Angiosperm-derived Triterpenoids Research Articles

Petrological and geochemical characteristics of xylites and associated lipids from the First Lusatian lignite seam (Konin Basin, Poland): Implications for floral sources, decomposition and environmental conditions

Single pieces of fossil wood fragments (xylites) were collected from the middle Miocene First Lusatian lignite seam at the Adamów, Jóźwin IIB and Tomisławice opencast mines and are characterized by maceral variety, cellulose contents and their molecular and isotopic composition. Biomarker composition of xylites and δ13C of their total organic matter, lipids and cellulose are used to provide insights into woody plant community and the effects of wood decomposition.The investigated xylites represent fragments of fossil wood from conifers, most likely species of Cupressaceae, indicated by terpenoid biomarkers characteristic for conifers and by the δ13C values of the extracted cellulose. This conclusion is confirmed by paleobotanical data highlighting Taxodium and Nyssa as the main elements of the wet forest swamps. Due to the wet swamp habitat and the higher-decay resistance exclusively wood fragments of conifers are found in the lignite seam. Minor abundances of angiosperm-derived triterpenoids in the xylites are explained by impurities from inherent detritic lignite.The xylites are characterized by minor to moderate extents of gelification, but elevated to high cellulose decomposition. The relationship between δ13C values of xylites and their cellulose contents reflects wood decomposition removing preferentially the 13C-enriched compounds, but decomposition did not affect the δ13C of cellulose. Despite of similar δ13C of xylites and detritic lignite, differences in isotopic composition of hopanoids argue for slightly different microbial communities involved in the decomposition of the respective OM. Thus, we conclude that wood decomposition proceeded in a freshwater environment under acidic conditions by fungi and bacteria.Variations in water availability during growth periods of the conifers are suggested as the most probable cause for the observed minor variations in isotopic composition of plant lipids. The positive relationship found between δ2H and δ13C of plant biomarkers, and cellulose of xylites can be explained by the ability of vascular plants to minimize evapotranspiration during dryer phases resulting in plant OM enriched in 13C and 2H. The significant differences in δ2H between diterpenoids of different structural types and n-alkanes are most likely caused by differences in isotopic fractionation during lipid biosynthesis.

A long-term, high-latitude record of Eocene hydrological change in the Greenland region

A range of proxy approaches have been used to reconstruct short-term changes to Earth's hydrological cycle during the early Eocene hyperthermals. However, little is known about the response of Earth's hydrological and biogeochemical systems to long-term Cenozoic cooling, which began following the Early Eocene Climatic Optimum (53.3 – 49.4 million years ago; Ma). Here, we use the molecular distribution and isotopic composition of terrestrial biomarkers preserved in marine sediments of ODP Site 913, East Greenland, to develop a long-term record of high-latitude hydrological change between 50 and 34 Ma. There is a marked decline in the concentration of conifer-derived diterpenoids and angiosperm-derived triterpenoids during the Eocene. As the input of wind-blown conifer pollen remains stable during this interval, this implies that decreasing di- and triterpenoid concentrations reflect declining influence of fluvial inputs – and perhaps terrestrial runoff – throughout the Eocene. Branched GDGTs and bacterial-derived hopanes indicate an increased input of soil- and kerogen-derived organic matter, respectively, after 38 Ma. This coincides with evidence for ice rafted debris and suggests input of organic matter via glacial processes. This also implies some continental glaciation occurred on East Greenland in the middle-to-late Eocene. Leaf wax hydrogen isotopes extending throughout this section – the first such long-term record from the Paleogene - indicate that precipitation δ2H was persistently higher than that of modern coastal Greenland, consistent with warmer ocean source waters and enhanced poleward moisture transport. Non-intuitively, however, this effect appears to have been smallest during the warmest part of the record, and higher δ2H values occur in the middle Eocene. Although interpretation of these hydrogen isotope trends is unclear, they clearly indicate – alongside the changes in biomarker abundances – a perturbed hydrological cycle through the Eocene in coastal Greenland. More long-term records are required to ascertain if this represents regional or global hydrological reorganisation.

Composition of lipids from the First Lusatian lignite seam of the Konin Basin (Poland): Relationships with vegetation, climate and carbon cycling during the mid-Miocene Climatic Optimum

Samples of detrital lignite have been collected for detailed organic geochemical and carbon isotope analyses from the First Lusatian lignite seam at the Adamów, Jóźwin IIB and Tomisławice opencast mines, deposited after the last peak of the Mid-Miocene Climatic Optimum. Carbon isotopic compositions of biomarkers from Polish lignite are reported for the first time. The aim of the study is to improve the chemotaxonomic value of biomarkers by relating the results to existing paleobotanical data, and to gain information about the influencing factors on δ13C of lignite and lipids. Furthermore, biomarker and isotopic proxies are tested for their applicability in paleoclimate studies.The molecular composition of the extracted lipids is highly variable, including leaf-wax n-alkanes in the C23 to C31 range, diterpenoids, hopanoids, and angiosperm-derived triterpenoids, as well as saturated fatty acids, long-chain n-alkanols and n-alkan-2-ones. The relative abundances of mid-chain (C23, C25) n-alkanes and their 1–2‰ higher δ13C values compared to long-chain n-alkanes (C29, C31) argue for a minor contribution of macrophytes (graminoids, etc.) to peat formation, enhanced during periods of raised water level. The presence of ferruginol and dehydroferruginol testifies the contribution of Taxodiaceae. The abundances of pimarane-type diterpenoids and the presence of non-aromatic abietane-derivatives argue for the contribution of Pinaceae. Based on the presence of lupeol and lupane-type triterpenoids, an input of Betulaceae can be concluded. The contribution of further angiosperms cannot be specified based on the composition of pentacyclic triterpenoids. However, the results indicate mixed vegetation, and are in agreement with paleobotanical data highlighting abundant conifers of the Taxodiaceae/Cupressaceae and Pinaceae families, as well as angiosperms of various families (e.g., Nyssa, Quercus, Fagus), including Betulaceae (e.g., Alnus, Betula, Corylus). Based on the relationship between the carbon preference index of n-alkanes and mean annual air temperatures, obtained from a global database of peatlands, an average temperature of 24.5 °C is obtained. This value is significantly higher as estimated from paleobotanical data (15.7–19.7 °C), probably due to the influence of changes in vegetation on carbon preference index.The relative abundances of diterpenoids versus di- plus angiosperm-derived triterpenoids in detrital lignite samples revealed variable contributions of gymnosperms and angiosperms during the middle Miocene. Consistent with these results, a positive relationship exists between the di-/(di- + tri-) terpenoid biomarker ratios and δ13C of lignite samples, indicating the dominating role of varying gymnosperm/angiosperm contributions on the carbon isotopic composition of lignite. The C-isotope data of long-chain n-alkanes, diterpenoids, and angiosperm-derived triterpenoids co-vary within the profiles, arguing for an overall control of changes in δ13C of atmospheric CO2 on δ13C of plant lipids. Fluctuations in δ13C of individual compounds may also be related to changes in carbon cycling within the peat, humidity and air temperature. The influence of local variations in ambient CO2 (e.g., the canopy effect) cannot be excluded.

Preservation of hopenol-B in Eocene dammar resins: Insights into the evolution of biochemical synthesis of angiosperm metabolites

Plants synthesize various types of triterpenoids as secondary metabolites to achieve greater fitness with respect to their surrounding environment. In last few decades, interest in biochemical synthesis and regulation of plant triterpenoids has been increased due to their scientific and economic significance. However, until now evolution of such triterpenoid synthesis over geological time is not clearly understood. In order to better understand the biosynthesis of triterpenoid in deep time, the present study reports hopenol-B (hop-22[29]-en-3β-ol), a plant secondary metabolite from fossil dammar resin of Eocene time, derived from Dipterocarpaceae family. The studied fossil resins were obtained from two lignite-bearing sequences of early and middle Eocene age from the Cambay and Kutch Basin, western India, respectively. This bioactive metabolite is recorded from several modern angiosperm trees. Hopenol-B is synthesized by the enzyme (oxidosqalene cyclase containing hopanoid skeleton)-mediated cyclization of 2,3-oxidosqualene by which other angiosperm-derived triterpenoids are also formed. In contrast, hopanoid class triterpenoids of bacterial and non-vascular plants origin are formed by the cyclization of squalene, catalyzed by squalene-hopene cyclases (SHCs). The present study provides the earliest signature of hopenol-B found so far and its occurrence in the analyzed samples suggests that the biosynthetic pathway of this compound in angiosperms had already been evolved during the early Eocene.

Evaluation of paleoenvironment using terpenoid biomarkers in lignites and plant fossil from the Miocene Tokiguchi Porcelain Clay Formation at the Onada mine, Tajimi, central Japan

We investigated terpenoid biomarkers in muds from lignite seams, clays from porcelain clay beds that slightly contain lignite, and from a conifer cone macrofossil from the Miocene Tokiguchi Porcelain Clay Formation of the Tokai Group in central Japan, as well as extant cones. The n-alkanes, n-alkanols (suberin origin), diterpenoids (conifer origin), hopanoids (bacteria origin) and steroids were mainly present in the lignite-containing muds and clays. On the other hand, the diterpenoids, triterpenoids (angiosperm origin), hopanoids and steroids were detected as major component in the conifer cone macrofossil. In addition, the diterpenoids were mainly detected in the extant conifer cones. The low hopane isomer ratios and the detection of biosterols are confirmed to be immature in the lignite, sediment and macrofossil in the formation. The stanol/sterol ratio values of the lignite-containing muds and clays are much higher than that of the macrofossil. The higher ratios in lignite-containing muds and clays are possibly attributed to enhanced microbial reduction of organic matter under reduced condition in the swampy environments. A large amount of angiosperm-derived triterpenoids detected in the conifer cone macrofossil are considered as contaminants in the sample from sedimentary organic particles originated from detrital waxes of angiosperms. Such contamination might occur by migration of organic compounds within sediment after deposition. The angiosperm-derived polar terpenoids may be hardly affected by contamination by migration of organic matter from the adjacent sediments because these are less abundant in the conifer macrofossil. Thus, it is suggested that the polar terpenoid biomarkers are more reliable as paleochemotaxonomic and paleovegetation indicators.

Aliphatic and aromatic terpenoid biomarkers in Cretaceous and Paleogene angiosperm fossils from Japan

The distributions of aliphatic and aromatic terpenoids in Cretaceous and Paleogene angiosperm fossils from Japan were investigated. Aliphatic A ring-degraded oleanane, ursane and lupane were found in all samples. In addition, aliphatic gymnosperm-derived diterpenoids were detected in significant quantities. Aromatic oleanane-type triterpenoids were the major components, with ursane- and lupane-type triterpenoids being minor compounds in all angiosperm fossils. In a Cretaceous gymnosperm fossil, major components included aliphatic labdane-, isopimarane- and abietane-type diterpenoids, aromatic abietane-type diterpenoids, and chrysene- and picene-type polyaromatic hydrocarbons (PAHs). Trace amounts of oleanane-, ursane- and lupane-type triterpenoids were also identified. It is likely that the aromatic triterpenoids were introduced to the gymnosperm fossil from the angiosperm-derived material in the sediments. We defined an angiosperm/gymnosperm index (al-AGI′) as an alternative to the aliphatic triterpenoid/diterpenoid ratio proposed in the literature. The al-AGI′ index may underestimate the angiosperm contribution, because the aliphatic angiosperm-derived triterpenoids are more readily converted to aromatic counterparts than the diterpenoids during diagenesis. An aromatic angiosperm/gymnosperm index (ar-AGI) can be calculated using aromatic diterpenoids and triterpenoids. We suggest that ar-AGI is best calculated using only the oleanane-, ursane- and lupane-type aromatic triterpenoids, and that the chrysene- and picene-type PAHs be excluded.

The middle Eocene Márkushegy subbituminous coal (Hungary): Paleoenvironmental implications from petrographical and geochemical studies

Samples from two coal seams of the Márkushegy underground mine (Hungary) were investigated for variations in maceral composition, petrography-based facies indicators and various geochemical parameters, using three seam profiles. Both seams originate from a topogenous mire and evolved within a peneplaned coastal area covered with eutrophic swamps. The presence of foraminifera and marine algae in the marly layers is indicative of marine ingressions. Coal facies characterisation from these parameters is combined with the results from biomarker analyses of soluble organic matter in order to reconstruct the depositional environment and to relate petrography-based indicators to the molecular composition. The contents of macerals of the liptinite group are positively correlated with soluble organic matter (SOM) yields and Hydrogen Index (HI). Consistent with maceral composition and high HI values, enhanced proportions of n-alkanes of intermediate molecular weight (n-C21–25), which are predominantly found in macrophytes, are obtained from samples of the marly shales. The final drowning of the mire is reflected by decreasing pristane/phytane ratios, due to the rise of the (ground)water table and the establishment of anaerobic conditions. The observed positive correlation between pristane/phytane ratios and inertinite percentages suggests that, at least in the Márkushegy deposit, both parameters reflect variations in redox conditions of the mire. The predominance of angiosperms in the peat-forming vegetation of the Márkushegy coal is evidenced by the high relative proportions of angiosperm-derived triterpenoids. The influence of the relative proportion of fossil wood on tissue preservation (TPI) is indicated by the positive relationship of the concentration of land plant-derived terpenoid hydrocarbons and TPI. The degree of gelification of plant tissue (GI) is governed by the microbial activity in the mire, as indicated by a negative relationship between GI and the steroids/hopanoids concentration ratios. The variation of the δ13C values of coal is obviously governed by the relative contribution of plant lipids to the biomass. The obtained negative relationship between δ13C of the coal and GI is explained by the effect of cellulose decomposition and microbial activity on the isotopic composition of the organic matter.

Organic geochemistry of the Lower Miocene Oberdorf lignite (Styrian Basin, Austria): its relation to petrography, palynology and the palaeoenvironment

In the Oberdorf trough at the northwestern margin of the Styrian Basin (Austria), an up to 36-m thick Lower Miocene (Ottnangian) lignite seam occurs within the fluvial Köflach–Voitsberg Formation. Previous results indicate that the lignite originated in a topogenous mire within a wet-forest swamp palaeoenvironment. Differences in soluble organic matter (SOM) yield of borehole samples from the lignite seam are related to free lipids present in plant waxes or resins and the presence of thermally labile polymers indicated by the contents of liptinite macerals (i.e., resinite, suberinite, and liptodetrinite). The n-alkane distribution patterns are dominated by high-molecular weight lipids with marked odd over even predominance, originating from plant waxes. A contribution of algae to the even numbered short-chain lipids, observed in considerable amounts in the footwall sediments is proposed. Terpenoid biomarkers characteristic for conifers and angiosperms were detected, consistent with palynomorphic spectra which are dominated by forest swamp pollen (Taxodiaceae–Cupressaceae) and pollen from plants living in a mixed mesophytic forest. Excellent relationships between higher plant biomarker composition and palynologic data indicate that the organic geochemical results reflect the varying inputs of coniferales vs. angiosperms. The data further imply that cuparene may be used for taxonomical differentiation of coniferales families. Organic geochemical data provide evidence that the content of land plant-derived biomarkers is controlled by the input of resin-rich conifers. Concentrations of hopanoids, dominated by hop-17(21)-ene, generally increase towards the top of the lignite, a section characterised by high extents of aromatisation of triterpenoid biomarkers. The results suggest that the aromatisation of angiosperm-derived biomarkers may be governed by the activity of anaerobic rather than by aerobic bacteria. However, changes in the depositional environment and palynologic facies during peat formation probably influenced the origin and fate of angiosperm-derived triterpenoids. The results indicate how biomarker composition may contribute to the evaluation of environmental changes. Cross-correlations of organic geochemical parameters with palynological data and petrography-based facies indicators will provide further insights in the peat-forming vegetation and biogeochemical activities in the mire.

Aliphatic and aromatic triterpenoid hydrocarbons in a Tertiary angiospermous lignite

The hydrocarbon biomarker assemlage of a liptinite-rich, early Tertiary angiospermous lignite has been characterized. The biomarker fistribution for the lignite confirms the low maturity and previous paleobotanic interpretations. The aliphatic hydrocarbon fraction consists predominantly of n-alkanes showing a strong odd-carbon predominance, and numerous de-A-triterpenoids and triterpenoids derived from higher plants. Bacterially-derived triterpenoids were represented primarily by homohopanes and hopenes. The aromatic hydrocarbon fraction contains a series of mono-, di-, and triaromatic de-A-triterpenoids and mono-, tri-, and tetraaromatic triterpenoids derived from higher plants. The concentration and abundance of monoaromatic triterpenoids containing one to three additonal degress of unsaturation have not seen previously observed in a single deposit. As such, a diagenetic scheme for angiosperm-derived triterpenoids is presented which confirms and extends previous hypothesis.