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.     

Steranes and terpanes in kerogen pyrolysis for correlation of oils and source rocks

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 $\text{5α}\text{5β}$-sterane ratios, jointly with $\text{17α(H)-hopane}\text{17β(H)-moretane}$ ratios, tricyclic terpane concentrations and $\text{17α(H)}\text{17β(H)}$-trisnorhopane ratios, allow the differentiation of kerogens from adjacent stratigraphies.     

Distribution Characteristics of Alkylcyclohexanes in Lower Paleozoic Strata on the Northern Margin of the Tarim Basin,China

Organic matter from the Lower Paleozoic strata on the northern margin of the Tarim Basin of China contains abundant alkylcyclohexanes.The n-alkylcyclohexanes show the even(C16-C20) and odd (C17-C21) carbon number predominance and smooth distribution,and the methyl-n-alkylcycolhexanes the odd carbon number predominance(C17-C21) and smooth distribution,which may be related to their depositional environments and organic precursors.There are some differences in carbon number distribution between the two series of monocyclic alkanes and the n-alkanes marked by smooth distribution.The genetic relationship between the three series of compounds needs to be further studied.     

Tri- and tetraterpenoid hydrocarbons in the Messel oil shale

The high molecular weight constituents of the branched and cyclic hydrocarbon fraction of the Messel oil shale (Eocene) have been examined by high resolution gas chromatography and combined gas chromatography-mass spectrometry. The following compounds are present: perhydrolycopene (1; lycopane), together with one or more unsaturated analogues with the same skeleton; a series of 4-methylsteranes (2c) in higher abundance than their 4-desmethyl analogues; two series of pentacyclic triterpanes, one series (C₂₇-C₃₂) based on the hopane structure (3a-e), and the other (C₂₇-C₃₁) based on the 17α-H hopane structure (3a-d, 17αH); and an intact triterpene hop-17 (21)-ene [3c, Δ 17(21)]. Only two additional triterpanes were detected in minor concentrations, viz. 30-normoretane (3b, 21αH) and a C₃₁ triterpane based on the hopane/lupane-type skeleton. The presence of these compounds suggests a significant microbial contribution to the forming sediment. Comparison of the tri- and tetraterpenoid hydrocarbons with those of the Green River Shale indicates differences in the organisms contributing to the two sediments.     

Isoprenoids in a Costa Rican seep oil

The isoprenoid alkanes present in a seep oil from Costa Rica have been examined using gas chromatography and mass spectrometry. In addition to the predominance of the C₁₆ and C₁₈-C₂₀ regular isoprenoid alkanes, the C₂₁ and C₂₃-C₂₅ regular isoprenoid alkanes were identified. The C₂₆, C₂₈ and C₃₀ regular isoprenoid alkanes were tentatively identified. No evidence for the regular C₁₇, C₂₂ or C₂₇ isoprenoid alkanes was found. The compounds 3,7,11- trimethyltetradecane and 3,7,11-trimethylhexadecane were tentatively identified. It is suggested that a higher regular isoprenoid structure (or structures) is required in addition to phytol to account for the distribution of isoprenoid alkanes.     

Oil-generating coals of the San Juan Basin, New Mexico and Colorado, U.S.A.

Coal beds of the Upper Cretaceous Fruitland Formation in the San Juan Basin of northwestern New Mexico and southwestern Colorado have significant liquid hydrocarbon generation potential as indicated by typical Rock-Eval Hydrogen Indexes in the range of 200–400 mg hydrocarbon/g organic carbon (type II and III organic matter). Small, non-commercial quantities of oil have been produced from the coal beds at several locations. The oils are characterized by high pristane/phytane (ca 4) and pristane/n-C₁₇ ratios (ca 1.2), abundant C₂₁₊ alkanes in the C₁₀₊ fraction with a slight predominance of odd carbon-numbered n-alkanes, abundant branched-chain alkanes in the C₁₅₊ region, and a predominance of methylcyclohexane in the C₄----C₁₀ fraction. The oils are indigenous to the Fruitland Formation coals and probably migrated at thermal maturities corresponding to vitrinite reflectance values in the range 0.7–0.8%. Although the oils found to date are not present in commercial amounts, these findings illustrate the potential of some coals to generate and expel oil under conditions of moderate thermal heating.     

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.     

Structure proof and significance of stereoisomeric 28,30-bisnorhopanes in petroleum and petroleum source rocks

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 $\text{D}\text{E}$cis 25,28,30-trisnorhopane has an application to maturation assessment in heavily biodegraded oils.     

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.     

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。     

Anthropogenic pollution and oxygen depletion in the lower Yangtze River as revealed by sedimentary biomarkers

The Yangtze River receives 37.5% of the municipal sewage of China, whose fate constitutes a major environmental and health concern. This study applied phytosterols, 5β(H)-stanols, tetrahymanol and 17α,21β(H)-C₃₀-hopane to examine sewage and petroleum-derived organic pollutants, and assess their impact on the biogeochemistry of the lower river benthic environment. The results showed that significant contributions from sewage and petroleum pollutants were preserved in the riverbed. These potentially contributed to O₂ depletion and apparently an anoxic environment in the riverbed, either directly or via an impact on primary productivity.     

n-alkane distribution coupled with organic carbon isotope composition in the shell bar section, Qarhan paleolake, Qaidam basin, NE Tibetan Plateau

Lipids extracted from lacustrine deposits in the paleolake Qarhan of the Qaidam basin in the northeastern Tibetan Plateau were determined by conventional gas chromatography-mass spectrometry. Several series of biomarkers were identified, mainly including n-alkanes, n-alkan-2-ones, n-alkanoic acids, branched alkanes, triterpenoids and steroids, indicative of various biogenic contributions. On the basis of cluster analysis, the n-C₁₅, n-C₁₇, n-C₁₉ alkanes were proposed to be derived from algae and/or photosynthetic bacteria, the n-C₂₁, n-C₂₃, n-C₂₅ homologues from aquatic plants, and the n-C₂₉, n-C₃₁ homologues from vascular plants. In contrast, the n-C₂₇ alkane is not categorized in the n-C₂₉ and n-C₃₁ group of alkanes, probably due to more complex origins including both aquatic and vascular plants, and/or differential biodegradation. Stratigraphically, layers-2, 4 and 5 were found to show a close relationship in n-alkane distribution, associated with a positive shift in carbon isotope composition of bulk organic matter (δ¹³C_org), inferring a cold/dry period. Layers-1 and 6 were clustered together in association with a negative δ¹³C_org, excursion, probably indicating a relatively warm/humid climate. The potential coupling between the n-alkane distributions and δ¹³C_org, suggests a consequence of vegetation change in response to climate change, with the late MIS3 being shown to be unstable, thought to be the climatic optimum in the Tibetan Plateau. Our results suggest that the cluster analysis used in this study probably provides an effective and authentic method to investigate the n-alkane distribution in paleolake sediments.     

Chemical and carbon isotopic evolution of hydrocarbons during prograde metamorphism from 100°C to 550°C: Case study in the Liassic black shale formation of Central Swiss Alps

Hydrocarbon distributions and stable isotope ratios of carbonates (δ¹³C_car, δ¹⁸O_car), kerogen (δ¹³C_ker), extractable organic matter (δ¹³C_EOM) and individual hydrocarbons of Liassic black shale samples from a prograde metamorphic sequence in the Swiss Alps were used to identify the major organic reactions with increasing metamorphic grade. The studied samples range from the diagenetic zone (<100°C) to amphibolite facies (∼550°C). The samples within the diagenetic zones (<100 and 150°C) are characterized by the dominance of C_<20n-alkanes, suggesting an origin related with marine and/or bacterial inputs. The metamorphic samples (200 to 550°C) have distributions significantly dominated by C₁₂ and C₁₃n-alkanes, C₁₄, C₁₆ and C₁₈n-alkylcyclopentanes and to a lesser extend C₁₅, C₁₇ and C₂₁n-alkylcyclohexanes. The progressive ¹³C-enrichment (up to 3.9‰) with metamorphism of the C_>17n-alkanes suggests the occurrence of cracking reactions of high molecular weight compounds. The isotopically heavier (up to 5.6‰) C_<17n-alkanes in metamorphic samples are likely originated by thermal degradation of long-chain homologous with preferential release of isotopically light C₁ and C₂ radicals. The dominance of specific even C-number n-alkylcyclopentanes suggests an origin related to direct cyclization mechanism (without decarboxylation step) of algal or bacterial fatty acids occurring in reducing aqueous metamorphic fluid conditions. The regular increase of the concentrations of n-alkylcycloalkanes vs. C_>13n-alkanes with metamorphism suggests progressive thermal release of kerogen-linked fatty acid precursors and degradation of n-alkanes. Changes of the steroid and terpenoid distributions are clearly related to increasing metamorphic temperatures. The absence of 18α(H)-22,29,30-trisnorneohopane (Ts), the occurrence of 17β(H)-trisnorhopane, 17β(H), 21α(H)-hopanes in the C₂₉ to C₃₁ range and 5α(H),14α(H),17α(H)-20R C₂₇, C₂₉ steranes in the low diagenetic samples (<100°C) are characteristic of immature bitumens. The higher thermal stress within the upper diagenetic zone (150°C) is marked by the presence of Ts, the disappearance of 17β(H)-trisnorhopane and thermodynamic equilibrium of the 22S/(22S + 22R) homohopane ratios. The increase of the ααα-sterane 20S/(20S + 20R) and 20R ββ/(ββ + αα) ratios (from 0.0 to 0.55 and from 0.0 to 0.40, respectively) in the upper diagenetic zone indicates the occurrence of isomerization reactions already at <150°C. However, the isomerization at C-20 (R → S) reaches thermodynamic equilibrium values already at the upper diagenesis (∼150°C) whereas the epimerisation at C-14 and C-17 (αα → ββ) arrives to constant values in the lower anchizone (∼200°C). The ratios Ts vs. 17α(H)-22,29,30-trisnorneohopane [(Ts/(Ts + Tm)] and 18α(H)-30-norneohopane (C₂₉Ts) vs. 17α(H),21β(H)-30-norhopane [C₂₉Ts/(C₂₉Ts + C₂₉)] increase until the medium anchizone (200 to 250°C) from 0.0 to 0.96 and from 0.0 to 0.44, respectively. An opposite trend towards lower values is observed in the higher metamorphic samples.The occurrence of specific hydrocarbons (e.g., n-alkylcyclopentanes, cadalene, hydrogenated aromatic compounds) in metamorphic samples points to kerogen degradation reactions most probably occurring in the presence of water and under reducing conditions. The changes of hydrocarbon distributions and carbon isotopic compositions of n-alkanes related to metamorphism suggest that the organic geochemistry may help to evaluate the lowest grades of prograde metamorphism.     

Iron porphyrins in coal from the United States

Iron porphyrins have been isolated from seven U.S. humic coals of various geological ages. Mass spectrometry shows that for the higher rank coals the porphyrins comprise an homologous series of alkyl derivatives (C₂₇-C₃₂). Mesoheme is detected in a Cretaceous lignite from Montana.     

Bitumen from Coalport tar tunnel

The Coalport (Shropshire, U.K.) Tar Tunnel bitumen has been known since 1787 and the first geochemical data are reported here. The bitumen was analyzed for molecular markers useful for correlational studies. Gas chromatographic analysis of aliphatic and aromatic hydrocarbons failed to detect any specific major components normally used for genetic correlational and maturational studies. A search for minor and trace components by gas chromatographic-mass fragmentographic analysis showed the presence of triterpenoid hydrocarbons primarily of the 17α (H)-hopane series (C₂₇ to C₃₅, ex. C₂₈) and a C₂₆ to C₃₁ series of ring A/B demethylated hopanes. Two homologous sterane series (C₂₇ to C₂₉) of the 5α, 14β, 17β (H)-sterane and 13β, 17α (H)-diasterane type were also detected. Pophyrins of the DPEP and etio series (C₂₇ to C₄₁, DPEP/etio > 1) were also found. Characterization of their alkyl substitution pattern demonstrated C₁, C₂ and C₃ substituents on the pyrole moieties of the parent petroporphyrins.The molecular markers detected in this bitumen indicate its biogenic origin and show evidence of diagenetic and geothermal maturation processes. The overall geochemical characteristics of the Coalport Tar Tunnel bitumen suggest that it corresponds to a well matured crude oil, which was heavily altered by in-reservoir biodegradation or close to surface exposure.     

Applications of steranes,terpanes and monoaromatics to the maturation,migration and source of crude oils

Novel biological marker parameters are applied to problems of geochemical correlation of crude oils in the McKittrick Field, California. An attempt is described to distinguish four diagenetic parameters; namely, source input, source maturation, migration and ‘in reservoir’ maturation. The tools include the absolute concentration of steranes, terpanes and paraffins (_{n + iso}) in combination with internal ratios of individual biomarkers such as primary/secondary terpanes, 17α(H)-trisnorhopane/18α(H)-trisnorhopane II (both maturation specific), 5β/5α-steranes, 5β-steranes/17α(H)-hopanes and rearranged steranes/5α-steranes (all migration oriented), 5α/5α-steranes and a number of terpane ratios of partially unknown chemical structure (source input specific).Among other new correlation parameters are: two series of mass chromatograms (m/e 253 and 239), signaling monoaromatized steranes, a series of presumably rearranged steranes (m/e 259), and a series of methylhopanes (m/e 205).The results obtained on the molecular level exceed the degree of information obtainable from organic geochemical ‘bulk’ parameters such as yields of saturates, aromatics, sulfur compounds and C¹³/C¹² ratios by far; however, both types of parameters are mutually supporting. All conclusions are consistent with subtle stratigraphie and overall geologic prerequisites.     

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     

In situ anaerobic degradation of petroleum alkanes in marine sediments: preliminary results

The degradation of acyclic petroleum hydrocarbons was studied during a 24-month experiment in Mediterranean coastal sediments (Gulf of Fos). Sediment cores entirely contaminated with oil (Arabian Light Crude Oil) were incubated in situ. The use of conservative tracers of sediment's particles reworking (luminophores) allowed the distinction of the reworked layer from the anoxic deeper sediments. Using the 17α,21βC₃₀ hopane (C₃₀H) as an inert internal reference, we could demonstrate that, after 24 months of experiment, acyclic petroleum hydrocarbons can be degraded under natural anaerobic conditions. The reactivity of individual alkanes appeared to depend on their chemical structure. To cite this article: D. Massias et al., C. R. Geoscience 335 (2003).To cite this article: D. Massias et al., C. R. Geoscience 335 (2003).     

Fatty acid geochemistry of a 200 m sediment core from Lake Biwa,Japan. Early diagenesis and paleoenvironmental information

Fatty acids (FAs), β- and ω-hydroxy acids, α,ω-dicarboxylic acids and n-alkanes were studied in a 200 m sediment core taken from Lake Biwa, Japan. FAs showed bimodal distribution with peaks at C₁₆ and C₂₂-C₂₈. Their distribution patterns clearly changed with depth from lower molecular weight (C₁₂-C₁₉) predominance to higher molecular weight (C₂₀-C₃₂) predominance in the upper 20 m interval. Analyses of related compounds (β- and ω-hydroxy acids and α, ω-dicarboxylic acids) suggest that β- and ω-oxidative degradation of C₁₂-C₁₉ FAs has occurred in the sediments.The ratio of bound C₁₂-C₁₉ to unbound FAs increases with depth in the upper 0–1 m sediments, suggesting that unbound FAs are more labile. However, the ratio varies significantly in deeper sections and may be associated with water temperature.In the sediments deeper than 20 m in depth, C₁₂-C₁₉ FAs gradually decrease. On the other hand, higher molecular weight FAs (HFAs: C₂₀-C₃₂), which were probably derived from terrestrial plants, increase in concentration from 20 m to 100 m, suddenly decrease at 100 m and show progressively lower concentration in deeper sediments. These fluctuations are interpreted in relation to paleolimnological changes of the lake and the drainage basin. ω-Hydroxy C₂₀-C₃₀ acids and C₂₀-C₃₀α, ω-dicarboxylic acids show a distribution pattern similar to HFAs. Branched chain FAs, ω-hydroxy acids and C₉-C₁₉α,ω-dicarboxylic acids show a major peak around 3–15 m in depth. This peak is probably caused by increased bacterial activity in the water column and surface sediments in the past, which may be associated with an increase in primary production of the lake.     

Occurrence of highly abundant bacterial hopanoids in Dajiuhu peatland, central China

Based on gas chromatography and gas chromatography-mass spectrometry analyses, an amazing amount of hopanoids was detected in the peat deposits in the Dajiuhu National Wetland Park in central China. The hopanoids identified included hopanes (C₂₇-C₃₁ αβ, C₂₇-C₃₂ ββ, C₂₉ βα), hopenes (hop-22(29)-ene, 22,29,30-trinorhop-17(21)-ene, hop-17(21)-ene, hop-13(18)-ene, etc.), hopanoic acids (C₃₁-C₃₄ ββ, C₃₂-C₃₃ βα, C₃₂ αβ), hopanols (C₃₂ ββ and αβ) and hopanone (22,29,30-trinorhop-21-one). C₃₁ αβ-22R hopane was found to be the dominant hopanoid, more abundant than individual nalkanes derived from higher plants. These hopanoids, exclusive of some hopenes, are proposed to be primarily from bacteria. The dominant C₃₁ αβ-22R hopane in young sediments, without any thermal maturation, might be formed through microbial epimerization under acidic conditions in the peatland as suggested before, or directly from aerobic bacteria. This finding highlights the importance of microbes in the formation of peatland as well as in the reconstruction of paleoenvironments.