Insights into preservation of fossil plant cuticles using thermally assisted hydrolysis methylation

The chemical composition of Cretaceous leaf remains showing exceptionally well preserved cuticles was investigated using pyrolysis gas chromatography–mass spectrometry (Py-GC–MS) and thermally assisted hydrolysis methylation (THM)-GC–MS. Samples of Coniferales (Frenelopsis) and Ginkgoales (Nehvizdya penalveri) leaf remains were collected from freshwater and coastal marine depositional environments. Material for pyrolysis included (i) untreated leaves and cuticles obtained after extraction from mineral rock matrix and bleaching, (ii) kerogen fraction from both materials, (iii) non-hydrolysable fraction from kerogen. The THM-GC–MS data from untreated leaves and bleached cuticles show that the fossil cuticle geopolymer essentially released aliphatic components upon thermal treatment, with a dominance of fatty acids (FAs) and n-alkanes/n-alkenes. The FAs are essentially resistant to bleaching and remain after solvent extraction. They occur mainly as short chain compounds ranging from C₆ to C₁₆ and with maximum abundance at C₈–C₉. The n-alkanes/n-alkenes from kerogen and the non-hydrolysable residue occur mainly as short chain compounds in the range C₁₀–C₁₆, with the highest abundance at C₉–C₁₂. The THM-GC–MS pyrograms of the fossil cuticles differ from those of cutan from fresh living plants. They support the preservation model via polymerization of monomers derived from cutin or from unsaturated cell FAs.     

Thermal alteration experiments on organic matter from recent marine sediments in relation to petroleum genesis

Three fractions of organic matter: lipid (benzene:methanol-extractable), humic acid (alkali-extractable) and kerogen (residue) were extracted from a young marine sediment (Tanner Basin, offshore southern California) and heated for different times (5–116 hr) and temperatures (150°–410°C). The volatile (gases) and liquid products, as well as residual material, were then analyzed. On a weight basis, the lipid fraction produced 58% of the total identified n-alkanes, the kerogen fraction 41%, and the humic acid <1%. Whereas n-alkanes produced from lipid show a CPI > 1.0, those produced by thermal alteration of kerogen display a CPI < 1.0. The volatiles produced by heating the lipid and humic acid fractions were largely CO₂ and water, whereas those produced from heated kerogen also included methane, hydrogen gas and small amounts of C₂–C₄ hydrocarbons. A mechanism for hydrocarbon production due to the thermal alteration of organic constituents of marine sediment is discussed.     

Kerogen of Toarcian shales of the Paris Basin. A study of its maturation by flash pyrolysis techniques

A set of 14 samples—both extracted and unextracted from the Toarcian of the Paris Basin have been investigated using Curie-point pyrolysis-mass spectrometry and Curie-point pyrolysis gas chromatography mass spectrometry. The relative amount of n-alkenes and n-alkanes in the pyrolyzates increases with increasing maximum burial depth of the samples. Comparison of the pyrolysis data of extracted and unextracted samples shows that generation of hydrocarbons from the kerogen starts at a maximum burial depth of ~ 1000m. The increase of pristane and phytane in the extracts of the deeper samples is correlated with the gradual decrease of the characteristic pyrolysis product prist-1-ene. Three samples yield pyrolyzates with high relative amounts of aromatic compounds. This phenomenon probably reflects a different type of contributing organic matter and/or a different environment of sedimentation.     

Analysis and simulated diagenesis of kerogen in a Recent bottom mud from Mono Lake,California: a comparison with selected ancient kerogens

The insoluble organic matter, or kerogen, in a Recent bottom mud (<1000yr old) from Mono Lake, California, has been analyzed by vacuum pyrolysis-GC-MS and compared with the kerogen from several Precambrian rocks, including the Belingwe and Transvaal stromatolites. The Mono Lake kerogen consists mainly of cyclic and acyclic aliphatic components with lesser amounts of aromatics present. It is less aromatic and more susceptible to thermal degradation than the Precambrian kerogens, and its products show a much greater diversity especially among the unsaturated aliphatics and the heteroatomic components. The presence of these compounds, most notably 2,5-dimethylfuran, in the Mono Lake kerogen indicates a relatively rapid formation and incorporation into a young kerogen and suggests that their presence in the Precambrian kerogens, such as the Belingwe stromatolite, may be consistent with an ancient biological origin.In simulated diagenesis experiments the Recent mud was heated at 150°C for 3 months or 225°C for 8 months. The former was insufficient to affect the kerogen pyrolysis products. The latter, however, caused a large decrease in the heteroatomic components and a slight increase in the abundance of n-alkanes relative to that of the cyclic and branched alkanes. This suggests that the presence of some of these components in Precambrian rocks should be consistent with a high degree of preservation of these rocks, as appears to be the case for the Belingwe and Transvaal stromatolites.     

Organic geochemistry of the kerogen and bitumen from the Ohio Shale by pyrolysis-gas chromatography

An exposure of the Ohio Shale at Bristol Ridge, Ohio in the Bellefontaine Outlier was sampled into 53 channel units. Proximate and elemental (CHN) analyses were performed on these samples to determine the concentration of organic matter. The organic content averaged 6.82% with the highest both in the lower half (11.08%) and extreme upper part (10.43%) of the section.Fragmentation of the kerogen of each of the whole rock samples was accomplished by pyrolyzing for 10 s at 750°C in the injection port of a gas chromatograph with a FID detector. The concentration and distribution of the diagnostic hydrocarbons fragmented at this temperature were used to infer the molecular construction of the high molecular weight kerogens. The suite of identified hydrocarbons for each of the samples throughout the section was similar, but a very large fluctuation in the amount of pyrolysis products was observed. This fluctuation is strongly related to organic richness as defined by the proximate and elemental analyses. The identification of diagnostic normal alkanes and aromatics and SCI indicates that the kerogen assemblage is composed of both marine and terrestial components — most likely a mixed Type II kerogen. The contribution of individual aromatic and normal alkanes is variable, which suggests that there were minor fluctuations in the proportions of terrestrial and marine organic matter during decomposition.Bitumen pyrolized from the whole rock and bitumen removed by Soxhlet extraction using a 4:1 benzene/methanol solvent mixture were analyzed. Comparison of these two techniques yield similar pristane/phytane ratios and Carbon Preference Index (CPI) values. On decomposition the whole rock bitumen exhibited a mean pristane/phytane ratio of 1.5 and a mean CPI value of 1.4, whereas the Soxhlet-extracted bitumen exhibited a mean pristane/phytane ratio of 1.6 and a mean value of 1.3. The low pristane/phytane ratios from this outlier indicates a possible marine environment, with reducing conditions existing immediately below the sediment-water interface. The CPI values also indicate the sedimentary sequence is thermally immature. Reflectance of the vitrinite (%R_o 0.05) and fluorescence (Q 0.93) of the algal bodies indicate a maturation at the beginning of the oil window or at boundary between thermal immaturity and maturity.     

Biomarker analysis of the upper Jurassic Naokelekan and Barsarin formations in the Miran Well-2, Miran oil field,Kurdistan region,Iraq

The Miran oilfield is one of the new oil fields in Kurdistan region, northern Iraq, located in the Sulaimani Governorate. Twelve Cuttings samples from the Upper Jurassic Naokelekan and Barsarin formations in well Miran-2 were selected for detailed organic geochemical investigations. All the samples were subjected to bitumen extraction in order to study any biomarkers present using gas chromatography-mass spectrometry. The dominance of low-molecular-weight n-alkanes and other calculated parameters indicate a marine source for the organic matter derived from planktonic algal and bacterial precursors deposited under anoxic conditions. The isoprenoids/n-alkanes ratios indicate type II and mixed II/III kerogen for both formations. The type II/III kerogen is characteristic of transitional environment under anoxic to dysoxic conditions as also indicated by the homohopane index for studied samples. More argillaceous carbonate rocks were deposited when reducing conditions were prevalent. Medium to high gammacerane index values in the rock extracts probably indicate a stratified water column during deposition of both formations. The studied samples from both formations have entered peak oil window maturity as reflected from the biomarker ratios from both aliphatic and aromatic fractions of the extracts.     

The effect of oil expulsion or retention on further thermal degradation of kerogen at the high maturity stage: A pyrolysis study of type II kerogen from Pingliang shale,China

High maturity oil and gas are usually generated after primary oil expulsion from source rocks, especially from oil prone type I/II kerogen. However, the detailed impacts of oil expulsion, or retention in source rock on further thermal degradation of kerogen at the high maturity stage remain unknown. In the present study, we collected an Ordovician Pingliang shale sample containing type II kerogen. The kerogens, which had previously generated and expelled oil and those which had not, were prepared and pyrolyzed in a closed system, to observe oil expulsion or oil retention effects on later oil and gas generation from kerogen. The results show that oil expulsion and retention strongly impacts on further oil and gas generation in terms of both the amount and composition in the high maturity stage. Gas production will be reduced by 50% when the expulsion coefficient reaches 58%, and gas from oil-expelled kerogen (less oil retained) is much drier than that from fresh kerogen. The oil expulsion also causes n-alkanes and gas compounds to have heavier carbon isotopic compositions at high maturity stages. The enrichment of ¹³C in n-alkanes and gas hydrocarbons are 1‰ and 4–6‰ respectively, compared to fresh kerogen. Oil expulsion may act as open system opposite to the oil retention that influences the data pattern in crossplots of δ¹³C₂–δ¹³C₃ versus C₂/C₃, δ¹³C₂–δ¹³C₃ versus δ¹³C₁ and δ¹³C₁–δ¹³C₂ versus ln(C₁/C₂), which are widely used for identification of gas from kerogen cracking or oil cracking. These results suggest that the reserve estimation and gas/source correlation in deep burial basins should consider the proportion of oil retention to oil expulsion the source rocks have experienced.     

Biomarkers and compound-specific stable carbon isotope of n-alkanes in crude oils from Eastern Llanos Basin,Colombia

Representative samples of crude oils from Cusiana, Cupiagua, Apiay, Castilla and Chichimene fields in the Eastern Llanos Basin of Colombia were analyzed to determine its compound-specific stable carbon isotope composition (CSIA) using gas chromatography–isotopic ratio–mass spectrometry (GC–IRMS). GC–IRMS analyses of n-alkanes allowed differentiating between Cretaceous and Cretaceous/Tertiary oil samples. Cretaceous sourced samples have δ¹³C-enriched values than Cretaceous/Tertiary sourced samples; the heavier isotope composition of these samples is due to their major terrigenous organic matter input. Their isotope distribution patterns suggest significant algal and/or bacterial contribution (marine origin). The analysis of the n-alkane fractions by GC–IRMS confirms that the organic matter has marine origin in those samples from Cusiana, Cupiagua and Apiay while Castilla and Chichimene have marine origin with terrestrial inputs. The results were confirmed by gas chromatography/FID and gas chromatography/mass spectrometry (GC/MS). Basic geochemical composition show that samples from Cupiagua/Cusiana fields and Apiay/Castilla/Chichimene fields in the Llanos basin, Colombia present different characteristics reflecting a specific for each depositional environment.     

Organic geochemistry across the Permian–Triassic transition at the Idrijca Valley,Western Slovenia

Bulk and molecular stable C isotopic compositions and biomarker distributions provide evidence for a diverse community of algal and bacterial organisms in the sedimentary organic matter of a carbonate section throughout the Permian–Triassic (P/Tr) transition at the Idrijca Valley, Western Slovenia. The input of algae and bacteria in all the Upper Permian and Lower Scythian samples is represented by the predominance of C₁₅–C₂₂ n-alkanes, odd C-number alkylcyclohexanes, C₂₇ steranes and substantial contents of C₂₁–C₃₀ acyclic isoprenoids. The occurrence of odd long-chain n-alkanes (C₂₂–C₃₀) and C₂₉ steranes in all the samples indicate a contribution of continental material. The decrease of C_org and C_carb contents, increase of Rock-Eval oxygen indices, and ¹³C-enrichment of the kerogen suggest a decrease in anoxia of the uppermost Permian bottom water. The predominance of odd C-number alkylcycloalkanes, C₂₇ steranes, and C₁₇ n-alkanes with δ¹³C values ∼−30‰, and ¹³C-enrichment of the kerogens in the lowermost Scythian samples are evidence of greater algal productivity. This increased productivity was probably sustained by a high nutrient availability and changes of dissolved CO₂ speciation associated to the earliest Triassic transgression. A decrease of C_org content in the uppermost Scythian samples, associated to a ¹³C-depletetion in the carbonates (up to 4‰) and individual n-alkanes (up to 3.4‰) compared to the Upper Permian samples, indicate lowering of the primary productivity (algae, cyanobacteria) and/or higher degradation of the organic matter.     

The influence of hydrocarbon expulsion on carbon isotopic compositions of individual n-alkanes in pyrolysates of selected terrestrial kerogens

Expulsion of petroleum from source rock is a complex part of the entire migration process. There exist fractional effects on chemical compositions in hydrocarbon expulsion. Does the carbon isotopic fractionation occur during expulsion and to what extent? Here the influence of hydrocarbon expulsion on carbon isotopic compositions of individual n-alkanes from pyrolysates of selected terrestrial kerogens from Tuha basin and Fushun, Liaoning Province of China has been experimentally studied. The pyrogeneration-expulsion experiments were carried out under semi-closed system. The carbon isotopic compositions of individual n-alkanes were measured by GC-IRMS. The main conclusions are as follows. First, there is carbon isotopic fractionation associated with hydrocarbon expulsion from Type III kerogens in Tuha Basin. There exist differences of carbon isotopic compositions between the unexpelled n-alkanes and expelled n-alkanes from Tuha desmocollinite and Tuha mudstone. Second, there is almost no carbon isotopic fractionation associated with hydrocarbon expulsion from Type II kerogens in Fushun and Liaohe Basin. Third, carbon isotopic fractionation in hydrocarbon expulsion should be considered in making oil-source correlation of Type III kerogens at least in the Tuha Basin. Further studies need to be carried out to determine whether this is true in other basins. Fourth, oil and source at different maturity levels cannot be correlated directly for Type III kerogens since the carbon isotopic compositions of expelled hydrocarbons at different temperatures are different. The expelled hydrocarbons are usually lighter (depleted in ¹³C) than the hydrocarbons remaining in the source rock at the same maturity.     

Primary alteration—oxidation of marine algal organic matter from oil source rocks of the North Sea and Norwegian Arctic: new findings

The presence of partially oxidized algal organic matter in oil-prone marine source rocks, is the rule rather than the exception. Partially oxidized, algal kerogen can still act as a significant source of liquid hydrocarbons. However, the corresponding peak of C₁₂ + hydrocarbon generation is shifted to a considerably lower maturity level compared with that of the classical Type II kerogen. The extent of primary alteration-oxidation of marine algal kerogen is monitored by means of solid state microfluorescence spectroscopy. A new parameter, the Primary Alteration Factor (PAF) is established, and the relationships between PAF and H/C, O/C, HI, TOC and between PAF and %₀δ¹³C are determined. The present data show large variations in the bulk chemistry of immature marine algal kerogens, and reveal evidence for gradational dehydrogenation/oxidation of the source organic matter. This contrasts with the recently proposed mechanism for kerogen formation. SEM analysis reveals a relationship between the physical breakdown of algal organic matter and the formation of liptodetrinite. FTIR analysis shows that the incorporation of primary oxygen in the kerogen macromolecules is not in the form of carbonyl or carboxyl functionalities. The presence of highly unreactive, stable oxygen, associated with aromatic structures in partially oxidized algal kerogen, is suggested by resistance of the kerogen to graphitization. The FTIR data also suggest the presence of aryl ether oxygen. The present findings raise fundamental questions regarding the mechanisms of kerogen cracking and kerogen formation, and have important implications for petroleum exploration.     

Possible carotenoid-derived structures in fossil kerogens

The unique KMnO₄ degradation products of β-carotene, previously identified as 2,2-dimethyl succinic acid (C₆) and 2,2-dimethyl glutaric acid (C₇) have been found in the oxidation products of Green River shale (Eocene, 52 × 10⁶yr) and Tasmanian Tasmanite (Permian, 220−274 × 10⁶yr) kerogens. These two compounds were also detected in KMnO₄ degradation products of young kerogens from lacustrine and marine sediments. The results indicate that kerogens incorporated carotenoids (possibly β-carotene) at the time of kerogen formation in surface sediments. Both acids are useful markers to obtain information on biological precursors contributing to the formation of fossil kerogens.     

Characteristics of amorphous kerogens fractionated from terrigenous sedimentary rocks

A preliminary attempt to fractionate amorphous kerogens from terrigenous bulk kerogen by a benzene-water two phase partition method under acidic condition was made. Microscopic observation revealed that amorphous kerogens and structured kerogens were fractionated effectively by this method. Characteristics of the amorphous and structured kerogens fractionated by this method were examined by some chemical analyses and compared with those of the bulk kerogen and humic acid isolated from the same rock sample (Haizume Formation, Pleistocene, Japan). The elemental and infrared (IR) analyses showed that the amorphous kerogen fraction had the highest atomic$\text{H}\text{C}$ ratio and the lowest atomic $\text{N}\text{C}$ ratio and was the richest in aliphatic structures and carbonyl and carboxyl functional groups. Quantities of fatty acids from the saponification products of each geopolymer were in agreement with the results of elemental and IR analyses. Distribution of the fatty acids was suggestive that more animal lipids participate in the formation of amorphous kerogens because of the abundance of relatively lower molecular weight fatty acids (such as C₁₆ and C₁₈ acids) in saponification products of amorphous kerogens. On the other hand, although the amorphous kerogen fraction tends to be rich in aliphatic structures compared with bulk kerogen of the same rock samples, van Krevelen plots of elemental compositions of kerogens from the core samples (Nishiyama Oil Field, Tertiary, Japan) reveal that the amorphous kerogen fraction is not necessarily characterized by markedly high atomic $\text{H}\text{C}$ ratio. This was attributed to the oxic environment of deposition and the abundance of biodegraded terrestrial amorphous organic matter in the amorphous kerogen fraction used in this work.     

Hydrocarbons generated by hydropyrolysis of suspended marine particulate organic matter: Relationship to the oceanography of the Black Sea and the Rhodes Gyre

The suspended particulate organic matter, SPOM, in the autumnal Black Sea has been characterised using catalytic hydropyrolysis (HyPy) of the total (bound plus free) lipid material. The technique, which generates maximum yields of volatile products from sediments, kerogens and phytoplankton, was followed using gas chromatography and gas chromatography/mass spectrometry. The generated alkanes were dominated by n-C₁₈, hypothesised to arise predominantly from unsaturated C₁₈ fatty acids. Steranes were generated from reductive conversion of free and bound sterols. The generation of branched alkanes and especially of hopanes provided formal evidence for the participation of bacteria in the mineralisation of the SPOM. Whereas similar distributions of n-alkanes were generated from SPOM sampled from different depths of the comparatively well-stirred Rhodes Gyre (eastern Mediterranean), mineralisation of the SPOM at each depth of the central Black Sea produced characteristic changes in the composition and concentration of the HyPy products. Depth profiles of the n-alkanes generated from SPOM in the region of the Rim Current were affected by the local hydrography. Polynuclear aromatic hydrocarbons (PAHs) of anthropogenic origin were present in the surface waters of the central Black Sea. Some methyl benzenes, thiophenes and pyrroles were also generated.     

Hydrocarbons and fatty acids in the Evergreen Shale,Surat Basin,Queensland, Australia

Alkane hydrocarbon and n-fatty acid distributions have been examined in cores taken over a 550 ft thickness through the lower Jurassic, largely non-marine Evergreen Shale, Surat Basin, Queensland, Australia. No depth trends in compound abundances or carbon preference indices are discernible. There is no evidence for significant generation of n-alkanes from kerogen nor for cracking of long-chain n-alkanes. The present distribution patterns of the biochemicals probably reflect closely the nature of the original organic matter. The general strong dominance of long-chain (C₂₀₊) n-alkanes; the lack of evidence for diagenetic change; and the absence of correlation between abundances of n-alkanes and n-fatty acids (among both the longer- and shorter-chain compounds), lead to the conclusion that at least the long-chain n-alkanes were largely deposited as such in the sediment, having originated in land-plant material, remains of which are abundant in the samples. In the upper 170 ft. (possibly marine), n-alkanes with chain lengths below C₂₀ become important, suggesting greater significance of aquatic life as a source of organic matter at the time of deposition, a conclusion which is in general accord with the geological history of the basin, although this history is not well known.     

Hydrocarbon source rock potential evaluation of the Late Paleocene Patala Formation,Salt Range,Pakistan: Organic geochemical and palynofacies approach

Organic geochemical and palynofacies analyses were carried out on shale intervals of the Late Paleocene Patala Formation at Nammal Gorge Section, western Salt Range, Pakistan. The total organic carbon content and Rock-Eval pyrolysis results indicated that the formation is dominated by type II and type III kerogens. Rock-Eval \({T}_{\mathrm{max}}\) vs. hydrogen index (HI) and thermal alteration index indicated that the analysed shale intervals present in the formation are thermally mature. \(S_{1}\) and \(S_{2}\) yields showed poor source rock potential for the formation. Three palynofacies assemblages including palynofacies-1, palynofacies-2 and palynofacies-3 were identified, which are prone to dry gas, wet gas and oil generation, respectively. The palynofacies assessment revealed the presence of oil/gas and gas prone type II and type III kerogens in the formation and their deposition on proximal shelf with suboxic to anoxic conditions. The kerogen macerals are dominated by vitrinite and amorphinite with minor inertinite and liptinite. The kerogen macerals are of both marine and terrestrial origin, deposited on a shallow shelf. Overall, the dark black carbonaceous shales present within the formation act as a source rock for hydrocarbons with poor-to-moderate source rock quality, while the grey shales act as a poor source rock for hydrocarbon generation.     

Alkaline permanganate oxidation of kerogens from Cretaceous black shales thermally altered by diabase intrusions and laboratory simulations

Potassium permanganate oxidative degradations were conducted for kerogens isolated from Cretaceous black shales (DSDP Leg 41, Site 368), thermally altered during the Miocene by diabase intrusions and from unaltered samples heated under laboratory conditions (250–500°C).Degradation products of less altered kerogens are dominated by normal C₄–C₁₅ α,ω-dicarboxylic acids, with lesser amounts of n-C₁₆ and n-C₁₈ monocarboxylic acids, and benzene mono-to-tetracarboxylic acids. On the other hand, thermally altered kerogens show benzene di-to-tetracarboxylic acids as dominant degradation products, with lesser or no amounts (variable depending on the degree of thermal alteration) of α,ω-dicarboxylic acids. Essentially no differences between the oxidative degradation products of naturally- and artificially-altered kerogens are observed.As a result of this study, five indices of aromatization (total aromatic acids/kerogen; apparent aromaticity; benzenetetracarboxylic acids/total aromatic acids; benzene-1,2-dicarboxylic acid/benzenedicarboxylic acids; benzene-1,2,3-tricarboxylic acid/benzenetricarboxylic acids) and two indices of aliphatic character (Total aliphatic acids/kerogen; Aliphaticity) are proposed to characterize the degree of thermal alteration of kerogens.Furthermore, a good correlation is observed between apparent aromaticity estimated by the present KMnO₄ oxidation method and that from the ¹³C NMR method (DENNIS et al., 1982).     

Characterization of the hydrogen isotopic composition of individual n-alkanes in terrestrial source rocks

In order to characterize the H isotopic compositions of individual lipid compounds from different terrestrial depositional environments, the δD values of C-bound H in individual n-alkanes from typical terrestrial source rocks of the Liaohe Basin and the Turpan Basin, China, were measured using gas chromatography–thermal conversion–isotope ratio mass spectrometry (GC–TC–IRMS). The analytical results indicate that the δD values of individual n-alkanes in the extracts of terrestrial source rocks have a large variation, ranging from −140‰ to −250‰, and are obviously lighter than the δD of marine-sourced n-alkanes. Moreover, a trend of depletion in ²H(D) was observed for individual n-alkanes from different terrestrial depositional environments, from saline lacustrine to freshwater paralic lacustrine, and to swamp. For example, the δD values of n-alkanes from a stratified saline lacustrine environment vary from −140‰ to −200‰, δD for n-alkanes from swamp facies range from −200‰ to −250‰, while those from freshwater paralic lacustrine–lacustrine environments fall between the δD values of the end members. The shift toward lighter δD from saltwater to freshwater environments indicates that the source water δD is the major controlling factor for the H isotopic composition of individual compounds. In addition, H exchange between formation water and sedimentary organic matter may possibly be important in regard to the δD of individual n-alkanes. Therefore, other lines of geochemical evidence must be considered when depositional paleoenvironments of source rocks are reconstructed based on the H isotopic composition of individual n-alkanes.     

Aliphatic and aromatic biomarkers from Gondwanan sediments of Late Ordovician to Early Devonian age: An early terrestrialization approach

Twenty one core samples of Late Ordovician to Early Devonian age from sections in southern Tunisia, North African Platform (Gondwana) and containing marine and terrestrial organic matter with microbial input were investigated to link the aliphatic and aromatic hydrocarbon distributions with the terrestrial and marine palynomorph content (e.g. acritarchs, prasinophytes, chitinozoans, cryptospores and trilete spores). In addition to several biomarkers of algal/bacterial origin, long chain n-alkanes that might be derived from land plants, as well as the terrestrial diterpane, norabietane, were found. Several land plant-derived biomarkers, such as retene, cadalene, simonellite, tetrahydroretene and C₁₉ isohexylalkyl naphthalene were observed in the aromatic fractions. While these terrestrial biomarkers could be clearly recognized in the middle Silurian-lower Devonian samples, their presence in the upper Ordovician-lower Silurian sediments is more doubtful, because of much lower relative abundances. The land plant biomarkers show a fairly good correlation with the occurrence and abundance of cryptospores and trilete spores, derived from bryophytes and tracheophytes, which covered the emerged areas around the Ghadamis Basin during the Silurian and Devonian. The early tracheophytes (e.g. Cooksonia, lycophytes and zosterophylls) are therefore suggested as a new terrestrial source for most of the saturated and aromatic biomarkers found in sediments of Middle Silurian to Early Devonian age.     

Distributions of n-alkanes and their hydrogen isotopic composition in plants from Lake Qinghai (China) and the surrounding area

Various aquatic plants from Lake Qinghai, the largest inland saline lake in China, and terrestrial plants from the surrounding area were investigated for the distribution of n-alkanes and their δD values. The n-alkanes in the samples range from C₁₅ to C₃₃ with C preference index (CPI) values of 4.0–29.7. The n-C₂₃ or n-C₂₅ alkane is the dominant compound in the aquatic submerged plants. The aquatic emergent and terrestrial plants have an abundance maximum at n-C₂₇, n-C₂₉ or n-C₃₁. The average chain length (ACL) values, ranging from 26.0 to 29.6, are closely related to the plant species. The n-alkanes from the aquatic plants have mean δD values of −169‰ to −121‰ and those from the terrestrial plants values of −173‰ to −109‰. The H isotopic composition (δD) and fractionation differ significantly among the plants studied. Comparison shows that additional evaporative enrichment of the lake water associated with saline lakes and humidity influence the δD values of the n-alkanes in aquatic and terrestrial plants, respectively. The mean δD values of n-alkanes in the plants decrease with increasing ACL value. The n-alkanes from the different types of plants are more depleted in D relative to environmental water and those from aquatic plants (with a mean value of −143‰) have a greater isotopic fractionation than terrestrial plants (mean value −113‰).