The source and paleoclimatic implication of hydrogen isotopic composition of n-alkanes in sediments from the Yixian Formation,western Liaoning Province,NE China

Hydrogen isotopic composition of n-alkanes was measured in sediments from an excavated profile of the Early Cretaceous Yixian Formation in Liaoning Province, NE China, aiming to assess the significance of the δD value of n-alkanes in ancient lacustrine sediments as the indicator for determining the source inputs of organic matters and paleoclimatic conditions. The δD values of n-alkanes are in the range of − 250‰ to − 85‰ and display an obvious three-stage variation pattern through the profile, which is consistent with the distribution of the dominated n-alkanes and the profile of their δ¹³C values. The δD and δ¹³C values of n-alkanes suggest that short-chain n-alkanes are primarily derived from photosynthetic bacteria and algae; n-C₂₉ and n-C₃₁ are mainly originated from terrestrial higher plants; n-C₂₈ and n-C₃₀ may be derived from the same precursor but via the different biological mechanism of hydrogen isotopic fractionation; while the source inputs of medium-chain n-alkanes are more complicated, with n-C₂₃ being derived from some specific algae or biosynthesized by various aquatic organisms. The paleoclimatic conditions are reconstructed via two approaches. The reconstructed hydrogen isotopic values of lake water and meteoric water (expressed as δD_LW and δD_MW, respectively) were at the intervals of − 51.8‰ to 17.0‰ and − 118.1‰ to − 43.5‰, respectively, indicating a general climate transition from semi-arid to arid. The calculated ΔδD_LW-MW values vary from 37.0‰ to 89.1‰ and display a similar but a significant large-scale variation trend with the ΔδD_{C23 ‐ long} (− 28.8‰ to 85.0‰; long represents long-chain n-alkanes) and ΔδD_mid-long (− 15.4‰ to 43.4‰; mid represents medium-chain n-alkanes) values. The discrepancy may be attributed to the source input overlap for n-alkanes and the uncertainties of ε_water/lipid values. The coupling of ΔδD_{C23 ‐ long}, ΔδD_mid-long and ΔδD_LW-MW values with the paleoclimatic evidence indicates that the δD values of n-alkanes could be more sensitive to the change of paleoclimatic conditions.     

Biomarkers in surface sediments from the Cross River and estuary system,SE Nigeria: Assessment of organic matter sources of natural and anthropogenic origins

Herein, lipid biomarker analysis is applied to surface sediments from the southeastern Niger Delta region for the quantitative determination of aliphatic lipids, steroids and triterpenoids in order to differentiate between natural (autochthonous vs. allochthonous) and anthropogenic organic matter (OM) inputs to this deltaic environment. This ecosystem, composed of the Cross, Great Kwa and Calabar Rivers, is receiving new attention due to increased human and industrial development activities and the potential effects of these activities impacting its environmental health. While the presence of low molecular weight n-alkanes (<C₂₂) and the fossil biomarkers pristane and phytane in all samples, are indicative of a minor petroleum related input, the total extractable organic component of the surface sediments of these rivers remains predominantly of a natural origin as characterized by the variety and predominance of lipid classes that are mainly derived from the epicuticular waxes of vascular plants and include n-alkanes, n-alkanols, n-alkan-2-ones, n-alkanoic acids, steroids and triterpenoids. In addition, recent OM inputs from microorganisms are indicated by the presence of lower molecular weight n-alkanoic acids (C_max = 16), while the major triterpenoids of the sediments, taraxerol and friedelin, and the major sterol, sitosterol, indicate recent OM inputs from vascular plants. Plankton-derived sterols, such as fucosterol and dinosterol, are also found in sediments from the Cross and Great Kwa Rivers and likely originate from autochthonous primary productivity. Furthermore, the coprosterols coprostanol and 24-ethylcoprostanol are present in most samples and indicate measurable anthropogenic contributions from domestic untreated sewage inputs and agricultural run-off, respectively. Of the three rivers studied, the Cross River system was excessively influenced by human and industrial development activities, including drivers such as urbanization and population center growth, land-use change to support agricultural production and animal husbandry, and petroleum exploration and production. These influences were found to be regionally specific as controlled by point sources of pollution based on the relative distributions measured and on the fact that the molecular characteristics of sedimentary OM were not distributed smoothly along a gradient.     

Reconstruction of the late Quaternary paleoenvironments of the Nussloch loess paleosol sequence,Germany, using n-alkane biomarkers

This study contributes to the paleoenvironmental reconstruction of the loess–paleosol sequence of Nussloch, Germany, by using n-alkanes as plant leaf-wax-derived lipid biomarkers. We found that n-alkane patterns and concentrations in the Saalian loess and the last interglacial Eemian paleosol of Nussloch point to very strong degradation and prevailing deciduous vegetation. Degradation effects in the overlying paleosols and loess layers are less pronounced and allow for the application of an end-member mixing model to estimate vegetation changes semi-quantitatively. Our findings highlight the potential for the interpretation of degradation-corrected n-alkane ratios. n-Alkane modelling results for loess layers, paleosols and an in-filled paleochannel dated to ~ 60–32 ka suggest that up to ~ 50% of the n-alkanes were derived from deciduous trees or shrubs. This finding is in agreement with the abundant occurrence of wood fragments and indicates a highly variable and dynamic landscape dominated by tundra shrubland. On the other hand, deciduous trees or shrubs did not contribute significantly to the soil organic matter in the late Weichselian loess layers and the intercalated Gelic Gleysols (~ 32–18 ka).     

Source characterization using molecular distribution and stable carbon isotopic composition of n-alkanes in sediment cores from the tropical Mundaú–Manguaba estuarine–lagoon system,Brazil

The Mundaú–Manguaba estuarine–lagoon system (MMELS) constitutes one of the most representative ecosystems in the state of Alagoas, NE Brazil. Approximately 30% or 60,000 ha of the lower surrounding drainage basin of the MMELS are covered by sugar cane and a total of 250,000 inhabitants contribute untreated effluent to the system. Short sediment cores from MMELS were collected in 2007 at three sites: Manguaba Lagoon (C03), Mundaú Lagoon (C07) and Mundaú River (C08) in order to characterize the delivery and deposition of n-alkanes over the past 40 yr. The n-alkanes ranged from C₁₅ to C₃₅, with total aliphatic hydrocarbon (TAH) concentration in the range 27.8–139.5 μg g⁻¹. An unresolved complex mixture (UCM) was observed in all sediments. The terrigenous/aquatic ratio (TAR), carbon preference index (CPI) and average chain length (ACL) showed that the terrigenous input dominated. The (δ¹³C) values of individual n-alkanes (C₁₆–C₃₃) varied between −22.6‰ and −34.2‰, suggesting a dominance of ¹²C-enriched n-alkanes that originated from C₃ plants and lacustrine algae. The data reflect how anthropogenic input (via sewage, industrial pollution and agriculture) has influenced the organic content of the system through time.     

Effect of climate change on delivery and degradation of lipid biomarkers in a Holocene peat sequence in the Eastern European Russian Arctic

Lipid biomarkers from a peat plateau profile from the Northeast European Russian Arctic were analyzed. The peat originated as a wet fen ca. 9 ka BP and developed into a peat bog after the onset of permafrost ca. 2.5 ka BP. The distributions and abundances of n-alkanols, n-alkanoic acids, n-alkanes, n-alkan-2-ones and sterols were determined to study the effect of degradation on their paleoclimate proxy information. Plant macrofossil analysis was also used in combination with the lipid distributions. The n-alkanol and n-alkanoic acid distributions in the upper part of the sequence generally correspond to compositions expected from plant macrofossil assemblages. Their carbon preference index (CPI) values increase with depth and age, whereas those of the n-alkanes decrease. The different CPI patterns suggest that n-alkanoic acids and n-alkanols deeper in the sequence may be produced during humification through alteration of other lipids. Excursions in the n-alkanoic acid content also suggest an important contribution of invasive roots to the lipid biomarker composition. The CPIs associated with these compounds show that under permafrost conditions organic material from Sphagnum is better preserved than material from vascular plants. Increasing stanol/stenol ratio values and decreasing n-alkane CPI values indicate progressive degradation of organic matter (OM) with depth. The n-alkan-2-one/n-alkane and n-alkan-2-one/n-alkanoic acid ratios were shown to be useful proxies that can reflect the degree of OM preservation and suggest that both microbial oxidation of n-alkanes and decarboxylation of n-alkanoic acids produce n-alkan-2-ones in this peat sequence.     

The occurrence of ultra-deep heavy oils in the Tabei Uplift of the Tarim Basin,NW China

Deeply buried heavy oils from the Tabei Uplift of the Tarim Basin have been investigated for their source origin, charge and accumulation time, biodegradation, mixing and thermal cracking using biomarkers, carbon isotopic compositions of individual alkanes, fluid inclusion homogenization temperatures and authigenic illite K–Ar radiometric ages. Oil-source correlation suggests that these oils mainly originated from Middle–Upper Ordovician source rocks. Burial history, coupled with fluid inclusion temperatures and K–Ar radiometric ages, suggests that these oils were generated and accumulated in the Late Permian. Biodegradation is the main control on the formation of these heavy oils when they were elevated to shallow depths during the late Hercynian orogeny. A pronounced unresolved complex mixture (UCM) in the gas chromatograms together with the presence of both 25-norhopanes and demethylated tricyclic terpanes in the oils are obvious evidence of biodegradation. The mixing of biodegraded oil with non-biodegraded oil components was indicated by the coexistence of n-alkanes with demethylated terpanes. Such mixing is most likely from the same phase of generation, but with accumulation at slightly different burial depths, as evidenced by overall similar oil maturities regardless of biodegradation level and/or amount of n-alkanes. Although these Ordovician carbonate reservoirs are currently buried to over 6000 m with reservoir temperatures above 160 °C, no significant secondary hydrocarbon generation from source rocks or thermal cracking of reservoired heavy oil occur in the study area. This is because the deep burial occurred only within the last 5 Ma of the Neogene, and there has not been enough heating time for additional reactions within the Middle–Upper Ordovician source rocks and reservoired heavy oils.     

The applicability of accelerated solvent extraction (ASE) to extract lipid biomarkers from soils

We investigated the ability of accelerated solvent extraction (ASE) to extract selected lipid biomarkers (C₁₉–C₃₄ n-alkanes, n-alcohols and n-fatty acids as well as dehydroabietic acid and β-sitosterol) from a sandy soil profile under Corsican pine. Two organic layers (moss and F1) as well as two mineral soil horizons (EA and C1) were sampled and extracted with DCM/MeOH (93:7 v/v) by ASE at 75 °C and a pressure of 6.9 × 10⁶ Pa or 17 × 10⁶ Pa. Soxhlet extractions were used as the established reference method. After clean-up and derivatization with BSTFA, the extracts were analyzed on GC/MS.Using Soxhlet as a reference, we found ASE to extract all compounds adequately. The n-alkanes, especially, were found to be extracted very efficiently from all horizons studied. Only the n-fatty acids and β-sitosterol from the organic layers seemed to be extracted at a slightly lower efficiency by ASE. In all but two instances the relative abundance of extracted lipids within a component class was the same regardless of the extraction method used.Using a higher pressure in the ASE extractions significantly increased the extraction efficiency for all component classes in the moss layer, except β-sitosterol. The effect was most pronounced for the n-alkanes. In the EA horizon, a higher pressure slightly reduced the extraction efficiency for dehydroabietic acid. The observed differences between ASE and Soxhlet extractions as well as the pressure effect can be explained by a decrease in polarity of the extractant due to the elevated pressure and temperature applied during ASE extractions as compared to Soxhlet extractions. This would mainly increase the extraction efficiency of the least polar biomarkers: the n-alkanes as was observed. In addition, a better penetration of still partially water-filled micro pores under elevated pressure and temperature may have played a role.     

Biomarkers of novel ecosystem development in boreal forest soils

Novel ecosystem development is occurring within the western boreal forest of Canada due to land reclamation following oil sand surface mining. Sphagnum peat is the primary organic amendment used to reconstruct soil in these novel ecosystems. We hypothesised that ecosystem recovery would be indicated by an increasing similarity in the biomolecular characteristics of novel soil organic matter (SOM) derived from peat to those of natural boreal ecosystems. We evaluated the use of the homologous series of long chain (⩾ C₂₁) n-alkanes with odd/even predominance to monitor the re-establishment of boreal forest on these anthropogenic soils. The lipids were extracted from dominant vegetation inputs and SOM from a series of natural and novel ecosystem reference plots. Twice the concentration of n-alkanes was extracted from natural than from novel ecosystem SOM (p < 0.01). We observed unique n-alkane signatures for the source vegetation, e.g. peat material was dominated by C₃₁, and aspen (Populus tremuloides Michx.) leaves by C₂₅. The n-alkane distribution differed between the two systems (p < 0.001) and reflected the dominant vegetation input, i.e. peat or tree species. Our results indicate that further research is required to clarify the influence of vegetation or disturbance on the signature of n-alkanes in SOM; however, the use of n-alkanes as biomarkers of novel ecosystem development is a promising application.     

Production of n-alkyl lipids in living plants and implications for the geologic past

Leaf waxes (i.e., n-alkyl lipids or n-alkanes) are land-plant biomarkers widely used to reconstruct changes in climate and the carbon isotopic composition of the atmosphere. There is little information available, however, on how the production of leaf waxes by different kinds of plants might influence the abundance and isotopic composition of n-alkanes in sedimentary archives. This lack of information increases uncertainty in interpreting n-alkyl lipid abundance and δ¹³C signals in ancient settings. We provide here n-alkyl abundance distributions and carbon isotope fractionation data for deciduous and evergreen angiosperm and gymnosperm leaves from 46 tree species, representing 24 families. n-Alkane abundances are significantly higher in angiosperms than gymnosperms; many of the gymnosperm species investigated did not produce any n-alkanes. On average, deciduous angiosperms produce 200 times more n-alkanes than deciduous gymnosperms. Although differences between angiosperms and gymnosperms dominate the variance in n-alkane abundance, leaf life-span is also important, with higher n-alkane abundances in longer-lived leaves. n-Alkanol abundances covary with n-alkanes, but n-alkanoic acids have similar abundances across all plant groups. Isotopic fractionation between leaf tissue and individual alkanes (ε_lipid) varies by as much as 10‰ among different chain lengths. Overall, ε_lipid values are slightly lower (−4.5‰) for angiosperm than for gymnosperm (−2.5‰) n-alkanes. Angiosperms commonly express slightly higher Δ_leaf (photosynthetic discrimination) relative to gymnosperms under similar growth conditions. As a result, angiosperm n-alkanes are expected to be generally 3-5‰ more depleted in ¹³C relative to gymnosperm alkanes for the same locality. Differences in n-alkane production indicate the biomarker record will largely (but not exclusively) reflect angiosperms if both groups were present, and also that evergreen plants will likely be overrepresented compared with deciduous ones. We apply our modern lipid abundance patterns and ε_lipid results to constrain the magnitude of the carbon isotope excursion (CIE) at the onset of the Paleocene-Eocene Thermal Maximum (55.8 Ma). When Bighorn Basin (WY) sediment n-alkanes are interpreted in context of floral changes and modern n-alkane production estimates for angiosperms and gymnosperms, the CIE is greater in magnitude (−5.6‰) by ∼1‰ compared to previous estimates that do not take into account n-alkane production.     

Thermal degradation of rye and maize straw: Lipid pattern changes as a function of temperature

Future climatic conditions may coincide with an increased potential for wildfires in grassland and forest ecosystems, whereby charred biomass would be incorporated into soils. Molecular changes in biomass upon charring have been frequently analysed with a focus on black carbon. Aliphatic and aromatic hydrocarbons, known to be liberated during incomplete combustion of biomass have been preferentially analysed in soot particles, whereas determinations of these compounds in charred biomass residues are scarce. We discuss the influence of increasing charring temperature on the aliphatic and aromatic hydrocarbon composition of crop grass combustion residues. Straw from rye, representing C₃ grasses and maize, representing C₄ grasses, was charred in the presence of limited oxygen at 300, 400 and 500 °C. Typical n-alkane distribution patterns with a strong predominance of long chain odd-numbered n-alkanes maximising at C₃₁ were observed in raw straw. Upon combustion at 300 °C aliphatic hydrocarbons in char were dominated by sterenes, whereas at 400 °C sterenes disappeared and medium chain length n-alkanes, maximising around n-C₂₀, with a balanced odd/even distribution were present. At a charring temperature of 500 °C n-alkane chain length shifted to short chain homologues, maximising at C₁₈ with a pronounced predominance of even homologues. Even numbered, short chain n-alkanes in soils may thus serve as a marker for residues of charred biomass. Aromatic hydrocarbons indicate an onset of aromatization of biomass already at 300 °C, followed by severe aromatization upon incomplete combustion at 400–500 °C. The diagnostic composition of aliphatic and aromatic hydrocarbons from charred biomass affords potential for identifying residues from burned vegetation in recent and fossil soils and sediments.     

Organic matter geochemistry and petrography of Late Cretaceous (Cenomanian-Turonian) organic-rich shales from the Belle Fourche and Second White Specks formations,west-central Alberta,Canada

Organic-rich mudstones with up to 10 wt% TOC from the upper portion of the Belle Fourche Formation and the lower part of the Second White Specks Formation in the Western Canada Sedimentary Basin were evaluated as source rocks. Both geochemistry and organic petrography indicate an open marine paleoenvironment with deposition of Type II kerogen based on the predominance of marine alginite and amorphous organic matter (OM), limited amounts of terrigenous vitrinite and inertinite macerals, the presence of marine fossils, and the low ratio of TOC to total sulfur (∼1.26). The prevalence of short-chain n-alkanes (n-C₁₃ to n-C₁₉), a predominance of C₂₈ αββ(H)-20S steranes, and small concentrations of oleanane confirm the dominantly algal and planktonic origin of OM. Alternating oxic to anoxic paleoenvironmental sedimentary conditions are proposed based on common bioturbation, abundant inoceramid prisms, and good organic richness. Biomarker distributions are consistent with intermittent anoxia, without unequivocal evidence for water column stratification or hypersalinity. The thermal maturity measured in seven sediment cores by different methods consistently indicates a westward increase in maturity according to vitrinite reflectance, T_max, and hopane and sterane biomarkers. Two cores are thermally immature (∼0.42 %Ro), one is early mature (∼0.65 %Ro), and four cores are within the oil window (∼0.78 to 0.89 %Ro). All thermally mature cores retain good to very good hydrocarbon potential (248 mg HC/g rock) and are dominantly oil-prone and minor gas-prone based on their maceral compositions. The upper Belle Fourche and lower Second White Specks Formations represent potential targets for unconventional light shale oil production.     

Radiolytic alteration of biopolymers in the Mulga Rock (Australia) uranium deposit

We investigated the effect of ionizing radiation on organic matter (OM) in the carbonaceous uranium (U) mineralization at the Mulga Rock deposit, Western Australia. Samples were collected from mineralized layers between 53 and 58.5 m depths in the Ambassador prospect, containing <5300 ppm U. Uranium bears a close spatial relationship with OM, mostly finely interspersed in the attrinite matrix and via enrichments within liptinitic phytoclasts (mainly sporinite and liptodetrinite). Geochemical analyses were conducted to: (i) identify the natural sources of molecular markers, (ii) recognize relationships between molecular markers and U concentrations and (iii) detect radiolysis effects on molecular marker distributions. Carbon to nitrogen ratios between 82 and 153, and Rock–Eval pyrolysis yields of 316–577 mg hydrocarbon/g TOC (HI) and 70–102 mg CO₂/g TOC (OI) indicate a predominantly lipid-rich terrigenous plant OM source deposited in a complex shallow swampy wetland or lacustrine environment. Saturated hydrocarbon and ketone fractions reveal molecular distributions co-varying with U concentration. In samples with <1700 ppm U concentrations, long-chain n-alkanes and alkanones (C₂₇–C₃₁) reveal an odd/even carbon preference indicative of extant lipids. Samples with ⩾1700 ppm concentrations contain intermediate-length n-alkanes and alkanones, bearing a keto-group in position 2–10, with no carbon number preference. Such changes in molecular distributions are inconsistent with diagenetic degradation of terrigenous OM in oxic depositional environments and cannot be associated with thermal breakdown due to the relatively low thermal maturity of the deposits (R_r = 0.26%). It is assumed that the intimate spatial association of high U concentrations resulted in breakdown via radiolytic cracking of recalcitrant polyaliphatic macromolecules (spores, pollen, cuticles, or algal cysts) yielding medium chain length n-alkanes (C₁₃–C₂₄). Reactions of n-alkenes with OH⁻ radicals from water hydrolysis produced alcohols that dehydrogenated to alkanones or through carbonylation formed alkanones. Rapid reactions with hydroxyl radicals likely decreased the isomerization of n-alkenes and decreased alkanone diversity, such that the alkan-2-one isomer is predominant. This specific distribution of components generated by natural radiolysis enables their application as “radiolytic molecular markers”. Breaking of C–C bonds through radiolytic cracking at temperatures much lower than the oil window (<50 °C) can have profound implications on initiation of petroleum formation, paleoenvironmental reconstructions, mineral exploration and in tracking radiolysis of OM.     

Preservation of an ancient grassland biomarker signature in a forest soil from the French Massif Central

In response to the lack of studies focussing on the residence time of molecular biomarkers in soils, the lipid content of three soil profiles from the French Massif Central with different land use history were examined. The free neutral lipid content of two reference soil profiles developed under grassland and forest vegetation, and of a former grassland soil converted to forest about 60 years ago, was analysed using gas chromatography–mass spectrometry (GC–MS). Wax esters as well as the ratio of major homologues of n-alkanes and n-alkan-2-ones could be used to characterise the overlying vegetation in the reference forest and grassland soil profiles, but failed to distinguish the respective grassland and forest contributions to the profile of the soil that had changed use. For n-alkanes and n-alkan-2-ones, the failure might be attributed either to mixing of the molecular patterns inherited from the former and current plant cover, whereas for compounds such as wax esters simple degradation is likely to be involved. Conversely, iso- and anteiso-C_15:0 fatty acid methyl esters (FAMEs; of bacterial origin), steroids (tracing cattle faecal contamination), tricyclic diterpenoids and their oxygenated derivatives, as well as methoxyserratenes (inherited from Pinaceae) and triterpenyl acetates (specific to the Asteraceae), proved to be effective in distinguishing current land use for the reference soil profiles and for the converted soil. The persistence of these compounds in the changed use soil allowed us to estimate their residence time in soil.     

Crassulacean acid metabolism influences D/H ratio of leaf wax in succulent plants

This study sought to characterize hydrogen isotopic fractionation during biosynthesis of leaf wax n-alkanes in succulent plants capable of crassulacean acid metabolism (CAM). The metabolic and physiological features of CAM represent crucial strategies for survival in hot and dry climates and have been hypothesized to impact hydrogen isotope fractionation. We measured the stable carbon and hydrogen isotopic compositions (δ¹³C and δD, respectively) of individual n-alkanes in 20 species of succulent plants from a global collection of the Huntington Botanical Gardens, San Marino, California. Greenhouse conditions and irrigation with water of constant δD value enabled determination of interspecies differences in net D/H fractionation between source water and leaf wax products. Carbon isotope ratios provide constraints on the extent of CAM vs. C₃ photosynthesis and indicate a wide range of CAM use, with δ¹³C values ranging from −33.01‰ to −18.54‰ (C₂₇–C₃₃ n-alkanes) and −26.66‰ to −17.64‰ (bulk tissue). Despite the controlled growth environment, we observed ca. 90‰ interspecies range in δD values from −193‰ to −107‰. A positive correlation between δ¹³C_bulk and δD_C31 values with R² = 0.60 (δ¹³C_C31 and δD_C31 values with R² = 0.41) implicates a metabolic isotope effect as the dominant cause of interspecies variation in the hydrogen isotopic composition of leaf wax n-alkanes in CAM-intermediate plants.     

Altitudinal shift in stable hydrogen isotopes and microbial tetraether distribution in soils from the Southern Alps,NZ: Implications for paleoclimatology and paleoaltimetry

The Southern Alps are an ideal locality for studying patterns of isotopic fractionation associated with orographic precipitation. We have evaluated whether altitudinal change is reflected in the stable hydrogen isotopic composition (δ²H) of stream water, plant stem water and leaf wax lipids (n-alkanes) from living plants and soils, as well as in soil temperature. Samples were collected along an altitudinal transect from the windward side of the Southern Alps to Lake Hawea in the rain shadow. The results indicate that δ²H values of stem water overlap with stream water, demonstrating a gradual decrease with elevation that complied with modeled Rayleigh distillation, reflecting an isotopic lapse rate of −18.0 (± 1.1, 1σ)‰/km. Leaf and soil n-alkanes shared similar δ²H values and were ²H depleted relative to stem/stream waters. The values for soil n-alkanes indicated an isotopic lapse rate of −21.8 (± 2.0, 1σ)‰/km, consistent with precipitation data and long term observations. MBT/CBT derived soil temperature values based on the relative distribution of microbial tetraether lipids were similar to midsummer temperature observations, displaying an elevational decrease rate of −5.6 (± 1.5, 1σ) °C/km, consistent with regional and global observations.The results indicate that sedimentary lipid δ²H and microbial tetraether temperature estimates captured altitudinal trends in the isotopic composition of precipitation and mean temperature and further support their application in the reconstruction of past climate and surface uplift histories. However, notable differences in isotopic composition and temperature estimates between in situ soils and those with downslope transport of material emphasize the importance of facies analysis when interpreting past systems.     

Occurrence and composition of solid bitumens from the Bulonggoer Devonian paleo-oil reservoir,North Xinjiang,China

The Bulonggoer paleo-oil reservoir (BPR) on the northwest Junggar Basin is the first Devonian paleo-oil reservoir discovered in North Xinjiang, China. Solid bitumens occur within sandstone pores and as veins filling fractures. Samples of both types were analyzed using stable carbon isotope and reflectance measurements, as well as molecular biomarker parameters.The extremely positive δ¹³C values and biomarker indicators of depositional environment/lithology, such as pristane/phytane (Pr/Ph), C₂₉/C₃₀ hopane, diasteranes/regular steranes and dibenzothiophene/phenanthrene ratios, indicate a siliciclastic source for the BPR and their deposition in a highly reducing hypersaline environment. The presence of long chain n-alkanes and abundant tetracyclic diterpanes, C₂₀–C₂₁ tricyclic terpanes and perylene are indicators of higher plant organic matter input. Moreover, the bimodal distribution of C₂₇ > C₂₈ < C₂₉ regular steranes and abundant methyltriaromatic steroids also support a contribution of microalgae as well as higher plants organic matter. The similar molecular composition and thermal maturity parameters indicate that the reservoir and veined solid bitumens were altered from a common paleo-petroleum, which originated from peak oil window matured source rocks.All solid bitumens from the BPR are characterized by relatively low bitumen reflectance values (Rb% < 0.7), suggesting that they were generated from low temperature processes rather than oil thermal cracking. Comparatively, the Rb% values for veined bitumens are higher than reservoir bitumens, indicating that the veined bitumens occurred earlier and experienced higher thermal conditions.     

Laboratory methods for evaluating migrated high molecular weight hydrocarbons in marine sediments at naturally occurring oil seeps

A laboratory study has been conducted to determine the best methods for the detection of C₁₀–C₄₀ hydrocarbons at naturally occurring oil seeps in marine sediments. The results indicate that a commercially available method using n-C₆ to extract sediments and gas chromatography–flame ionization detection (GC–FID) to screen the resulting extract is effective at recognizing the presence of migrated hydrocarbons at concentrations from 50 to 5000 ppm. When non-biodegraded, the amount of oil charge is effectively tracked by the sum of n-alkanes in the gas chromatogram. However, once the charge oil becomes biodegraded, with the loss of n-alkanes and isoprenoids, the amount of oil is tracked by the quantification of the unresolved complex mixture (UCM). Gas chromatography–mass spectrometry (GC–MS) was also found to be very effective for the recognition of petroleum related hydrocarbons and results indicate that GC–MS would be a very effective tool for screening samples at concentrations below 50 ppm oil charge.     

Precise indices based on n-alkane distribution for quantifying sources of sedimentary organic matter in coastal systems

Precise indices based on n-alkane signatures were developed in order to determine the sources and composition of sedimentary organic matter (SOM) in coastal systems. The Arcachon Bay (France), a well-studied temperate lagoon, was used as an example of a complex coastal system sheltering a wide diversity of OM sources. Three main groups of sources were well discriminated from their n-alkane signatures: seagrass (Zostera sp.) produced mainly n-C₁₇, n-C₁₉, n-C₂₁, n-C₂₃ and n-C₂₅ alkanes, algae (Rhodophyta, Chlorophyta) produced n-C₁₅ and n-C₁₇ and the terrigenous input [Quercus sp., Spartina sp. and river suspended particulate OM (SPOM)] was characterized by n-C₂₅, n-C₂₇, n-C₂₉, n-C₃₁ and n-C₃₃. From the above and literature n-alkane fingerprints, we developed a set of indices (n-alkane ratios) to quantify the contribution of these three major sources of the SOM. At the Arcachon Bay scale, they indicated that SOM was composed mainly of seagrass (ca. 53 ± 19%) and terrestrial (ca. 41 ± 17%) material, followed by algae (ca. 6 ± 9%). Moreover, the new n-alkane indices exhibited more relevant spatial patterns than classical ones – the TAR (C₂₇ + C₂₉ + C₃₁/C₁₅ + C₁₇ + C₁₉; terrestrial to aquatic ratio) and the P_aq (C₂₃ + C₂₅/C₂₃ + C₂₅ + C₂₉ + C₃₁; aquatic plant %) – with a greater contribution from marine sources in the central part of the lagoon where a high density of Zostera seagrass was observed. Therefore, the development of precise indices adapted to the local diversity of OM sources is needed when using n-alkanes for quantifying the source composition of SOM in complex coastal systems.     

Scarcity of the C30 sterane biomarker, 24-n-propylcholestane,in Lower Paleozoic marine paleoenvironments

24-n-Propylcholestane (24-npc), a C₃₀ sterane compound derived from sterol precursors which are the major sterol constituents of modern pelagophyte microalgae, occurs in certain Neoproterozoic rocks and oils and throughout the Phanerozoic rock record. This broad distribution leads 24-npc to be widely considered a reliable indicator of open to partially restricted marine depositional conditions for source rocks and oils. Here we report two significant hiatuses in the occurrences of 24-npc in the Lower Paleozoic marine rock record: the first in the Middle–Late Cambrian and the second in the Late Ordovician–early Silurian transition for a range of lithofacies (carbonates and siliciclastic rocks), organic carbon contents (both organic-lean and organic-rich), and paleoceanographic environments (shelf and deeper water marine settings) and observed offshore of two paleocontinents, Laurentia and Baltica. The Ordovician–Silurian gap is at least 9 million years, and possibly up to 20 million years, in duration. Robust older occurrences of 24-npc steranes in some Neoproterozoic rocks and oils suggest that oceanographic conditions in our intervals of Lower Paleozoic time were unfavorable for the proliferation of pelagophyte algae as phytoplankton. Caution should therefore be applied when interpreting a lacustrine versus marine depositional environmental setting for source rocks and oils in these intervals of Early Paleozoic time using lipid biomarker assemblages.     

Organic geochemistry and depositional environment of the Aptian bituminous limestone in the Kale Gümüşhane area (NE-Turkey): An example of lacustrine deposits on the platform carbonate sequence

The Jurassic–Lower Cretaceous aged carbonate sequence is widely exposed in the southern zone of Eastern Pontides. Aptian black bituminous limestone is found in the upper part of this sequence in the Kale area (Gümüşhane). This limestone contains faunal remains (e.g., gastropod, ostracod, characean stems and miliolid type benthic foraminifera) that indicate a freshwater, lacustrine depositional environment.The total organic carbon (TOC) values of the bituminous limestone samples range from 0.11–1.30% with an average TOC value of 0.54%. The hydrogen index (HI) varies from 119–448 mg HC/g TOC (average HI 298 mg HC/g TOC) indicating that the limestone contains gas prone as well as oil prone organic matter. Pyrolysis data prove that the organic matter content in the bituminous limestone consists of Type II kerogen. The average T_max value for bituminous limestone samples is 438 °C (434–448 °C). Bitumen/TOC ratios for bituminous limestone are 0.05 and 0.04. The T_max values and the ratios indicate that the bituminous limestone samples contain early mature to mature organic matter.Analysis of solvent extracts from the two richest bituminous limestones show a predominance of high carbon number (C₂₆–C₃₀) n-alkanes. The Pr/Ph ratio and CPI value are 1.34 and 0.96, respectively. C₂₉ is the dominant sterane, with C₂₉ > C₂₇ > C₂₈. The bituminous limestone samples have low C₂₂/C₂₁ ratios, high C₂₄/C₂₃ tricyclic terpane ratios and very low C₃₁R/C₃₀ hopane ratios (<0.25). These data are consistent with the bituminous limestones being deposited in a lacustrine environment.