Identification and occurrence of 25-norbenzohopanes in biodegraded bitumen from Palaeozoic carbonates in northern Alberta

In addition to the previously reported 25-norhopanes and 25-norhopanoic acids, for the first time we report the identification of 25-norbenzohopanes. The hydrocarbon composition of the bitumen from Palaeozoic carbonates in northern Alberta displays molecular evidence for severe levels of biodegradation characterised by the removal of C₃₀–C₃₅ hopanes. Biodegradation is also indicated by the removal of C₃₂ and C₃₃ benzohopanes. The appearance of C₃₁ and C₃₂ 25-norbenzohopanes corresponds to the decrease in C₃₂ and C₃₃ benzohopanes, suggesting that 25-norbenzohopanes originate by demethylation of benzohopane counterparts. Demethylation at C-10 in the hopanoids affects a broader class of compounds that so far includes the hopanes and hopanoic acids, as well as the benzylated hopanoid species.     

Geochemical Characteristics of Different Kinds of Crude Oils in the Tarim Basin,Northwest China

Based on the compositions and distributions of biomarkers in thirty-five representative oil samples, oils from the Tarim Basin of northwestern China are mainly divided into two oil families. One oil family contains relatively low amounts of C₁₅-C₂₀ isoprenoid hydrocarbons and shows pristane predominance with Pr/Ph ratios ranging from 1.50 to 3.00. The GC/MS analytical data of these oils show the occurrence of abundant hopanes, and low concentrations of steranes and tricyclic terpanes with hopanes/steranes ratios from 6.25 to 12.24 and tricyclic terpanes/hopanes ratios from 0.03 to 0.24. These oils contain low drimane relative to homodrimane (C₁₅/C₁₆ < 1.0) and abundant rearranged bicyclanes in bicyclic sesquiterpanes. They are dominated by low carbon number (C₁₉-C₂₁) compounds in the tricyclic terpanes, and are rich in rearranged hopanes, C₂₉Ts and an unknown C₃₀ compound in pentacyclic triterpanes. These geochemical characteristics suggest that the oils were generated mainly from terrigenous organic matter. The other oil family shows remarkably different biomarker compositions and distributions. The oils revealed Pr/Ph ratios of about 1.0, high drimane/homodrimane ratios (>1.0), low hopanes/steranes ratios (0.65–2.50), high tricyclic terpanes/hopanes ratios (0.30–2.00) and a dominant peak at C₂₃ in tricyclic tepanes, suggesting a marine organic origin. Oil-source rock correlation indicates that these two oil families seem to have been derived from Mesozoic Jurassic-Triassic terrestrial source rocks (shales and coal seams) and Lower Paleozoic Ordovician-Cambrian marine source rocks, respectively.     

A natural pyrolysis experiment — hopanes from hopanoic acids?

The formation or generation of hopanes are important processes during both the natural heating of organic-rich sediments and laboratory pyrolysis experiments. Molecular maturity parameters as well as the amounts (ng/g rock) of the C₃₁ hopanes and C₃₀–C₃₂ hopanoic acids were quantified in a Jurassic silty shale horizon (Isle of Skye, Scotland) as a function of distance from an igneous intrusion. The maturity profiles of the homohopanes and the hopanoic acids are comparable. There is also a correlation between the decreasing amounts of C₃₀–C₃₂ hopanoic acids and concomitant increases in C₂₉–C₃₁ hopanes suggesting that free hopanoic acids could be one potential source of hopanes in this particular horizon. Other possible sources could include hopanoic acids that are bound into the macromolecular fraction.     

Novel side chain methylated and hexacyclic hopanes: Identification by synthesis, distribution in a worldwide set of coals and crude oils and use as markers for oxic depositional environments

Novel side chain methylated and hexacyclic hopanes have been identified in coals and oils from around the world. Extended hopanes (>C₃₂) with an additional methyl in the side chain (“isohopanes”) were identified by comparison with synthetic standards. The major C₃₃-C₃₅ isohopanes are 31-methylbishomohopanes, 32-methyltrishomohopanes and 33-methyltetrakishomohopanes. Extended hopanes methylated at C-29 were not detected. The 17α(H),21β(H)-31-methyltrishomohopanes show four peaks on gas chromatography because of the extra asymmetric carbon at C-31. Like regular hopanes, the isohopanes extend beyond C₃₅. Low concentrations of novel hexacyclic hopanes having 35 or more carbons were also detected in oils and coal extracts. The C₃₅ hexacyclic hopanes were identified as 29-cyclopentylhopanes. Isohopanes are released from the kerogen by hydrous pyrolysis and hydropyrolysis. The 22S/(22S + 22R) ratio for 31-methylbishomohopanes and other isohopanes is around 0.60 at equilibrium in geological samples. They isomerize slightly more slowly than regular C₃₃ hopanes. Isohop-17(21)-enes, 2α-methylisohopanes and two series of rearranged isohopanes were tentatively identified. Isohopanes can be biodegraded to form the corresponding 25-norhopanes. When 25-norhopanes are not formed, the isohopanes are much more resistant to biodegradation than regular hopanes. In biodegraded oil seeps from Greece, 30-norisohopanes were tentatively assigned. The composition and relative abundance of C₃₃ and C₃₄ isohopanes in a worldwide set of coals and crude oils was determined. Isohopanes are abundant in coal and coal-generated oils, where they can account for more than 5% of all extended hopanes, and low in abundance in oils from source rocks deposited under anoxic conditions.     

The stereochemistry of bound and extractable pentacyclic triterpenoids during closed system pyrolysis

The distributions of hopanoic acids, ranging from C₃₀ to C₃₄, in the Messel oil shale were characterized in both the free and bound states. The bound acids were released by thermochemolysis in the presence of tetramethylammonium hydroxide (TMAH). These were compared with the distributions of the hopanoic acids and hopanes released or generated from Messel oil shale kerogen following closed system microscale pyrolysis. This comparison revealed that epimerization had occurred at C-17, C-21 and C-22 during heating. It was also clear that the residual bound hopanoic acids had undergone configurational isomerization. During the pyrolysis there is a large loss of hopanoic acids following their rapid release from the kerogen into the free fraction even at 250 °C. In these particular experiments this loss does not appear to result in exclusive formation of hopanes, by way of decarboxylation or reduction reactions, unless the resulting hopanes are either themselves rapidly transformed into other compounds or the reaction rates are a function of the total number of carbon atoms in each hopanoic acid precursor.     

Demethylated hopanes in crude oils and their applications in petroleum geochemistry

Analyses of some Australian crude oils show that many contain varying concentrations of A/ B-ring demethylated hopanes. These range from C₂₆ to C₃₄ and have been identified from their retention times and mass spectral data as 17α(H)-25-norhopanes. Comparison of hopane and demethylated hopane concentrations and distributions in source-related, biodegraded oils suggests that demethylated hopanes are biotransformation products of the hopanes. Further, it appears that the process occurs at a late stage of biodegradation, after partial degradation of steranes has occurred. Demethylated hopanes are proposed as biomarkers for this stage of severe biodegradation. The presence of these compounds in apparently undegraded crude oils is thought to be due to the presence of biodegraded crude oil residues which have been dissolved by the undegraded crude oil during accumulation in the reservoir sands. The timing of hopane demethylation, relative to the degradation of other compounds, has been assessed and the progressive changes in crude oil composition with increasing extent of biodegradation have been identified. The use of demethylated hopanes as maturity parameters for severely biodegraded crude oils, and the applicability of established biomarker maturity parameters to such oils, are also discussed.     

Geochemical characteristics and genetic types of crude oils from Qinjiatun and Qikeshu oilfields in the Lishu Fault Depression,Songliao Basin,northeastern China

The Qinjiatun and Qikeshu oilfields are new Mesozoic petroleum exploration targets in Lishu Fault Depression of Songliao Basin, northeastern China. Currently, researches on geochemistry of crude oils from Qinjiatun and Qikeshu oilfields have not been performed and the genesis of oils is still uncertain. Based on bulk analyses, the crude oils in the Qinjiatun and Qikeshu oilfields of Lishu Fault Depression from the Lower Cretaceous can be classified as three types. TypeⅠoils, from Quantou and Denglouku formations of Qikeshu oilfield, are characterized by high C24tetracyclic terpane/C26tricyclic terpanes ratios, low gammacerance/C30hopane ratios, tricyclic terpanes/hopanes ratios, C29Ts/C29norhopane ratios and 17α(H)-diahopane/17α(H)-hopane ratios, indicating a brackish lacustrine facies. TypeⅡoils, from Shahezi Formation of Qikeshu oilfield show low C24tetracyclic terpane/C26tricyclic terpanes, high gammacerance/C30hopane ratios, tricyclic terpanes/hopanes ratios, C29Ts/C29 norhopane and C30diahopane/C30hopane ratios, thus suggesting that they originated from source rocks deposited in a weak reducing brackish lacustrine environment, or clay-rich sediments. Type oilsⅢ, from some wells of Qikeshu oilfield have geochemical characteristics intermediate between those two types and may be mixture of typeⅠand Ⅱoils.     

Distribution and significance of novel low molecular weight sterenes in an immature evaporitic sediment from the Jinxian Sag,North China

An unusual series of C₂₂–C₂₇ monounsaturated sterenes and C₂₄–C₃₀ tetracyclic terpanes (17,21-secohopanes) were detected in relatively high concentrations in an immature evaporitic marl sediment of the Jinxian Sag, Bohai Bay Basin, North China. The site of unsaturation in these novel sterenes is assigned tentatively to the D ring on the basis of mass spectral interpretation, which also distinguishes them from reported unsaturated sterenes. Other hydrocarbon biomarker or stable isotope characteristics are indicative of microbial (e.g. methyl hopanes), phytoplankton or higher plant (depleted δ¹³C values of isoprenoids and hopanes) inputs and an anoxic carbonate depositional environment (hexacyclic hopanes; tetracyclic terpanes). The hydrocarbon composition showed no obvious biodegradation and the relatively high concentration of unsaturated terpenoids (e.g. gammacerene) and low values of other established maturity parameters (T_s/T_m = 0.23; R_o = 0.44%; T_max = 417 °C), are consistent with sediments of low maturity. The novel, low molecular weight sterenes and the tetracyclic terpanes may be early diagenetic products of microbial sources in a carbonate environment.     

Molecular and stable carbon isotopic compositions of hopanoids in seep carbonates from the South China Sea continental slope

The lipid biomarkers of hopanoids in cold seep carbonates from the South China Sea continental slope were investigated by gas chromatography–mass spectrometer (GC–MS) and gas chromatography-isotope ratio-mass spectrometer (GC-ir-MS). The distribution of hopanes/hopenes shows a preference for the ‘biological’ 17β(H), 21β(H)-over the ‘geological’ 17α(H), 21β(H)-configuration. This interpretation is in agreement with the strong odd–even preference of long-chain n-alkanes in those samples, suggesting that the ββ hopanes may be the early diagenetic products of biohopanoids and the αβ, βα configurations of hopanes were mainly derived from allochthonous sources contributing to the organic matter of the carbonates. In terms of hopanoid acids, the C₃₀ to C₃₃ 17β(H), 21β(H)-hopanoid acids were detected with C₃₂ 17β(H), 21β(H)-hopanoid acid being the most abundant. However, there is a significant difference in stable carbon isotopic compostions of the C₃₂ 17β(H), 21β(H)-hopanoic acid among samples (−30.7‰ to −69.8‰). The δ¹³C values match well with the carbon isotopic compositions of SRB-derived iso-/anteiso-C_15:0 fatty acids in the samples, which strongly depend on the carbon utilization types by microbe. The most abundant compound of hopanols detected in the samples, C₃₀-17β(H), 21β(H)-hopanol, may be a good indicator of diagenetic product of type I methanotrophs. The molecular and carbon isotopic compositions of hopanoids demonstrate clearly that there is a combination contribution of both SRB and type I or type X methanotrophs to the source organism in the seep carbonates from the South China Sea continental slope.     

The occurence of unusual C27 and C29 sterane predominances in two types of Oman crude oil

Two types of Oman crude oils reveal unusual sterane distributions. Type “A”, which is the more common (74 examples), is characterised by a predominance of C₂₉ iso- and normal-steranes and generally none or only very low relative concentrations of rearranged-steranes. The triterpanes are characterised by the predominance of the C₂₉ 17αH, 21βH norhopane over the C₃₀ 17αH, 21βH hopane and non-predominant C₂₀–C₃₀ tricyclic terpanes. The C₂₉ steranes of this type of crude were not derived from the C₂₉ sterols of land-plant origin (frequently proposed as the source of C₂₉ steranes) since there is good geological evidence that these crudes were generated from a pre-Cambrian source rock, a geological period when land-plants did not exist.The type “B” crude oil (11 known examples) is characterised by a strong predominance of C₂₇ iso-, normal- and rearranged-steranes, relatively lower concentrations of 17αH, 21βH hopanes and relatively high concentrations of C₂₀–C₃₀ tricyclic terpanes.The remarkably different biomarker characteristics of these crude oils imply that the organisms active in the depositional environment of the respective source rocks were significantly different.     

四川南桐地区二叠系龙潭煤层生物标记物及其地质意义

四川南桐地区二叠系龙潭煤层具有良好的生油潜力。其生物标记物包括正构和异构烷烃,类异戊二烯烷烃,倍半萜烷,二萜烷,三环萜烷,藿烷,一种未知结构的五环三萜烷(C₃₀),甾烷,4-甲基甾烷等。煤层生物标记物特征表明在其形成过程中有藻类和细菌等微生物物质的加入。     

A geochemical investigation of crude oils and source rocks from Biyang Basin, China

China has a number of petroliferous lacustrine sedimentary basins of varying salinity and age (mainly Eocene). A geochemical investigation has been undertaken on several oils and source rocks from the Eocene lacustrine Biyang Basin. The distributions of n-alkanes, isoprenoids, steranes, and terpanes have been studied and used to characterize the sedimentary environment of deposition, maturity, biodegradation and undertake possible correlations. The ratios of C₃₀-hopane/gammacerane, 4-methyl-steranes/regular steranes, steranes/hopanes, C₂₁ tricyclic/C₃₀ hopane are proposed to be indicative of the depositional environment whereas ß-carotane appears to be a source related indicator. The geochemical data obtained in this study suggest that the major source rocks in the Biyang Basin were deposited in a saline/hypersaline depositional environment.     

Geochemical characteristics of Lower Permian coal-measure source rocks in Northeast Ordos Basin

General characteristics and biomarker distributions of Lower Permian coal-measure source rocks in northeastern Ordos Bsain have been analyzed in this paper. The results show that the source rocks are type III kerogen, thermally mature, with high content of total organic carbon. The extracts of the source rock samples with different lithologies from Well Su 27 feature high Pr/Ph ratios, high C19TT and C24Te, high rearranged hopanes, a predominance of C29 sterane in regular steranes, and the absence of C30 4-methylsteranes. These data suggest that the source rocks were deposited in suboxic to oxic conditions with dominantly terrigenous higher plant input. In contrast, the source rocks from wells Shuang 1 and Yu 20, are characterized by low Pr/Ph ratios, low C19TT and C24Te, high C23TT, similar content of C27 sterane and C29 sterane, and the presence of C30 4-methylsteranes, showing that the source rocks were deposited in reducing environment with algae and/or microorganisms and terrigenous higher plant input.     

Selective enrichment of steroid and triterpenoid hydrocarbons from crude oil using gel permeation chromatography for stable carbon isotope analysis

Gel permeation chromatography (GPC) using a high performance liquid chromatography (HPLC) system was studied for the separation and enrichment of steroid and hopanoid hydrocarbons from crude oil for stable carbon isotope analysis. A crude oil sample was pretreated using silica gel chromatography and 5A molecular sieve to remove polycyclic aromatic hydrocarbons and n-alkanes. The GPC behavior of both the pretreated saturated hydrocarbon fraction of the oil and standard steroid [5α(H), 14α(H), 17α(H) C₂₇–C₂₉ steranes], hopanoid [17α(H) C₂₇ trisnorhopane, 17α(H), 21β(H) C₂₉–C₃₂ hopanes] and triterpenoid [18α(H)-oleanane, gammacerane] mixtures were examined. The results indicate that 17α(H), 21β(H) hopanes as well as steranes could be enriched efficiently using GPC and that they could be obtained without removing n-alkanes from the oil saturated hydrocarbon fraction. The GPC behavior of steroid and triterpenoid hydrocarbons was controlled by molecular size and shape.     

Novel family of hexacyclic hopanoid alkanes (C32C35) occurring in sediments and oils from anoxic paleoenvironments

Four novel hexacyclic alkanes, fairly common in crude oils and rock extracts from evaporitic series, have been tentatively identified on the basis of GC/MS data as C₃₂, C₃₃, C₃₄ and C₃₅ hexahydrobenzohopanes. These structures, only recorded in carbonate-anhydrite sequences, i.e. very anoxic paleoenvironments, tend to concentrate when pristane to phytane ratios increase. Changes in their relative concentration to αβ hopanes appear to be more related to variations in source and/or environmental conditions than to maturity. The ratio of the novel hexacylic C₃₅ hopane to C₃₅ αβ hopane, compared with other biomarker ratios, suggests that hexacyclic alkanes and hopanes are byproducts of the same hopanoid precursors via different chemical reactions. In addition the novel hexacyclic alkanes are bacterially resistant and may serve as a useful family to define the paleoenvironment (viz. very anoxic) of the parent source rock of a drastically biodegraded oil.     

Petroleum geochemistry of the Potwar Basin, Pakistan: 1. Oil-oil correlation using biomarkers, δC and δD

Geochemical characterisation of 18 crude oils from the Potwar Basin (Upper Indus), Pakistan is carried out in this study. Their relative thermal maturities, environment of deposition, source of organic matter (OM) and the extent of biodegradation based on the hydrocarbon (HC) distributions are investigated. A detailed oil-oil correlation of the area is established. Gas chromatography-mass spectrometry (GC-MS) analyses and bulk stable carbon and hydrogen isotopic compositions of saturated and aromatic HC fractions reveals three compositional groups of oils. Most of the oils from the basin are typically generated from shallow marine source rocks. However, group A contains terrigenous OM deposited under highly oxic/fluvio-deltaic conditions reflected by high pristane/phytane (Pr/Ph), C₃₀ diahopane/C₂₉Ts, diahopane/hopane and diasterane/sterane ratios and low dibenzothiophene (DBT)/phenanthrene (P) ratios. The abundance of C₁₉-tricyclic and C₂₄-tetracyclic terpanes are consistent with a predominant terrigenous OM source for group A. Saturated HC biomarker parameters from the rest of the oils show a predominant marine origin, however groups B and C are clearly separated by bulk δ¹³C and δD and the distributions of the saturated HC fractions supporting variations in source and environment of deposition of their respective source rocks. Moreover, various saturated HC biomarker ratios such as steranes/hopanes, diasteranes/steranes, C₂₃-tricyclic/C₃₀ hopane, C₂₈-tricyclic/C₃₀ hopane, total tricyclic terpanes/hopanes and C₃₁(R + S)/C₃₀ hopane show that two different groups are present. These biomarker ratios show that group B oils are generated from clastic-rich source rocks deposited under more suboxic depositional environments compared to group C oils. Group C oils show a relatively higher input of algal mixed with terrigenous OM, supported by the abundance of extended tricyclic terpanes (up to C₄₁₊) and steranes.Biomarker thermal maturity parameters mostly reached to their equilibrium values indicating that the source rocks for Potwar Basin oils must have reached the early to peak oil generation window, while aromatic HC parameters suggest up to late oil window thermal maturity. The extent of biodegradation of the Potwar Basin oils is determined using various saturated HC parameters and variations in bulk properties such as API gravity. Groups A and C oils are not biodegraded and show mature HC profiles, while some of the oils from group B show minor levels of biodegradation consistent with high Pr/n-C₁₇, Ph/n-C₁₈ and low API gravities.     

Evidence for the rapid incorporation of hopanoids into kerogen

Hopanoids bound into the insoluble organic matter (kerogen) of Recent sediments from a freshwater lake (Priest Pot) and an anoxic sulphidic fjord (Framvaren) were released by hydropyrolysis and examined by gas chromatography-mass spectrometry. Bound hopanoids are present in high concentration (190-1400 μg/g TOC) and represent 22 to 86% of the total analysable hopanoids (i.e., bound and solvent-soluble), this proportion increasing with depth in Framvaren Fjord. The hopanes generated by hydropyrolysis contain higher amounts of the C₃₅, C₃₂, and C₃₀ homologues, reflecting the carbon number distribution of the bound hopanoids and indicating that both biohopanoids (C₃₀ and C₃₅) and their diagenetic products (dominated by C₃₂) are incorporated into the kerogen on a timescale of only 0 to 350 years. Sequential (multiple temperature) hydropyrolysis experiments gave an indication of the relative strengths of bonds being cleaved in association with hopane generation: The hopanoids of a sediment from Priest Pot are almost entirely bound by strong covalent bonds, interpreted to be mainly ether linkages, whilst a Framvaren sediment contains hopanoids that are bound by a mixture of weak di-/polysulphide linkages and stronger ether bonds. Labelling with deuterium indicated that the strong covalent linkages dominate, even for the Framvaren sediment.     

Constraining the genetic relationships of 25-norhopanes,hopanoic and 25-norhopanoic acids in onshore Niger Delta oils using a temperature-dependent material balance

Analysis of oil samples from the Niger Delta (Nigeria) revealed a range of structurally related hopanes, including 25-norhopanes, and hopanoic and 25-norhopanoic acids. 25-Norhopanes were detected in all medium and heavily biodegraded oils and were most abundant in the heavily degraded oils. Hopanoic acids (C₃₀-C₃₃) and 25-norhopanoic acids (C₃₀-C₃₁) were most abundant in moderately degraded oils and occurred in reduced concentration in heavily degraded oils but were absent from, or in trace concentration in, slightly degraded oils. Consideration of the structures suggests that 25-norhopanoic acids form via carboxylation of 25-norhopanes or demethylation of hopanoic acids. Mass balance for the onshore Niger Delta oils suggests that formation of 25-norhopanes operates independently of 25-norhopanoic acid formation and that 25-norhopanoic acids are likely transient intermediates for only a small proportion of the 25-norhopanes.     

Thermodynamic stability of various alkylated, dealkylated and rearranged 17α- and 17β-hopane isomers using molecular mechanics calculations

The thermodynamic stability of selected alkylated, dealkylated and rearranged 17α- and 17β-hopane isomers in the C₂₇, C₂₈, C₂₉, C₃₀ and C₃₁ families were calculated using molecular mechanics (MM2) methods and, where possible, calculated equilibrium ratios of certain isomers were compared with observed ratios of isomers in thermally mature crude oil samples. Those calculated and observed ratios having similar values include: (1) the relative distributions among 17β(H)/17α(H) and 21β(H)/21α(H)-hopanes including the absence of the 17β(H),21β(H)- and 17α(H),21α(H)-hopanes; (2) the 22R/22S ratios in 30-methyl-17α-hopane and 30-methyl-17β-moretane; (3) the relative distributions among 17α(H)/17β(H)- and 21α(H)/21β(H)-28,30-bisnorhopanes and among 25,28,30-trisnorhopanes, including the relatively greater stability of 17β(H) isomers in contrast to the regular hopane series; and (4) the ratios of 28(18−17S)abeo hopanes with respect to their unrearranged counterparts including the C₂₇ compounds, Ts/Tm.     

An assessment of paleodepositional environment and maturity of organic matter in sediments of the Setap Shale and Belait formations in West Sabah,East Malaysia by organic geochemical methods

The black shale samples collected from two Neogene formations in the Klias Peninsula area, West Sabah, have been assessed and characterized in details by gas chromatography, gas chromatography-mass spectrometry and a variety of organic geochemical parameters. The aims of this study are to describe the characteristics of organic matter of these sediments in terms of source/type of the organic matter, assess its thermal maturity and paleoenvironment of deposition, based primarily on biomarker distributions. The results of both formations do not reveal significant differences within the rock extracts. The gas chromatograms of the saturated hydrocarbon fractions of the Setap Shale and the Belait formations displayed monomodal n-alkane distributions and nearly identical regular sterane compositions with a predominance of C₂₇ regular steranes. These are consistent with open marine depositional environments dominated by marine biological matter. Another related feature of these rock extracts is the presence of a high relative abundance of gammacerane, indicating anoxic marine hypersaline source depositional environment. The relatively high abundance of common land plant-derived biomarkers, such as bicadinanes and oleananes, is a clear indication of a major terrigenous input to the source of the extractable organic matter. The predominance of oleanane biomarkers in both formations is indicative of angiospermis input and Tertiary source rocks. The high C₂₉/C₃₀ hopane ratios, moderate development of C₃₃–C₃₅ hopanes, high abundance of tricyclic terpanes and a slight predominance of C₂₇ regular sterane over C₂₈ and C₂₉ steranes are characteristic features tending to suggest a significant marine influence on these source rocks, thereby suggesting a mixed source input. The 22S/(22S+22R)C₃₂ hopane ratio has reached equilibrium, and this is supported by the high maturity level as indicated by the 22S/22SC_31–33 extended hopane ratios and 20S/(20S+20R)C₂₉ regular steranes ratios.