Petroleum geochemistry of the Potwar Basin,Pakistan: II – Oil classification based on heterocyclic and polycyclic aromatic hydrocarbons

In a previous study, oils in the Potwar Basin (Upper Indus) of Pakistan were correlated based on the dissimilarity of source and depositional environment of organic matter (OM) using biomarkers and bulk stable isotopes. This study is aimed at supporting the classification of Potwar Basin oils into three groups (A, B and C) using the distribution of alkylnaphthalenes, alkylphenanthrenes, alkyldibenzothiophenes, alkyldibenzofurans, alkylfluorenes, alkylbiphenyls, triaromatic steroids, methyl triaromatic steroids, retene, methyl retenes and cadalene. The higher relative abundance of specific methyl isomers of naphthalene and phenanthrene and the presence of diagnostic aromatic biomarkers clearly indicate the terrigenous and oxic depositional environment of OM for group A oil. Group B and C oils are of marine origin and the aforementioned heterocyclic and polycyclic aromatic hydrocarbons (HCs) differentiate them clearly into two different groups. The relative percentages of heterocyclic aromatic HCs reveal that the distribution of these compounds is controlled by the depositional environment of the OM. Sulfur-containing heterocyclic aromatic HCs are higher in crude oils generated from source rocks deposited in suboxic depositional environments, while oxygen-containing heterocyclic aromatic HCs in combination with alkylfluorenes are higher in marine oxic and deltaic oils. Biomarker and aromatic HC parameters do not indicate significant differences in the thermal maturity of Potwar Basin oils. Triaromatic and methyl triaromatic steroids support the division of Potwar Basin oils into the three groups and their relative abundances are related to source OM rather than thermal maturity. Significantly higher amounts of C₂₀ and C₂₁ triaromtic steroids and the presence or absence of long chain triaromatic steroids (C₂₅, C₂₆, C₂₇, and C₂₈) indicates that these compounds are probably formed from different biological precursors in each group. Different isomers of methyl substituted triaromatic steroids are present only for short chain compounds (C₂₀–C₂₂) and the origin of these compounds may be short chain methyl steranes from unknown biological precursors.     

Terpenoid biomarker distributions in low maturity crude oils

Twenty-seven heavy crude oils of diverse origin were geochemically assessed with respect to both bulk and mlecular composition for the purpose of identifying and quanttfying valid biomarker parameters for low maturity oils. The low thermal maturity level of many of these oils is evident from the bulk and alipathic chromatographic data, and oil sourced from both marine and terrigenous organic matter are represented. Selective metastable ion monitoring (SMIM) was employed to measure separately the distribution of C₂₇, C₂₈, and C₂₉ sterane isomers. The useful maturity indicators include the C₂₉ 5α(H) 20S/20R ratio, the relative quantity of the biological sterane configuration in each of the total normal C₂₇, C₂₈, and C₂₉ steranes, and the rearranged to normal sterane ratio. In addition, C₂₇ rearranged steran es appear to form at a faster rate than C₂₈ or C₂₉ rearranged steranes. However, the isomerization of the C₂₇ biological component appears to occur at a slower rate than the C₂₉ counterpart suggesting that the former may be used as a maturity parameter at higher levels of thermal maturation. In the triterpane distributions, the C₂₇ trisnorhopane isomers and the moretane to hopane ratios appear to be both source and maturity related and cannot be used as successful maturity parameters in oils unless they share a common source. The C₃₁₊ hopane 22S/22R equilibrium ratio appears to increase with increasing molecular weight (C₃₁–C₃₄).     

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.     

The effects of thermal maturity on distributions of dimethylnaphthalenes and trimethylnaphthalenes in some Ancient sediments and petroleums

The distributions of di- and trimethylnaphthalenes in two sedimentary sequences from Western Australia have been examined by capillary gas chromatography and combined gas chromatography-mass spectrometry. A general decrease was observed in the relative proportions of αα-dimethylnaphthalenes and ααβ-trimethylnaphthalenes with increasing thermal maturity. Similar trends were also observed for six crude oils which have very different ratios of ethylcholestane epimers indicating very different thermal histories. These results suggest that changes in the relative abundances of certain methyl substituted naphthalenes may be useful indicators of thermal maturity of sedimentary organic matter, and the use of a number of isomer ratios is illustrated.     

Effects of thermal maturation on steroid hydrocarbons as determined by hydrous pyrolysis of Phosphoria Retort Shale

Hydrous pyrolysis experiments on the Phosphoria Retort Shale generate bitumen extracts and expelled oils that have steroid hydrocarbons with m/z 217-, 231-, and 253-mass Chromatographic distributions that are similar to those of bitumens and crude oils in the natural system. These experiments agree with the natural observations that diasteroid hydrocarbons increase relative to their regular counterparts with increasing thermal stress, while their C₂₇ through C₂₉ proportionality shows a slight enrichment in C₂₇. Relative concentrations of 20S to 20R configurations of 24-ethyl-14α,17α-cholestane show the expected increase with increasing thermal stress into the early part of the primary oil generation stage, but thereafter decrease with increasing thermal stress. If this reversal is found in high maturity sections of the natural system, the utility of this transformation as a maturity index will be limited. Triaromatic- to monoaromatic-steroid hydrocarbon concentrations increase with increasing thermal stress as observed in the natural system. Preferred migration of monoaromatic steroid hydrocarbons from bitumen extracts to expelled oils places considerable doubt on currently employed kinetic models for this aromatization reaction. As in the natural system, the experiments show relative concentrations of low-molecular weight- to high-molecular weight-triaromatic steroid hydrocarbons to increase with increasing thermal stress. Assuming a first-order reaction rate, the apparent activation energy and pre-exponential factor for this apparent side-chain cleavage reaction are 175.59 kJ mol⁻¹ and 2.82 × 10¹³ hr⁻¹, respectively. These kinetic parameters are geologically reasonable and are similar to those for the overall generation of expelled oil.     

Methylbiphenyl,ethylbiphenyl and dimethylbiphenyl isomer distributions in some sediments and crude oils

Petroleum samples and organic extracts from two sedimentary sequences have been analysed using capillary gas chromatography and GC-MS techniques for isomeric methylbiphenyls, ethylbiphenyls and dimethylbiphenyls. The relative abundances of isomers with substituents in the ortho positions decrease with increasing depth (maturity) in both sedimentary sequences. Accordingly, these compounds appear to offer potential as indicators of thermal maturity of sediments.     

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.     

The origin and fate of 4-methyl steroids—II. Dehydration of stanols and occurrence of c30 4-methyl steranes

Certain features of the distributions of sedimentary 4-methyl steroid hydrocarbons have been investigated: (i) competitive dehydration experiments with stanols adsorbed on a shale suggests a possible explanation for the low abundance of 4-methyl sterenes relative to their desmethyl counterparts in immature sediments, (ii) a 4-methyl spirostene which is a minor product of the backbone rearrangement of 4-methylcholest-4-ene in the laboratory has been tentatively assigned; its presence in a Toarcian black shale with a second isomer provides further evidence that the sedimentary backbone rearrangement of 4-methyl sterenes is analogous to that of their desmethyl counterparts and (iii) the major C₃₀ 4-methyl steranes in Semécourt shale (Toarcian, Paris Basin) differ from those in an Eocene lacustrine shale from China; this indicates the potential complexity of C₃₀ steroidal alkanes (both 4-methyl and desmethyl) which can occur in sedimentary organic matter and shows that care must be taken in using m/z 217 mass chromatograms alone for routine input and maturity assessment using steroidal alkanes.     

Distribution Patterns of Pentacyclic TriterpenoidHydrocarbons in Low-Mature Source Rocksfrom Eastern China

Four typical distribution patterns of pentacyclic triterpenoid hydrocarbons (types A-D) are distinguished in the low-mature source rocks from eastern China. Type A has a relatively high content of pentacyclic triterpenes. It exists in immature sediments and the distribution and abundance of triterpenes vary with the maturity of the sediments. An unknown C30 triterpene (UCT2) has also been detected in very shallow sediments. This compound is very unstable and disappears rapidly with the increase of depth. Type B is characterized by a relatively high amount of 17α(H), 21β(H)-30-homohopane. This kind of distribution pattern is common in coals and terrestrial sediments of low maturity. Type C has a relatively high content of diahopane and neohopane series. The analysis shows that this distribution pattern may have an indirect relationship with the input of higher plants despite its microbial source. There are C30-unconfirmed triterpane (UCT2) and a relatively high content of C35 hopane in type D. The dist     

Tricyclic terpane maturity parameters: response to heating by an igneous intrusion

The effects of thermal maturation upon the abundance and composition of the tricyclic terpanes have been investigated within a single sedimentary horizon within the Dun Caan Shale Member (Isle of Skye, Scotland) intruded by a 0.9 m thick Tertiary dolerite dyke. Heating by the igneous body caused the concentrations of all 13β(H),14α(H) and 13α(H),14α(H) tricyclic terpanes to increase towards or within the effective ‘oil window’, recording generation from abundant non-hydrocarbon precursors, such as kerogen- and asphaltene-bound components. Progressive changes in tricyclic terpane composition accompany these concentration changes. An increase in the C₂₃ βα/αα maturity parameter towards the dyke resulted from the relatively greater rate of generation of the βα isomer, combined with the earlier decline in concentration (by degradation or isomerisation) of the αα component. The tricyclics/(tricyclics+hopanes) parameter shows a dramatic increase within the latter part of the oil window, due to the greater relative thermal stability of the tricyclic terpanes. The quantitative data demonstrate the importance of the processes of generation (from non-hydrocarbon fractions of the sedimentary organic matter) and thermal degradation in the operation of tricyclic terpane maturity parameters.     

Prediction of source rock characteristics based on terpane biomarkers in crude oils: A multivariate statistical approach

The distributions of eight tricyclic and eight pentacyclic terpanes were determined for 216 crude oils located worldwide with subsequent simultaneous RQ-mode factor analysis and stepwise discriminate analysis for the purpose of predicting source rock features or depositional environments. Five categories of source rocks are evident: nearshore marine (i.e., paralic/deltaic); deeper-water marine; lacustrine; phosphaticrich source beds; and Ordovician age source rocks. The first two factors of the RQ-mode factor analysis describe 45 percent of the variation in the data set; the tricyclic terpanes appear to be twice as significant as pentacyclic terpanes in determining the variation among samples. Lacustrine oils are characterized by greater relative abundances of C₂₁ diterpane and gammacerane; nearshore marine sources by C₁₉ and C₂₀ diterpanes and oleanane; deeper-water marine facies by C₂₄ and C₂₅ tricyclic and C₃₁ plus C₃₂ extended hopanes; and Ordovician age oils by C₂₇ and C₂₉ pentacyclic terpanes. Although thermal maturity trends can be observed in factor space, the trends do not necessarily obscure the source rock interpretations. Also, since bacterial degradation of crude oils rarely affects tricyclic terpanes, biodegraded oils can be used in predicting source rock features. The precision to which source rock depositional environments are determined might be increased with the addition of other biomarker (e.g., steranes) and stable isotope data using multivariate statistical techniques.     

Geochemical characteristics of aromatic hydrocarbons in saline lacustrine crude oils and their significance as exemplified by the south area of western Qaidam Basin

Based on quantitative GC-MS analysis of 40 crude oil samples collected from the south area of western Qaidam Basin,one of the largest saline lacustrine basins in China,the geochemical characteristics of aromatic hydrocarbons in oils were studied systematically in this paper.Among those constitutes,naphthalene(43% 59%),phenanthrene(12% 21%) and taromatic-sterane series(6% 28%) were the main ones of aromatic hydrocarbons.The ratio of aromatic hydrocarbon maturity parameter vs.saturated hydrocarbon maturity parameter C 29 20S/(20S+20R) shows that some aromatic hydrocarbon maturity parameters are not suitable for low-mature oils,including MPI,MNR,DNR,etc.Meanwhile,maturity parameters for dibenzothiophene and taromatic-sterane series are more appropriate for low maturity saline lacustrine crude oils.Based on the ratio of 4,6-DMDBT/1,4-DMDBT,the R c values are within the range of 0.59% 0.72%.However,the abundance of dibenzothiophene(DBT) is low,and the dibenzofuran(DBF) content is even lower,suggesting that the crude oils were formed in a saline lacustrine anaerobic environment.The high abundance of C 26 triaromatic steroid also indicates that the source material is brackish water-saline water with strong reducibility.     

Use of biomarker distributions and compound specific isotopes of carbon and hydrogen to delineate hydrocarbon characteristics in the East Sirte Basin (Libya)

Biomarker ratios, together with stable carbon (δ¹³C) and hydrogen (δD) isotopic compositions of individual hydrocarbons have been determined in a suite of crude oils (n = 24) from the East Sirte Basin to delineate their sources and respective thermal maturity. The crude oil samples are divided into two main families (A and B) based on differences in source inputs and thermal maturity. Using source specific parameters including pristane/phytane (Pr/Ph), hopane/sterane, dibenzothiophene/phenanthrene (DBT/P), Pr/n-C₁₇ and Ph/n-C_l8 ratios and the distributions of tricyclic and tetracyclic terpanes, family B oils are ascribed a marine source rock deposited under sub-oxic conditions, while family A oils have a more terrigenous source affinity. This genetic classification is supported by the stable carbon isotopic compositions (δ¹³C) of the n-alkanes. Using biomarker maturity parameters such as the abundance of Pr and Ph relative to n-alkanes and the distribution of sterane and hopane isomers, family A oils are shown to be more thermally mature than family B oils. The contrasting maturity of the two families is supported by differences between the stable hydrogen isotopic compositions (δD) of Pr and Ph and the n-alkanes, as well as the δ¹³C values of n-alkanes in their respective oils.     

Determination of thermal maturity and organic matter type by principal components analysis of the distributions of polycyclic aromatic compounds

The thermal maturity and organofacies sensitivity of polycyclic aromatic compound (PAC) distributions was explored by examination of the aromatic fractions of solvent extracts from a diverse set of 53 shales, coals and kerogen macerals which have undergone either natural or artificial maturation and which represent all three principal sedimentary organic matter (OM) types. Systematic changes with maturation were observed in the following groups of isomers: tri- and tetramethylnaphthalenes, methyl- and dimethylphenanthrenes, methyl- and dimethyldibenzothiophenes, methylpyrenes, and methylchrysenes. The maturity differences were quantified by mathematical ratios of the relative concentrations of the more thermally stable isomers to the less stable, on the basis of theoretical considerations and empirical observations. The PAC maturity parameters, unlike those derived from saturated biomarker stereoisomers, are typically effective across the entire oil generation window. To compensate for the effects of OM type on the maturity parameters, they were combined using principal components analysis. The resulting first principal component was in good agreement with independent indicators of maturity. The relative distributions of C₀–C₃ alkylphenanthrenes, dibenzothiophene, methyldibenzothiophenes and methyldibenzofurans were evaluated by a separate principal components analysis. The results permitted an independent grouping of the samples by OM type and suggested additional, simple molecular ratios that allow graphical recognition of OM type, including the ratio of dibenzothiophenes to dibenzofurans and a ratio using C₂-alkylphenanthrene isomers.     

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.     

Organic geochemistry of the oils from the southern geological Province of Cuba

The aliphatic hydrocarbon composition (acyclic isoprenoids, hopanoids and steroids) of oils from the most productive fields in the southern geological Province of Cuba have been studied. This province is defined by its position with respect to the Cretaceous overthrust belt generated during the formation of oceanic crust along the axis of the proto-Caribbean Basin. The relative abundances of 18α(H)-22,29,30-trisnorneohopane, gammacerane and diasteranes suggest that Pina oils are related to the carbonate oils from the Placetas Unit in the northern province (low T_s/(T_s+T_m) and C_27,29 rr/(rr+sd) ratios). The Cristales and Jatibonico oils exhibit some differentiating features such as higher T_s/(T_s+T_m) and absence of gammacerane. The oils from this province do not exhibit significant differences in either hopane, C₃₂ 22S/(S+R) and C₃₀ αβ/(αβ+βα), or sterane, C₂₉ αα 20S/(S+R), maturity ratios. However, the relative content of 5α(H),14β(H),17β(H)-cholestanes (C₂₉ ββ/(ββ+αα) ratio) indicates that Pina oils are more mature than Cristales and Jatibonico oils. Several of these oils (Cristales, Jatibonico and Pina 26) are heavily biodegraded, lacking n-alkanes, norpristane, pristane and phytane (the two former oils do not contain acyclic isoprenoid hydrocarbons). Other biodegradation products, the 25-norhopanes, are found in all the oils. Their occurrence is probably due to mixing of severely biodegraded oil residues with undegraded crude oils during accumulation in the reservoir.     

Oil geochemistry derived from the Qinjiatun–Qikeshu oilfields: insight from light hydrocarbons

A suite of 27 oils from the Qinjiatun–Qikeshu oilfields in the Lishu Fault Depression of the Songliao Basin was analyzed using whole oil gas chromatography. In combination with the relative distribution of C₂₇, C₂₈, and C₂₉ regular steranes, detailed geochemical analyses of light hydrocarbons in oil samples revealed crude oils characterized by the dual input of lower aquatic organisms and higher terrestrial plants. Several light hydrocarbon indicators suggest that the liquid hydrocarbons have maturities equivalent to vitrinite reflectances of around 0.78%–0.93%. This is consistent with the maturity determination of steranes C₂₉ 20S/(20S + 20R) and C₂₉ ααβ/(ααα + αββ). Crude oils derived from the two distinct oilfields likely both have source rocks deposited in a lacustrine environment based on light hydrocarbon parameters and on higher molecular weight hydrocarbon parameters. The results show that light hydrocarbon data in crude oils can provide important information for understanding the geochemical characteristics of the Qinjiatun–Qikeshu oils during geologic evolution.     

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.     

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.     

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.