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1.
Joseph A Curiale William E. Harrison Garmon Smith 《Geochimica et cosmochimica acta》1983,47(3):517-523
Solid bitumens (grahamite and impsonite) of southeastern Oklahoma have been shown to originate from near-surface alteration of crude oil (Curiale, 1981; Curiale and Harrison, 1981). Pyrolysis of these solids has been employed to compare the sterane distribution of geographically proximate oils to that of the bitumens. The ratio of rearranged to regular steranes is higher in the pyrolyzates than in the oils, a finding consistent with a bitumen origin due to biodegradation of oil. The remaining presence of steranes, particularly regular steranes, in the bitumens suggests that sterane occlusion may have occurred prior to or during the alteration process, thus removing tetracyclic compounds from the influence of microbial attack. These data suggest that pyrolysis- offers a viable approach to correlation problems involving solid bitumens. 相似文献
2.
W.K Seifert 《Geochimica et cosmochimica acta》1978,42(5):473-484
Comparison of biological marker alkanes in the kerogen pyrolyzate and bitumen from a sediment is a useful test for the indigenous nature of sediment extracts. For the pyrolysis conditions used, the bulk of the hydrocarbons is released from the kerogen matrix between 375° and 550°C; and its steriochemistry is almost the same as that observed in the extractable bitumen in a genuine source rock. Examples are given to demonstrate that, during pyrolysis, the sterane/terpane ratio decreases and secondary terpanes are generated at the expense of primary ones.The mechanism of artificial petroleum generation by pyrolysis differs from ‘natural’ diagenesis during geological time and is reflected in the composition of certain C27-C29 steranes, as demonstrated by simulation experiments and C29-C30 moretanes and hopanes. The -sterane ratios, jointly with ratios, tricyclic terpane concentrations and -trisnorhopane ratios, allow the differentiation of kerogens from adjacent stratigraphies. 相似文献
3.
Solid bitumen occurs extensively in the paleo-reservoirs of marine sequences in southern China. The fluids in these paleo-reservoirs have usually experienced severe secondary alteration such as biodegradation and/or thermal maturation. The concentrations of extractable organic matter (EOM) in the resulting solid bitumens are too low to satisfy the amount required for instrumental analysis such as GC–MS and GC–IRMS. It is also difficult to get enough biomarkers and n-alkanes by dry pyrolysis or hydrous pyrolysis directly because such solid bitumens are hydrogen poor due to high maturities. Catalytic hydropyrolysis (HyPy) can release much more EOM from solid bitumen at mature to highly over-mature stages than Soxhlet extraction, dry pyrolysis and hydrous pyrolysis. However, whether the biomarkers in hydropyrolysates can be used for bitumen-source or bitumen–bitumen correlations has been questionable. In this study, a soft biodegraded solid bitumen sample of low maturity was thermally altered to various maturities in a closed system. HyPy was then employed to release bound biomarkers and n-alkanes. Our results show that the geochemical parameters for source and maturity based on biomarkers released from these thermally altered bitumen residues by HyPy are insensitive to the degree of thermal alteration. Furthermore, the maturity parameters are indicative of lower maturity than bitumen maturation products at a corresponding temperature. This suggests that biomarker source and maturity parameters, based on the products of HyPy, remain valid for bitumens which have suffered both biodegradation and severe thermal maturation. The distributions of δ13C of n-alkanes in hydropyrolysates are also insensitive to the temperature used for bitumen artificial maturation. Hence, the δ13C values of n-alkanes in hydropyrolysates may also provide useful information in bitumen–bitumen correlation for paleo-reservoir solid bitumens. 相似文献
4.
卡塔克隆起中1井储层沥青地球化学特征与成因 总被引：1，自引：0，他引：1
塔里木盆地海相原油的成因至今仍有争议,而对储层沥青的地球化学特征剖析,能为探索海相原油的成因提供依据。选取卡塔克隆起上的中1井不同层系储层沥青,详尽剖析了其地球化学特征。研究结果揭示,中1井储层沥青的Pr/Ph为1.14～1.39,CPI值 1.01～1.08,OEP值0.98～1.05,无奇偶优势或偶奇优势,伽玛蜡烷、C28甾烷丰度低,硫芴系列丰富。甾烷成熟度参数和Ts/(Ts+Tm)均指示中1井储层沥青处于成熟—高成熟热演化范畴。依据特征生物标志物的分布对沥青的成因示踪,中1井储层沥青与上奥陶统烃源岩有成因关系,而中1井储层沥青与塔东2井寒武系原油分子特征的迥异也佐证该认识。 相似文献
5.
Noriyuki Suzuki 《Geochimica et cosmochimica acta》1984,48(11):2273-2282
A geochemical method for estimation of the maximum temperature of mudstones is proposed. The extents of epimerization of the sterane and the hopane are used. The temperature function is: where U = ln (1 ? α/0.54), V = ln(1 ? β/0.61), α = 20S-/20S- + 20R-24-ethyl-5α(H), 14α(H), 17α(H)-cholestane(C29-sterane) and β = 22S-/22S- + 22R-17α(H), 21β(H)-bishomohopane(C32-hopane). The value of dU/dV can be obtained from the tangent to the evolution curve in the UversusV. This temperature function is applicable to the temperature analysis in the range of 50°C–150°C. 相似文献
6.
V. N. Melenevskii 《Geochemistry International》2012,50(5):425-436
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. 相似文献
7.
本研究系统采集了四川盆地东北部大普光、元坝地区上三叠统须家河组、下三叠统飞仙关组、上二叠统长兴组和鄂西渝东地区中石炭统黄龙组储层固体沥青样品,进行了岩石热解、有机元素、碳同位素和饱和烃、芳烃组分GC/MS的分析,以确定其成因、性质和来源。这些沥青总体上具有低溶性(多数氯仿抽提物/TOC<8%)、高反射率(换算的Ro>1.4%)、低H/C原子比(<0.6)的性质,属焦沥青类,是古油藏原油或运移烃经热裂解成气的残留物。其中,飞仙关组、长兴组碳酸岩储层沥青的S/C原子比值普遍较高(主要在0.025~0.085范围),且硫同位素δ34S值(主要在12‰~24‰)接近硬石膏,说明可能包含有部分TSR成因的沥青。这些高热演化沥青中饱和烃生物标志物的组成和分布出现了异常变化,基本失去了其常规应用意义。芳烃中2,6-/2,10-DMP(二甲基菲)、1,7-/1,9-DMP和4-/1-MDBT(甲基二苯并噻吩)比值,可用来指示沥青烃源岩的有机质生源构成和沉积环境性质。须家河组陆相沥青中这些芳烃比值较高,表征其烃源母质中陆源有机质占优势,且形成于氧化性的环境;而飞仙关组、长兴组及黄龙组海相沥青中这些参数值低得多,意味着其烃源岩有机质生源应以水生生物为主,并沉积于还原性环境。经沥青/烃源岩的碳同位素和二苯并噻吩系列组成对比,认为须家河组储层沥青来源于本层位烃源岩,飞仙关组和长兴组沥青同源于二叠系烃源层。鄂西渝东地区的黄龙组沥青碳同位素偏重(δ13C值为-23.2‰~-26.4‰),原始烃源可能主要来自中、下志留统韩家店组及小河坝组地层。 相似文献
8.
M.D Lewan 《Geochimica et cosmochimica acta》1983,47(8):1471-1479
Acquiring crude oils that have been expelled from the same rock unit at different levels of thermal maturation is currently not feasible in the natural system. This prevents direct correlation of compositional changes between the organic matter retained in a source rock and its expelled crude oil at different levels of thermal maturation. Alleviation of this deficiency in studying the natural system requires the use of laboratory experiments. Natural generation of petroleum from amorphous type-II kerogen in the Woodford Shale may be simulated by hydrous pyrolysis, which involves heating crushed rock in contact with water at subcritical temperatures (<374°C). Four distinct stages of petroleum generation are observed from this type of pyrolysis; (1) pre-oil generation, (2) incipient-oil generation, (3) primary-oil generation, and (4) post-oil generation.The effects of thermal maturation on the δ13C values of kerogen, bitumen, and expelled oil-like pyrolysate from the Woodford Shale have been studied through these four stages of petroleum generation. Similar to the natural system, the kerogens isolated from the pyrolyzed rock showed no significant change in δ13C. This suggests that the δ13C value of kerogens may be useful in kerogen typing and oil-to-source rock correlations. δ13C values of bitumens extracted from the pyrolyzed rock showed an initial decrease during the incipient-oil generation stage, followed by depletion during the primary- and post-oil generation stages. This reversal is not favorable for geochemical correlation or maturity evaluation. Saturated and polar components of the bitumen show the greatest δ13C variations with increasing thermal maturation. The difference between the δ13C of these two components gives a unidirectional trend that serves as a general indicator of thermal maturation and is referred to as the bitumen isotope index (BII).δ13C values of the expelled pyrolysates show a unidirectional increase with increasing thermal maturation. The constancy and similarity of δ13C values of the aromatic components in the expelled pyrolysates and bitumens, with increasing thermal maturation, encourages their use in oil-to-oil and oil-to-source rock correlations. Isotopic type-curves for expelled pyrolysates indicate that they may be useful in oil-to- oil correlations, but have a limited use in oil-to-source rock correlations. 相似文献
9.
10.
《Applied Geochemistry》1993,8(3):245-254
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. 相似文献
11.
从普光气田及邻近地区二叠系和下三叠统15个含沥青碳酸盐储集岩样品分步提取了自由态油气组分和油气包裹体组分,并且应用限定体系(金管)热解实验获取了固体沥青热解组分.各组分进一步做色谱和色谱-质谱分析获取了生物标志物组成.分析结果表明,从油气包裹体组分、自由态油气组分至固体沥青热解组分,伽马蜡烷/C31升藿烷比值依次增高.同时油气包裹体组分 C23三环萜烷/(C23三环萜烷+C30藿烷)、C21/(C21+ΣC29)甾烷、C27重排甾烷/(C27重排甾烷+C27规则甾烷)、20S/(20R+20S) C29甾烷和αββ/(ααα+αββ) C29甾烷等成熟度指标与自由态组分相近,而明显高于固体沥青热解组分.根据分子指标,可以推断古油藏的原油来源于不同的烃源岩,早期充注的原油来源于下志留统烃源岩,具有较低的伽马蜡烷含量和较高的成熟度;晚期充注的原油来源于上二叠统烃源岩,具有较高的伽马蜡烷含量和较低的成熟度.固体沥青主要为晚期充注、来源于上二叠统烃源岩的原油裂解生气的产物 相似文献
12.
Familiar since antiquity, and subject in contemporary times to various characterization schemes, the exact nature of solid bitumen is not yet fully known. Bitumens have ‘random polymer-like’ molecular structures, are mobile as highly viscous fluids or were once fluids but have since turned into solids. Solid bitumens consist mainly of large moieties, of polyclyclic aromatic hydrocarbons, occasionally with finely admixed, fine-grained cryptocrystalline graphite. Solid bitumens are distinguished from kerogen, which is the syngenetic and generally finely dispersed particulate organic matter in sedimentary rock that virtually does not migrate following its deposition. Occurrences of solid bitumens are relevant to petroleum exploration as well as the search for, and evaluation of, a variety of metallic mineral deposits. Genesis of bitumen is in many cases linked to the thermal and hydrothermal history of organic matter in sedimentary rock. Apparently bitumen, or more specifically organic acids generated along with bitumen during diagenesis, may alter porosity of reservoir rocks or otherwise prepare the ground for ore deposition. Bitumen is also relatively sensitive to alteration processes, some of which, such as oxidative weathering, water leaching, biodegradation (contact) metamorphism and ionizing radiation may likewise affect its nature. Elemental composition of bitumen commonly reflects the nature of mineral deposits. Is is possible that in petroleum exploration, trace metal abundances of bitumen may eventually allow prediction of crude oil types and volumes anticipated from a given source rock? Beside transition elements, notably Ni and V, highly anomalous concentrations of U, Pt and Au occur in some solid bitumens. During the generation of petroleum from kerogen, the trend in δ13C is toward lighter values. The opposite seems to occur when liquid petroleum is subjected to thermal cracking (and /or related processes) yielding solid bitumen enriched in 13C, and isotopically light methane. In fact, except for deasphalting and possibly some irradiation processes, the result of thermal cracking, oxidation, water leaching, inspissation (drying) and bacterial degradation of crude oil is that lower molecular weight hydrocarbons are removed leaving bitumen residues enriched in aromatic hydrocarbons, heteroatomic compounds (NSO) and 13C. Such phenomena are relevant to bitumen paragenesis in petroleum reservoir rocks, to certain Phanerozoic occurrences of multiple generations of bitumens, and to bitumens in mineral deposits. 相似文献
13.
14.
Crayton J. Yapp 《Geochimica et cosmochimica acta》1983,47(7):1277-1287
The dehydration of a natural goethite to hematite is accompanied by a systematic hydrogen isotope fractionation. Closed system dehydration at, and below, 250°C results in a significantly greater degree of isotopic fractionation than does open system dehydration. This relationship is apparently reversed at 300°C. Both processes produce a progressive decrease in the ratio of the mineral hydrogen with increasing degree of dehydration. At temperatures of 160°C to 250°C the closed system mineralvapor fractionation factor is independent of temperature, while above 250°C, it varies strongly with temperature. The mineral-vapor fractionation factor associated with open system dehydration appears to be independent of temperature over the interval 160°C to 300°C. The closed system fractionation suggests that natural goethite undergoing dehydration in the presence of water can isotopically exchange with that water.CO2 loss from goethite during dehydration is correlated with the loss of H2O. The CO3 is thought to be present in carbonates which exist as impurities in the goethite. Loss of both H2O and CO2 appears to be diffusion-controlled. 相似文献
15.
J.Michael Moldowan Wolfgang K. Seifert Edward Arnold Jon Clardy 《Geochimica et cosmochimica acta》1984,48(8):1651-1661
Two C28H48-pentacyclic triterpanes were isolated from Monterey shale. X-ray crystallography of a crystal containing both compounds proved their structures as 17β,18α,21α(H)-28,30-bisnorhopane and 17β,18α,21β(H)-28,30-bisnorhopane. Several differences are found between 28,30-bisnorhopanes and the regular hopanes. Unlike the regular hopane epimers, for practical purposes the three epimeric 28,30-bisnorhopanes [17α,21β(H)-, 17β,21α(H)-, and 17β,21β(H)-]cannot be distinguished by their mass spectra. Special conditions are needed to separate them by gas chromatography. The diagenetically first-formed epimer is thought to be 17α,21β(H)- because it predominates in immature shales. The order of thermodynamic stability is 17β,2lα(H) < > 17α,21β(H) > 17β,21β(H), and all three epimers are present in petroleum. 25,28,30-Trisnorhopanes can be analyzed in similar fashion and are found to have similar thermodynamic characteristics. The percent of the ring D/E cis epimer of 28,30-bisnorhopane and/or 25,28,30-trisnorhopane is a useful maturation parameter similar to the 20S/20R sterane ratio. Evidence indicates 25-demethylation of 28,30-bisnorhopane to 25,28,30-trisnorhopane during advanced stages of biodegradation. Hence, percent ring cis 25,28,30-trisnorhopane has an application to maturation assessment in heavily biodegraded oils. 相似文献
16.
C.M. Ekweozor 《Organic Geochemistry》1986,10(4-6)
The major steranes of the non-asphaltene fraction of Nigerian tar sand bitumen (maltene) are the c27-c29 diasteranes [13β(H),17α(H); 20R + S] and C28-C29 regular steranes [14β (H),17β (H); 20S]. The reducing metal reaction products of the corresponding asphaltenes (maltene-I) contain mainly C27-C29 regular steranes with the 14β(H),17β(H); 20R + S and 14α(H),17α(H); 20R + S configurations as well as the corresponding diasteranes having the 13β(H),17α(H); 20R + S configuration. These sterane distributions suggest that maltene-I corresponds to an unaltered oil whilst the maltene is equivalent to the product of severe biodegradation of maltene-I. This is consistent with maltene-I being the remnant of “original oil” trapped within the asphaltene matrix and protected from the effect of in-reservior biodégradation.Degradation of Nigerian asphaltenes by refluxing with ferric chloride-acetic anhydride or methanolic potassium hydroxide also releases soluble reaction products having the characteristics of unaltered oil such as the presence of n-alkanes having an unbiased distribution. These methods appear to be milder and more suitable than reducing metal reactions for releasing hydrocarbons occluded by asphaltenes. 相似文献
17.
Hydrous and anhydrous closed-system pyrolysis experiments were conducted on a sample of Mahogany oil shale (Eocene Green River Formation) containing Type-I kerogen to determine whether the role of water had the same effect on petroleum generation as reported for Type-II kerogen in the Woodford Shale. The experiments were conducted at 330 and 350 °C for 72 h to determine the effects of water during kerogen decomposition to polar-rich bitumen and subsequent bitumen decomposition to hydrocarbon-rich oil. The results showed that the role of water was more significant in bitumen decomposition to oil at 350 °C than in kerogen decomposition to bitumen at 330 °C. At 350 °C, the hydrous experiment generated 29% more total hydrocarbon product and 33% more C15+ hydrocarbons than the anhydrous experiment. This is attributed to water dissolved in the bitumen serving as a source of hydrogen to enhance thermal cracking and facilitate the expulsion of immiscible oil. In the absence of water, cross linking is enhanced in the confines of the rock, resulting in formation of pyrobitumen and molecular hydrogen. These differences are also reflected in the color and texture of the recovered rock. Despite confining liquid-water pressure being 7-9 times greater in the hydrous experiments than the confining vapor pressure in the anhydrous experiments, recovered rock from the former had a lighter color and expansion fractures parallel to the bedding fabric of the rock. The absence of these open tensile fractures in the recovered rock from the anhydrous experiments indicates that water promotes net-volume increase reactions like thermal cracking over net-volume decrease reactions like cross linking, which results in pyrobitumen. The results indicate the role of water in hydrocarbon and petroleum formation from Type-I kerogen is significant, as reported for Type-II kerogen. 相似文献
18.
Colin M. Graham Simon M.F. Sheppard Timothy H.E. Heaton 《Geochimica et cosmochimica acta》1980,44(2):353-364
Fractionation factors between epidote minerals and water, and between the AlO(OH) dimorphs boehmite and diaspore and water, have been determined between 150 and 650°C. Small water mineral ratios were used to minimise the effect of incongruent dissolution of epidote minerals. Waters were extracted and analysed directly by puncturing capsules under vacuum. Hydrogen diffusion effects were eliminated by using thick-walled capsules. Exchange rates are very fast between epidote and water (and between boehmite and water), complete exchange taking only minutes above 450°C but several months at 250°C. Exchange between zoisite and water (and between diaspore and water) is very much slower, and an interpolation method was necessary to determine fractionation factors at 450 and below.For the temperature range 300–650°C, the equilibrium fractionation factor (αe) between epidote and water is independent of temperature and Fe content of the epidote, and is given by 1000 In αepidote-H2Oe = ?35.9 ± 2.5, while below 300°C 1000 In , with a ‘cross-over’ estimated to occur at around 185°C. By contrast, zoisite-water fractionations fit the relationship 1000 In .All studied minerals have hydrogen bonding. Fractionations are consistent with the general relationship: the shorter the O-H -- O bridge, the more depleted is the mineral in D.On account of rapid exchange rates, natural epidotes probably acquired their H-isotope compositions at or below 200°C, where fractionations are near or above 0%.; this is in accord with the observation that natural epidotes tend to concentrate D relative to other coexisting hydrous minerals. 相似文献
19.
Characterization of solid bitumens originating from thermal chemical alteration and thermochemical sulfate reduction 总被引：1，自引：0，他引：1
Simon R. Kelemen Peter J. Kwiatek Mobae Afeworki William A. Lamberti Hans G. Machel Trudy Bolin 《Geochimica et cosmochimica acta》2010,74(18):5305-4687
Solid bitumen can arise from several reservoir processes acting on migrated petroleum. Insoluble solid organic residues can form by oxidative processes associated with thermochemical sulfate reduction (TSR) as well as by thermal chemical alteration (TCA) of petroleum. TCA may follow non-thermal processes, such as biodegradation and asphaltene precipitation, that produce viscous fluids enriched in polar compounds that are then altered into solid bitumens. It is difficult to distinguish solid bitumen formed by TCA from TSR since both processes occur under relatively high temperatures. The focus of the present work is to characterize solid bitumen samples associated with TSR- or TCA-processes using a combination of solid-state X-ray Photoelectron Spectroscopy (XPS), Sulfur X-ray Absorption Near Edge Structure Spectroscopy (S-XANES), and 13C NMR. Naturally occurring solid bitumens from three locations, Nisku Formation, Brazeau River area (TSR-related); La Barge Field, Madison Formation (TSR-related); and, the Alaskan North Slope, Brooks Range (TCA-related), are compared to solid bitumens generated in laboratory simulations of TSR and TCA.The chemical nature of solid bitumens with respect to organic nitrogen and sulfur can be understood in terms of (1) the nature of hydrocarbon precursor molecules, (2) the mode of sulfur incorporation, and (3) their concentration during thermal stress. TSR-solid bitumen is highly aromatic, sulfur-rich, and nitrogen-poor. These heteroatom distributions are attributed to the ability of TSR to incorporate copious amounts of inorganic sulfur (S/C atomic ratio >0.035) into aromatic structures and to initial low levels of nitrogen in the unaltered petroleum. In contrast, TCA-solid bitumen is derived from polar materials that are initially rich in sulfur and nitrogen. Aromaticity and nitrogen increase as thermal stress cleaves aliphatic moieties and condensation reactions take place. TCA-bitumens from the Brooks Range have <75% aromatic carbon. TCA-bitumens exposed to greater thermal stress can have a higher aromaticity, like that observed in TSR-bitumens. Organic sulfur in TCA-organic solids remains relatively constant with increasing maturation (S/C atomic ratio <0.035) due to offsetting preservation and H2S elimination reactions. Although S-XANES and 13C NMR provide information needed to understand changes in structure and reactivity that occur in the formation of petroleum solids, in some cases XPS analysis is sufficient to determine whether a solid bitumen is formed by TCA or TSR. 相似文献
20.
Ger Van Graas 《Organic Geochemistry》1986,10(4-6)
Biomarker distributions in a suite of asphaltenes and kerogens have been analysed by flash pyrolysis directly coupled to a GCMS system. Attention has been focussed on biomarkers of the sterane and triterpane types. The sample suite under investigation consists of sediments with different kerogen types and some crude oils. Biomarker distributions in the pyrolysates have been compared with the “free” biomarkers in the corresponding saturated hydrocarbon fractions.The analyses show significant differences between the distributions of the free biomarkers and those in the pyrolysates. The latter have lower amounts of steranes while diasteranes are absent or present at low concentrations only. In the triterpane traces a shift of maximum intensity from C30 (free compounds) to C27/C29 is observed. Furthermore, the pyrolysates contain a set of triterpenes (not present among the free compounds), and there is a selective loss of “non-regular” triterpanes that are present in the saturated hydrocarbon fractions. The observed differences between pyrolysates and free hydrocarbons can be explained partly by the processes occurring during pyrolysis such as bond rupture and subsequent stabilisation of primary pyrolysis products. To a certain extent these differences also show that maturation processes occurring in sediments have effects on free biomarker molecules different from those on molecules that are enclosed in a macromolecular matrix (kerogen or asphaltenes).Differences between biomarker distributions of asphaltene and kerogen pyrolysates are relatively small. A comparison with the pyrolysates from extracted whole sediments suggests that these differences are mainly caused by interactions between the organic material and the mineral matrix during pyrolysis.Oil asphaltenes behave differently from sediment asphaltenes as their pyrolysates are more similar to the corresponding saturated hydrocarbon fractions, i.e. the differences described above are observed to a much smaller extent. This different behaviour appears to be the result of coprecipitation of a part of the maltene fraction with the oil asphaltenes. 相似文献