃源岩样品） 凝析油总产率最低，产率峰值仅为0.92 mg/g TOC，可能表明III型有机质生成凝析油潜力较差。     

Hydrocarbons generation potential of the Jurassic–Lower Cretaceous Formation, Ajeel field, Iraq

Organic geochemical analysis and palynological studies of the organic matters of subsurface Jurassic and Lower Cretaceous Formations for two wells in Ajeel oil field, north Iraq showed evidences for hydrocarbon generation potential especially for the most prolific source rocks Chia Gara and Sargelu Formations. These analyses include age assessment of Upper Jurassic (Tithonian) to Lower Cretaceous (Berriasian) age and Middle Jurassic (Bathonian–Tithonian) age for Chia Gara and Sargelu Formations, respectively, based on assemblages of mainly dinoflagellate cyst constituents. Rock-Eval pyrolysis have indicated high total organic carbon (TOC) content of up to 18.5 wt%, kerogen type II with hydrogen index of up to 415 mg HC/g TOC, petroleum potential of 0.70–55.56 kg hydrocarbon from each ton of rocks and mature organic matter of maximum temperature reached (T_max) range between 430 and 440 °C for Chia Gara Formation, while Sargelu Formation are of TOC up to 16 wt% TOC, Kerogen type II with hydrogen index of 386 mg HC/g TOC, petroleum potential of 1.0–50.90 kg hydrocarbon from each ton of rocks, and mature organic matter of T_max range between 430 and 450 °C. Qualitative studies are done in this study by textural microscopy used in assessing amorphous organic matter for palynofacies type belonging to kerogen type A which contain brazinophyte algae, Tasmanites, and foraminifera test linings, as well as the dinoflagellate cysts and spores, deposited in dysoxic–anoxic environment for Chia Gara Formation and similar organic constituents deposited in distal suboxic–anoxic environment for Sargelu Formation. The palynomorphs are of dark orange and light brown, on the spore species Cyathidites australis, that indicate mature organic matters with thermal alteration index of 2.7–3.0 for the Chia Gara Formation and 2.9–3.1 for the Sargelu Formation by Staplin's scale. These characters have rated the succession as a source rock for very high efficiency for generation and expulsion of oil with ordinate gas that charged mainly oil fields of Baghdad, Dyala (B?aquba), and Salahuddin (Tikrit) Governorates. Oil charge the Cretaceous-Tertiary total petroleum system (TPS) are mainly from Chia Gara Formation, because most oil from Sargelu Formation was prevented passing to this TPS by the regional seal Gotnia Formation. This case study of mainly Chia Gara oil source is confirmed by gas chromatography–mass spectrometry analysis for oil from reservoirs lying stratigraphically above the Chia Gara Formation in Ajeel and Hamrine oil fields, while oil toward the north with no Gotnia seal could be of mainly Sargelu Formation source.     

Comparison of petroleum generation kinetics by isothermal hydrous and nonisothermal open-system pyrolysis

This study compares kinetic parameters determined by open-system pyrolysis and hydrous pyrolysis using aliquots of source rocks containing different kerogen types. Kinetic parameters derived from these two pyrolysis methods not only differ in the conditions employed and products generated, but also in the derivation of the kinetic parameters (i.e., isothermal linear regression and non-isothermal nonlinear regression). Results of this comparative study show that there is no correlation between kinetic parameters derived from hydrous pyrolysis and open-system pyrolysis. Hydrous-pyrolysis kinetic parameters determine narrow oil windows that occur over a wide range of temperatures and depths depending in part on the organic-sulfur content of the original kerogen. Conversely, open-system kinetic parameters determine broad oil windows that show no significant differences with kerogen types or their organic-sulfur contents. Comparisons of the kinetic parameters in a hypothetical thermal-burial history (2.5 °C/my) show open-system kinetic parameters significantly underestimate the extent and timing of oil generation for Type-IIS kerogen and significantly overestimate the extent and timing of petroleum formation for Type-I kerogen compared to hydrous pyrolysis kinetic parameters. These hypothetical differences determined by the kinetic parameters are supported by natural thermal-burial histories for the Naokelekan source rock (Type-IIS kerogen) in the Zagros basin of Iraq and for the Green River Formation (Type-I kerogen) in the Uinta basin of Utah. Differences in extent and timing of oil generation determined by open-system pyrolysis and hydrous pyrolysis can be attributed to the former not adequately simulating natural oil generation conditions, products, and mechanisms.     

Release of sulfur- and oxygen-bound components from a sulfur-rich kerogen during simulated maturation by hydrous pyrolysis

An immature sulfur-rich marl from the Gessosso-solfifera Formation of the Vena del Gesso Basin (Messinian, Italy) has been subjected to hydrous pyrolysis (160 to 330°C) to simulate maturation under natural conditions. The kerogen of the unheated and heated samples was isolated and the hydrocarbons released by selective chemical degradation (Li/EtNH₂ and HI/LiAlH₄) were analysed to allow a study of the fate of sulfur- and oxygen-bound species with increasing temperature. The residues from the chemical treatments were also subjected to pyrolysis–GC to follow structural changes in the kerogens. In general, with increasing hydrous pyrolysis temperature, the amounts of sulfide- and ether-bound components in the kerogen decreased significantly. At the temperature at which the generation of expelled oil began (260°C), almost all of the bound components initially present in the unheated sample were released from the kerogen. Comparison with an earlier study of the extractable organic matter using a similar approach and the same samples provides molecular evidence that, with increasing maturation, solvent-soluble macromolecular material was initially released from the kerogen, notably as a result of thermal cleavage of weak carbon–heteroatom bonds (sulfide, ester, ether) even at temperatures as low as 220°C. This solvent-soluble macromolecular material then underwent thermal cleavage to generate hydrocarbons at higher temperatures. This early generation of bitumen may explain the presence of unusually high amounts of extractable organic matter of macromolecular nature in very immature S-rich sediments.     

Stable sulfur isotope partitioning during simulated petroleum formation as determined by hydrous pyrolysis of Ghareb Limestone, Israel

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.     

δC of low-molecular-weight organic acids generated by the hydrous pyrolysis of oil-prone source rocks

Low-molecular-weight (LMW) aqueous organic acids were generated from six oil-prone source rocks under hydrous-pyrolysis conditions. Differences in total organic carbon-normalized acid generation are a function of the initial thermal maturity of the source rock and the oxygen content of the kerogen (OI). Carbon-isotope analyses were used to identify potential generation mechanisms and other chemical reactions that might influence the occurrence of LMW organic acids. The generated LMW acids display increasing ¹³C content as a function of decreasing molecular weight and increasing thermal maturity. The magnitudes of observed isotope fractionations are source-rock dependent. These data are consistent with δ¹³C values of organic acids presented in a field study of the San Joaquin Basin and likely reflect the contributions from alkyl-carbons and carboxyl-carbons with distinct δ¹³C values. The data do not support any particular organic acid generation mechanism. The isotopic trends observed as a function of molecular weight, thermal maturity, and rock type are not supported by either generation mechanisms or destructive decarboxylation. It is therefore proposed that organic acids experience isotopic fractionation during generation consistent with a primary kinetic isotope effect and subsequently undergo an exchange reaction between the carboxyl carbon and dissolved inorganic carbon that significantly influences the carbon isotope composition observed for the entire molecule. Although generation and decarboxylation may influence the δ¹³C values of organic acids, in the hydrous pyrolysis system described, the nondestructive, pH-dependent exchange of carboxyl carbon with inorganic carbon appears to be the most important reaction mechanism controlling the δ¹³C values of the organic acids.     

Modeling of catagenetic transformation of organic matter from a Riphean mudstone in hydrous pyrolysis experiments: Biomarker data

The catagenesis of organic matter (OM) was modeled by the hydrous pyrolysis of a Riphean mudstone. Microscopic observations of the processes operating during kerogen heating to 600°C were conducted in a diamond anvil cell. The results of pyrolysis in an aqueous environment were used to calculate the activation energies of kerogen cracking and derive chemical kinetic models for OM catagenesis. Isothermal experiments were carried out for 3 days at temperatures of 300, 310, …, 360, and 370°C. The maximum bitumen yield was obtained at 330°C followed by thermal cracking at higher temperatures. The aromatic and saturated hydrocarbons from rock bitumen, hydrous pyrolyzates, and kerogen flash pyrolyzates were analyzed by chromatography-mass spectrometry. We also discuss the problem of extrapolation of high-temperature pyrolysis results to geologic observations under the conditions of regional catagenesis.     

烃源岩生气增压定量评价模型及影响因素

Ⅲ型干酪根烃源岩生气增压定量评价是一个复杂过程, 因为Ⅲ型干酪根以生气为主的同时伴生少量的油生成, 而且在达到一定的温度条件下原油还将逐渐裂解成天然气.在考虑烃源岩生烃过程中天然气的渗漏和排出、氢指数对生烃量的影响、原油裂解成气、生烃作用产生的超压对孔隙水, 油和干酪根的压缩作用、天然气在孔隙水和石油中的溶解作用等因素的基础上建立了Ⅲ型干酪根烃源岩生烃增压定量评价模型, 并对模型参数进行敏感性分析.Ⅲ型干酪根烃源岩生气增压受到烃源岩孔隙度、成熟度、有机质丰度、天然气残留系数等多种参数的影响.有机碳含量、氢指数和天然气残留系数3个参数中以氢指数对Ⅲ型干酪根烃源岩生烃增压产生的影响最大, 天然气残留系数影响最小.天然气残留系数只要大于0.2就可以产生超压, 表明保存条件不是Ⅲ型干酪根烃源岩形成生烃增压最主要的控制因素.