Composition Of N-alkanes Research Articles

Distribution and Genesis of Aliphatic Hydrocarbons in Bottom Sediments of Coastal Water Areas of the Crimea (the Black and Azov Seas)

The aim of the article is to assess the level of aliphatic hydrocarbon (AHC) contamination in bottom sediments of the Azov–Black Sea coast of the Crimea, as well as to identify potential sources of its formation. Bottom sediment samples obtained from 19 stations during the research cruise of the R/V “Professor Vodyanitsky” (June 2020) were used as the material for this investigation. Sampling stations were located along the coast of the Crimean Peninsula and the Caucasus coastlines (the Black and Azov Seas). N-hexane extracts of sediments were studied by gas chromatography to determine the AHC amount and composition. It was established that AHC concentrations in the study area varied from 1.30 to 127.8 mg/100 g. Generally, bottom sediments of the Black and Azov Seas were characterized by low AHC contents, while increased AHC contents were found in the outer harbor of Sevastopol and Yalta regions. To identify potential hydrocarbon sources, various hydrocarbon markers were used. In most of the study areas, n-alkane composition was determined by similar sources of inputs and organic compound transformation. At the same time, oil pollution linked with use of fuel was recorded almost everywhere.

Paleoclimate, paleoenvironment, and human impact over the last 400 years based on lipid biomarkers from Lake Höglwörth, Germany

Lipid biomarkers are valuable proxies for reconstructing paleoclimate and paleoenvironmental changes as well as human impact. However, little attention has been paid on evaluating how the combination of biomarkers can be used to reconstruct various aspects of local paleoenvironmental conditions. This study presents a suite of lipid biomarker records from a sediment core from Lake Höglwörth, southern Germany, covering the past 400 years. Compound-specific hydrogen isotopic compositions (δD) of terrestrial n-alkanes (n-C29-alkane) and n-alkanoic acids (n-C30-acid) indicate minor changes in isotopic composition of precipitation. The δD of n-C22-acid is interpreted to record the isotopic composition of the lake water and evaporative enrichment, which drops after 1700 CE, coinciding with the construction of a mill and the related rerouting of a creek into Lake Höglwörth. The δD of n-C25-alkane is also enriched but decoupled from the reconstructed isotopic composition of precipitation and lake water. Therefore, we suggest that δD of n-C25-alkane reflects the leaf water isotopic composition of Sphagnum, which is present in the catchment and undergoes transpirative enrichment. Both short-chain compounds have become more enriched over the last century, maybe related to increasing temperature associated with anthropogenic climate warming. The faecal biomarkers record the changes in human population, partly related to the history of the local Monastery, the World Wars I and II as well as the intensive farming after the mid-20th century. Polycyclic aromatic hydrocarbons (PAHs) reveal a significant change in combustion activities associated with human activities such as the industrial revolution, biomass burning, and environmental cleanup as well as the implementation of emission standards. Our study demonstrates that the combination of plant wax compounds, faecal biomarkers, and PAHs from lacustrine sediment serves as a valuable tool to reconstruct and distinguish various aspects of paleoclimate and paleoenvironmental changes including human impacts.

Impact of paleohydrological conditions on wetland organic carbon accumulation in the monsoon-arid transition zone of North China during the Holocene

Wetlands rich in carbon are important ecosystems for storing organic carbon, with their carbon storage capacity closely linked to water levels. Therefore, it is valuable to explore the relation between paleohydrological conditions and the organic carbon accumulation in carbon-rich deposits. This study examined the total organic carbon concentration and the molecular and carbon isotope compositions of n-alkanes in Ganhai, a dried up lake located in a region transitioning from a monsoon to an arid climate in north China. The results showed that the apparent carbon accumulation rates (CAR) increased as the East Asian summer monsoon intensified (averaged at 26.5 g C m−2 yr−1, 1 σ = 8.6), but decreased when precipitation levels peaked (averaged at 15.8 g C m−2 yr−1, 1 σ = 2.2). The above relation between precipitation and CAR in Ganhai is supported by the correlation analysis (r = −0.35, p = 0.003). This suggests a threshold relation between wetland carbon accumulation and precipitation in this region. The output of a Bayesian multi-source mixing model, based on the molecular and carbon isotope compositions of long-chain n-alkanes, underscores the significant role of aquatic plants in influencing carbon accumulation in Ganhai during the mid-Holocene, with submersed plants dominating during high CAR periods and floating plants being more prevalent during peak precipitation. The study emphasizes the importance of understanding the hydrological threshold for carbon sequestration and vegetation restoration in carbon-rich wetlands.

Stable hydrogen isotope evidence of late-Holocene precipitation variability on the Caribbean slope of the Cordillera Central, Costa Rica

In Central America and the Caribbean, periods of increased aridity that correspond to the Terminal Classic Drought (TCD; 1200–850 cal yr BP) and the Little Ice Age (LIA; 500–100 cal yr BP) have been documented in many paleoclimate records. Compound-specific hydrogen (δDalkane) and carbon (δ13Calkane) isotopic compositions of n-alkanes in lake sediment can be used to interpret changes in paleoprecipitation and terrestrial paleovegetation, respectively. To assess the climate forcing mechanisms that drove the TCD and LIA, we established a multidecadal to centennial-scale late-Holocene reconstruction of precipitation variability and vegetation change at mid-elevation on the Caribbean slope of Costa Rica, developed from new δDalkane, δ13Calkane, and geochemical analyses and previous pollen and microscopic charcoal analyses from a sediment core from Laguna María Aguilar. Laguna María Aguilar is a freshwater lake located at 770 m elevation on the Caribbean slope of the Cordillera Central. During the TCD, δDalkane data for María Aguilar indicate relatively wet conditions compared to the mean δDalkane value for the entire record. Other proxy records for the TCD indicate that the Pacific slope of Costa Rica and sites above 3400 m near the continental divide experienced generally drier conditions than mid- and low-elevations on the Caribbean slope. We conclude that the TCD may have been driven by both Pacific and Atlantic climate-forcing mechanisms. During the LIA, the Laguna María Aguilar δDalkane record indicates an increase in hydroclimate variability, with some of the highest recorded δDalkane values (driest conditions) during the earliest portions of the LIA, but conditions were not persistently dry for the entirety of the LIA. Based on regional paleoclimate records overall, the LIA drought appears to be more clearly expressed on the Caribbean slope than on the Pacific slope of Costa Rica, indicating that the LIA was perhaps driven primarily by Atlantic Ocean conditions and climate dynamics.

Biomarker Hydrocarbons and Carbon Isotopes of Individual n-Alkanes in Paraffin Oils and Bitumens of the Middle Devonian–Lower Frasnian Terrigenous Complex of the Timan–Pechora Basin

Abstract ––The objects of study were bitumens of sedimentary rocks and paraffin oils of the Middle Devonian–lower Frasnian terrigenous complex of the Timan–Pechora basin. We studied the composition of biomarker hydrocarbons and the carbon isotope composition of individual n-alkanes of bitumens from the cores of the wells of the Omra–Lyzha saddle. The results were compared with similar data on the composition of paraffin oils from the south of the Pechora–Kozhva megaswell. The generation potential and thermal maturity of organic matter were studied by the Rock-Eval pyrolysis method. The maturity of organic matter in the rocks of the studied complex in the Omra–Lyzha saddle and the Pechora–Kozhva megaswell corresponds to the oil window. Data on the carbon isotopy of n-alkanes and on the composition of biomarker hydrocarbons do not contradict the possible genetic relationship between paraffin oils and the organic matter of the host sedimentary complex. Both the studied paraffin oils and the rock bitumens contain early eluting rearranged hopanes atypical of oils of other petroliferous complexes and show high contents of n-alkanes relative to iso-alkanes and polycyclic biomarkers. The content of 13C tends to decrease with an increase in the number of carbon atoms in the n-alkane molecule in both oils and bitumen rocks.

Multiple isotopes (C-S-N-H) and bound biomarkers in asphaltenes: New constraints on the classification and genesis of reservoir bitumens from the northwestern Sichuan Basin, South China

Reservoir bitumens in the northwestern Sichuan basin are significant for elucidating the sources and charging history of oil and gas, given their widespread occurrence in multiple strata in the area and abundant biomarkers. The debate regarding the origin and genesis of these bitumens has persisted for a long time, due to severe biodegradation and the development of multiple sets of high maturity source rocks with few biomarkers for oil-source correlation. To resolve these questions, asphaltenes, which are more resistant to biodegradation than free hydrocarbons, were systematically analyzed with the bulk multi-isotopes (C-S-N-H), bound molecules and the carbon isotopic compositions of bound individual n-alkanes. These characteristics were then compared to those of bulk bitumen and free hydrocarbons, leading to three main conclusions. In most samples, relatively abundant 25-norhopanes and 17-nortricylic terpanes were identified along with n-alkanes in free hydrocarbons, suggesting at least two oil charging events. In the samples having free n-alkanes, the carbon isotopic compositions of asphaltene-bound n-alkanes closely resemble those of corresponding free n-alkanes. Moreover, the bulk C-S-N isotopic compositions of asphaltene also approach those of corresponding bulk bitumen. These results suggest that the source of the oil charges occuring at different times are mostly the same for an individual sample, though different bitumen samples may have distinct sources. Free hydrocarbons, including n-alkanes and biomarkers, may have been produced by the secondary cracking of asphaltenes. Second, the integration of bulk C-S-N isotopic compositions of the asphaltenes and bitumens has enabled the studied samples to be classified into four groups. Source facies is the primary control of the distinct isotopic compositions with other factors like biodegradation, thermal maturity and migration having only minor influence. In combination with biomarkers, the organic matter and sedimentary environment of source rocks could be characterized for each group. A careful comparison of the bulk C-S-N isotopic compositions of asphaltenes and bitumens with those previously reported for source rocks (organic C and S and bulk N isotopes) suggests the main source rocks in the Upper Ediacarian-Lower Cambrian Formations, supporting the conclusions of previous studies. Furthermore, those source rocks in much younger formations, such as the Middle Permian as well as the Middle Devonian Formations, may also have contributed significantly to the widespread reservoir bitumens in the region. These findings highlight the usefulness of bulk C-S-N isotopic composition of asphaltenes for distinguishing oils with complex genesis and large gas exploration potential of the Upper Paleozoic source rocks in the region.

CHROMATOMASS SPECTROMETRIC STUDY OF LEAVES OF RUBUS IDAEUS L. AND SORBUS AUCUPARIA L. SOUTH OF THE TOMSK REGION

The features of the distribution of fat-soluble organic compounds in the leaves of deciduous shrubs Rubus idaeus and Sorbus aucuparia growing in identical weather conditions in mixed and pine forests of the southern taiga of Western Siberia are shown. The composition of n-alkanes, saturated and unsaturated fatty acids, n-aldehydes, n-alkane-2-ones, n-alkanols, acyclic isoprenoids, steroids and pentacyclic triterpenoids was studied by chromatomass spectrometry. It was found that the microclimate of pine forest and mixed forest influences the composition of organic compounds in the leaves of single-species plants. In a mixed forest, among acyclic compounds, the total proportion of n-alkanes and the relative content of high-molecular homologues of n-alkanes, n-aldehydes and n-alkane-2-ones in rowan and raspberry leaves were increased. The composition of steroids is dominated by sitosterol, while in the bushes of mixed forest, unlike pine forest, there is a higher proportion of keto-substituted stigmast-4-en-3-one and the hydrocarbon stigmast-3,5-diene. Pine raspberries are distinguished by the presence of cholesterol, lanosterol and lanost-8-en-3-one, an increased content of cycloartenol. The leaves of ash among the pentacyclic triterpenoids identified a- and β-amerins, and the leaves of the raspberry a-, β- and d-amerins, among which in the pine forest increased the proportion a- amerin, and in the mixed forest – d-amerin. Raspberry leaves are dominated by neolup-12-en-3-ol, whereas in the leaves of mountain ash of mixed forest – lupeol, and pine forest – presumably 28-norneogop-18-en-3-ol. It is shown that the distribution of fat-soluble compounds depends not only on the type of plant, but also on the conditions of its growth, which must be taken into account when planning the practical use of plant raw materials.

Leaf wax n-alkane distribution and hydrogen isotopic fractionation in fen plant communities of two Mediterranean wetlands (Tenaghi Philippon, Nisí fen—Greece)

Many continental paleoclimate archives originate from wetland sedimentary sequences. While several studies have investigated biomarkers derived from peat-generating vegetation typical of temperate/boreal bogs (e.g., Sphagnum), only scant information is available on emergent plants predominant in temperate/subtropical coastal marshlands, peri-lacustrine and fen environments. Here, we address this gap, focusing on two wetlands in the Mediterranean (Nisí fen and Tenaghi Philippon, Greece). We examined the concentration, homologue distribution, and hydrogen stable isotopic composition (δ2H) of leaf wax n-alkanes in 13 fen plant species, their surrounding soil, and surface water during the wet growing season (spring) and the declining water table period (summer). Our findings indicate that local graminoid species primarily contribute to the soil n-alkane signal, with a lesser influence from forbs, likely owing to differences in morphology and vegetation structure. The δ2H values of surface and soil water align with local average annual precipitation δ2H, reflecting winter-spring precipitation. Consistently, the average δ2H of local surface, soil, and lower stem water showed negligible evaporative enrichment, confirming minimal 2H-fractionation during water uptake. We find that δ2H values of source water for wax compound synthesis in local fen plants accurately mirror local annual precipitation. Furthermore, despite differences between leaves and lower stems in n-alkane production rates, their δ2H values exhibit remarkable similarity, indicating a shared metabolic substrate, likely originating in leaves. Our net 2H-fractionation values (i.e., precipitation to leaf n-alkanes) align with those in Chinese highlands and other similar environments, suggesting consistency across diverse climatic zones. Notably, our data reveal a seasonal decrease in the carbon preference index (CPI) in plant samples, indicating wax lipid synthesis changes associated with increased aridity. Additionally, we introduce a new parity isotopic difference index (PID) based on the consistent δ2H difference between odd and even n-alkane homologues. The PID demonstrates a strong anticorrelation with plant CPI, suggesting a potential avenue to trace long-term aridity shifts through δ2H analysis of odd and even n-alkane homologues in sedimentary archives. While further development of the PID is necessary for broad application, these findings highlight the intricate interplay between plant physiology, environmental parameters, and sedimentary n-alkanes in unravelling past climatic conditions.

Life-cycle profiling of cuticular hydrocarbons in the cotton bollworm Helicoverpa armigera (Lepidoptera: Noctuidae)

Cuticular hydrocarbons (CHCs) are the main components of the wax layer present on insects’ surface, serving as protective agents against environmental stress and/or as communication signals. It has been documented that the chemical composition of CHCs varies with species and even with developmental stage or sex of the same species. However, studies involving in a life-cycle identification of CHCs are rare. In this work, we attempted to profile the components and relative abundance of CHCs in the cotton bollworm Helicoverpa armigera at all the four developmental stages and in both sexes of pupae and adults. A total of 29 CHCs were putatively identified by gas chromatography-mass spectrometer analysis, including 14 n-alkanes, 4 methyl-branched alkenes and 11 methyl-branched alkanes, with 15 of them being detected at all the four developmental stages. Of the 29 CHCs, the straight-chain alkanes with 27, 29 and 31 carbon atoms were the major CHCs. All three classes of CHCs (n-alkanes, methyl-branched alkanes and methyl-branched alkenes) were found in both larvae and pupae, while no unsaturated hydrocarbons were observed in eggs and adults. Methyl-branched alkanes were the main component found in eggs and adults, while the composition of n-alkanes and methyl-branched alkanes in larvae and pupae varied with ages. Principal component analysis (PCA) revealed that the CHC profiles in larvae and adults changed significantly with ages, while the CHC profiles in early pupae (1-day-old) showed distinct difference from those of late pupae. Furthermore, sexual dimorphism in the CHC profile was observed in mature adults (3-day-old and 5-day-old), with male adults possessing more n-C31 and n-C33, but less 3-MeC29 than females.

Organic Geochemical Evidence for the Formation of Condensate from Coaly Source Rocks in the Wumaying Buried Hill of the Huanghua Depression, Bohai Bay Basin.

Although oil and gas from coaly source rocks have been widely discovered worldwide, the role of oil generated from coal measures in marine-continental coaly deposits during the Carboniferous-Permian period in the Bohai Bay Basin has long been a subject of debate. The recent discovery of a condensate reservoir in the Wumaying buried hill within the Huanghua Depression of the Bohai Bay Basin offers new potential insights into this issue. In this study, we employed organic geochemical methods to explore the possibility of the Carboniferous-Permian coal deposit being a primary source of the condensate. The distribution of light hydrocarbons and the biomarker assemblage indicate that the condensate did not undergo significant secondary alterations such as thermal cracking, gas invasion fractionation, or biodegradation. The hydrocarbon generation potential of the Carboniferous-Permian coaly source rocks suggests that they could be an important contributor to the formation of condensate. High pristine/phytane ratios (1.0-7.5), an abundant presence of benzene series, and the dominance of C29 steranes (>50%) within the condensate could be indicative of coaly organic matter. These features are comparable to those found in coaly source rocks. Moreover, the stable carbon isotopic compositions of n-alkanes in the condensate, ranging from -26.0 to -30.0‰, correlate well with those from coaly mudstone (-25.4 to -30.0‰). This suggests that the condensate of the Wumaying buried hill may predominantly originate from the Carboniferous-Permian coaly mudstone. When integrated with the geological background, the results distinctly demonstrate that the Carboniferous-Permian coaly source rocks have significantly contributed to the formation of the condensate reservoir in the Wumaying buried hill. This provides an essential reference for future exploration of oil and gas resources derived from the carboniferous-Permian coaly source rocks in the Bohai Bay Basin.

Decreased Westerly moisture transport leads to abrupt vegetation change in northern Central Asia during late MIS3: Evidence from Zeketai Loess, Ili Basin

Moisture transportation to (semi-)arid Central Asia is influenced by the interplay of multiple atmospheric circulation patterns. The mechanism underlying the hydroclimate evolution in CA has recently received increasing attention. In northeastern CA, most of the precipitation falls in summer, counter to other westerly-dominated regions of CA where precipitation maximizes in boreal winter. The marine isotope stage (MIS) 3 offers a unique opportunity to examine the mechanisms driving hydroclimate variations during warm periods of the ice age in the CA. However, due in part to reliable proxies for reconstruction, the hydroclimate and vegetation change during MIS3 in northeastern CA have not been well studied. Here, we use grain size and magnetic susceptibility data from the Zeketai loess profile to reconstruct historical shifts in precipitation patterns during MIS3 in the Ili Basin from arid Central Asia (ACA). Notably, abrupt changes around 35 ka are evident in the grain size and magnetic susceptibility records, reflecting a transition to reduced wind intensity and increased aridity. Subsequent analysis of plant leaf waxes (n-alkanes), hydrogen isotopic composition of n-alkanes (δDn-alkane), and stable carbon isotope ratios of total organic carbon (δ13Corg) within the loess profile indicates a concurrent shift towards more shrubs, aligning with reduced moisture availability. The δ13Corg record further elucidates that during MIS3, the Ili Basin predominantly harbored C3 vegetation. However, the alteration in δ13Corg and δDn-alkane to more positive values at approximately 35 ka substantiates the transition to more drought-resistant vegetation. Furthermore, we link the paleo-hydroclimate variations to the decrease in solar radiation and the strengthening of the Atlantic Meridional Overturning Circulation (AMOC) and Siberian High during late MIS3. This joint influence weakens the Westerly winds and subsequently diminishes the conveyance of moisture to CA.

Characteristics of n-alkyl lipids in cultivated Sphagnum and their preservation potential in the topsoil of Sphagnum farmlands in southwest China

Sphagnum, a crucial peat-forming plant, is essential for sustaining the ecosystem and counteracting climate change. In recent years, attempts have been made to cultivate Sphagnum commercially to reduce the environmental impacts of harvesting the natural Sphagnum. However, research on the distribution of lipids in cultivated Sphagnum and their potential for preservation potential in the underlying soil is still limited. This study examined the distribution of n-alkyl lipids and the carbon isotope composition of n-alkanes in both natural and cultivated Sphagnum, as well as the underlying topsoil in southwestern China. Results show that the distributions of n-alkyl lipids in the cultivated Sphagnum are similar to those of the natural Sphagnum in the same region. Additionally, the δ13C values of mid-chain n-alkanes (C23 and C25) in the cultivated Sphagnum are significantly negative compared to those of long-chain homologs (C29 and C31; one-way ANOVA, p < 0.05), indicating that symbiotic methanotrophs are relatively active in the cultivated Sphagnum. Furthermore, the n-fatty acids and n-alkan-2-ones in the topsoil are mainly imported from Sphagnum, while the n-alkanes in the topsoil may originate from both Sphagnum and vascular plants. These findings contribute to a better understanding of the ecological benefits of Sphagnum cultivation and the contribution and fate of Sphagnum-derived carbon in soil profiles.

HYDROCARBON CONTAMINATION IMPACT ON SANDY SOILS WITHIN THE DZUNBAYAN OIL FIELD (EASTERN MONGOLIA)

The data are presented on the particle-size distribution, content of hydrocarbons, n-alkanes in their composition and the number of microorganisms in the soils of Dzunbayan oil production area (Mongolia, the Eastern Gobi desert steppe). The soils studied are characterized by the dominance of sand and fluid fraction (99.50–99.8%) with particles of 2–20 μm. The soils show alkaline reaction (pH 8.2–8.7), they are slightly saline in the control areas and highly saline (water extract salinity 0.13–2.34‰) near the production well. The content of petroleum hydrocarbons (HC) in soils of the study area varied from 9 to 60 mg/kg, with a maximum near the well. The study of the molecular composition of n-alkanes revealed the dominance of long-chain homologues (66.3–79.2% of the total n-alkanes), occurring at various stages of physicochemical and microbiological weathering. According to a number of features, the microbial community of soils is characterized by a high degree of adaptation to the conditions of the arid zone, salinity, and high pH values; at the same time, these conditions limit the development of typical representatives of soil microbiocenoses, i.e., actinomycetes and, to a greater extent, microscopic fungi. The total number of heterotrophic bacteria (HBGs) in the studied soil samples varied within 1.22–3.49 million CFU/g of soil. The proportion of oil-oxidizing bacteria (NOB) was 12.6–18.9% OBA, which corresponded to the high adaptive capacity of the community to hydrocarbons. Specific climatic conditions, features of soil composition, as well as oil with a predominance of heavy paraffin fractions of the Dzunbayan deposit, characterize the low potential ability of soils to self-purify under the oil pollution.

Compound-specific carbon isotope measurements of individual lipid biomarkers from immature Ediacaran rocks of Baltica

Compound-specific carbon isotope ratios (CSIA) were measured for a suite of lipid biomarker compounds extracted from immature, late Ediacaran sedimentary rocks from drill cores sampled across Baltica. Using a newly developed picomolar‐scale CSIA (pico‐CSIA) method, we measured carbon isotope compositions of the abundant n-alkanes and hopanes, as well as C29 sterane, pristane, and phytane. Total organic carbon (TOC) of the Kotlin Regional Horizon in Baltica (Saint Petersburg area, Utkina Zavod drill core), from a low-salinity coastal environment, is consistently enriched in 13C by up to 10‰, compared to that for Redkino and Kotlin marine rocks from other locations in Baltica. This 13C enrichment is also recorded by the n-alkanes, hopanes, phytane, and C29 sterane. In all locations, the δ13C values of the C29 sterane are within 2‰ of the bacterial hopane δ13C values and within 0.7‰ of δ13CTOC, suggesting that the abundant hopanes within these sediments could be derived from RuBisCO Calvin-Benson-Bassham pathway-utilizing organisms, as well as from bacterial heterotrophs. Since δ13Clipid signature tracks δ13CTOC values for the Kotlin Regional Horizon samples from Utkina Zavod location, the significant 13C enrichments in this interval reflect either the δ13C composition of DIC used for autotrophy or a muted magnitude of carbon isotope fractionation during lipid biosynthesis, but are not due to enhanced preservation of organic compounds and geopolymers derived from 13C-enriched biochemicals. Pico-CSIA and biomarker data provide evidence for both regional environmental heterogeneity and secular changes in carbon cycling during deposition of sediments of the Kotlin and Redkino Regional Horizon intervals.

Controls on hydrocarbon accumulation in the pre-rift paleozoic and late syn-rift cretaceous sandstones in PTAH oil field, north Western Desert, Egypt: Insights from seismic stratigraphy, petrophysical rock-typing and organic geochemistry

North Western Desert (NWD) of Egypt is one of the most petroliferous provinces in North Africa. Mesozoic rift basins in the NWD host several active petroleum systems in their syn- and post-rift sedimentary successions. Also, numerous oil reserves were recently discovered in the pre-rift Paleozoic reservoirs. However, the genetic link between the pre-rift hydrocarbon plays and the syn- and post-rift accumulations is still ambiguous. Additionally, controls on distribution of the optimum rock types in the pre-rift reservoirs need further investigation. Therefore, this study integrates geochemical, seismic-stratigraphic, and petrophysical approaches to better understand these issues based on oil, seismic, and well data retrieved from the Paleozoic pre-rift “Shiffah” and the Cretaceous late syn-rift “Alam El Bueib (AEB)” sandstones in PTAH oil Field in the NWD.Oil retrieved from Shiffah and AEB pay zones displays a similar n-alkane composition dominated by cycloalkanes and nC20+ alkanes. The oil samples retain biomarker signatures of pre-Cretaceous terrestrial organofacies where oleanane is absent, isoprenoid ratio (prestane/phystane) is high (>5) and C29/C27 steranes is greater than 1.5. Shiffah and AEB oils have a common source rock and display compositional characteristics similar to NWD oils derived from the Middle Jurassic Khatatba Formation fluvio-deltaic organofacies. Deep-seated rift-faults cross-cutting the entire syn- and pre-rift successions provide the paths for the upward and downward hydrocarbon migration from Khatatba organofacies to AEB and Shiffah sandstones, respectively. Distribution of the reservoir rock types (RRTs) controlled the thickness of the hydrocarbon column. Reservoir quality decreases from RRTI to RRTIII. RRTI rocks occur in the Shiffah fluvial basin-fill facies, whereas the best RRTs in AEB are classified as RRTII and are exclusively associated with the prograding deltaic facies. Correlation between seismic facies and RRT allows the prediction of their lateral and vertical distribution. Our results highlight existence of excellent reservoir rock types in the pre-rift succession connected with the Jurassic kitchen which charged the entire syn- and post-rift reservoirs.

Differential effects of clay mineralogy on thermal maturation of sedimentary n-alkanes

Clay minerals serve as important catalysts for the degradation of a range of biomolecules during diagenesis, yet their effects are seldom considered when interpreting organic molecular and isotopic data in the context of paleoenvironmental reconstruction. We investigated the thermal maturation of immature sedimentary organic matter in the presence of two clay minerals (kaolinite and montmorillonite) using a series of laboratory-based anhydrous pyrolysis experiments. Organic matter was extracted from a modern terrestrial sediment, mixed with each clay mineral, and heated at 100–300 °C for up to 30 days – in this way, initial organic matter was identical in each system. Abundances, molecular distributions, and paired compound-specific stable isotopic compositions (δDn-alkane and δ13Cn-alkane) of n-alkanes were measured as a function of heating time. For both kaolinite and montmorillonite amended experiments, the shifts in molecular distributions are highly controlled by significant secondary production of n-alkanes from molecularly large lipid precursors, as evidenced by significant increases in the total amount of n-alkanes accompanying increased thermal maturation. Significant decreases in carbon preference index (CPI) are observed before minor decreases in average chain length (ACL), leading to behavior in CPI-ACL space that is fundamentally different from identical systems free of clay minerals. Furthermore, distinct distributions of secondary n-alkanes between the clay mineral systems indicate differential mechanisms and sites of precursor degradation. In the presence of clay minerals, δ13Cn-alkane of immature bituminous organics initially decreases with increasing thermal maturation, opposite most data reported from experimental alteration of relatively mature sedimentary matter. This shift is similarly driven by secondary production of n-alkanes, arising from kinetic fractionation associated with preferential cleavage of 12C12C bonds from parent molecules – the kinetics of this process vary per clay mineralogy but are controlled by the same process. Conversely, we see an enrichment in δDn-alkane with increasing maturation, indicating control of the two isotopic systems by separate mechanisms. Moreover, kaolinite and montmorillonite exhibit differential control on δDn-alkane, leading to separate domains in dual isotopic space. Overall, the changes in δ13Cn-alkane and δDn-alkane are relatively small over the timescales studied, even at temperatures as high as 300 °C (less than ∼0.6–1‰ for δ13Cn-alkane and ∼8–15‰ for δDn-alkane). Considering these factors on a geological timescale, variations in clay mineralogy through a buried sedimentary sequence may impart matrix effects on molecular and isotopic signatures that can bias interpretation of paleoenvironmental conditions.

Molecular Composition, Seasonal Variation, and Size Distribution of n-Alkanes, PAHs, and Saccharides in a Medium-Sized City of Guanzhong Plain, Northwest China: Evaluation of Control Measures Executed in the Past Decade.

Baoji is a medium-sized city in the Guanzhong Plain of northwest China. The compositions of three important organic groups, namely n-alkanes, polycyclic aromatic hydrocarbons (PAHs), and saccharides in atmospheric aerosol with different aerodynamic diameters in power were determined. Both seasonal and daily trends of the target organic chemical groups were demonstrated. The concentration levels of total quantified n-alkanes and saccharides in total suspended particles (TSP) in winter were 541 ± 39 and 651 ± 74 ng·m-3, respectively, much higher than those of the other three seasons. A high total quantified PAHs concentration level of 59.6 ± 6.4 ng·m-3 was also seen in wintertime. n-Alkanes showed a bimodal percent distribution in spring, autumn, and winter. Two peaks were found with the particle sizes of 0.7 μm < Dp < 2.1 μm and 3.3 μm < Dp < 4.7 μm, respectively. In summer, a unimodal was seen with a peak of 4.7 μm < Dp < 5.8 μm. Dehydrated saccharides and PAHs present a unimodal size distribution peaking at the aerodynamic diameters of 0.7 µm < Dp < 2.1 µm. In contrast to glucose and fructose, they mainly exist in the coarse mode particles and have the highest concentrations at aerodynamic diameters of 4.7 µm < Dp < 9.0 µm. The geometric mean diameters (GMD) of n-alkanes and saccharides of the fine particles in winter were higher than in the other seasons. Compared with the data in 2008, the fossil fuel-derived n-alkanes and PAHs in winter decreased by nearly an order of magnitude in 2017. Both the carbon preference index (CPI) of n-alkanes and the diagnostic ratios of PAHs suggest that coal combustion and vehicle exhaust were the major pollution sources of the organic groups in the two decades. It should be noted that the contribution of traffic emissions greatly increased from 2008 to 2017, consistently with a large raise of registered vehicles in Baoji city. The overall results confirm that the control measures conducted by the local government in the recent decade mitigated the air pollution in this city.

Geochemistry of hydrocarbons-biomarkers and carbon isotopes of organic matter in the Domanik Deposits of the Timan-Pechora Basin

It has been established that the average values of some hydrocarbons biomarker coefficients of bitumens from the Domanik deposits and oils from the Domanik–Tournaisian complex coincide. These are the proportions of C27–C29 steranes, tri-/pentacyclanes ratio, and coefficients 2 × С17/С16 + С18 and 2 × С27/С26 + С28 calculated from n-alkane composition. Such indicators as the Pr/Ph, (Pr + Ph)/(n‑C17 + n‑C18), dia-/reg-steranes, and the sterane/hopane ratios in oils are slightly lower than in the bitumen. The average values of δ13C in asphaltene, resin, aromatic hydrocarbons, and aliphatic hydrocarbons fractions from oils of the Domanik genotype and in the studied bitumens are similar. The carbon isotope composition of asphaltenes in oils is depleted in 13С compared to those of resins and aromatic hydrocarbons, and vice versa in bitumens. A heterogeneous composition of the bacterial flora in the sediments of the Domanik Sea is suggested. In some places, species with high concentrations of diplopterol or hexafunctional bacteriohopanes likely dominated over bacteriohopantetrol.

Quantitative reconstruction of the relative humidity by a coupled δ18O-δ2H approach during the Younger Dryas in central China

Paleoclimate records in central China reveal asynchronous hydroclimate changes to those from both northern and southern China during the Holocene. Whether such a spatial mode works for the Younger Dryas event (YD), a prominent abrupt climate change during the transition from the last glacial to the Holocene, is poorly constrained by quantitative records. In this study, we apply the novel coupled hydrogen isotope composition of leaf wax n-alkanes and oxygen isotope of hemicellulose (δ2Hn-alkane-δ18Osugar) paleohygrometer approach to reconstruct the paleo relative humidity (RH) on a peat layer spanning 13.1–10.0 cal ka BP in the Dajiuhu peatland, central China. The coupled δ2Hn-alkane-δ18Osugar approach reveals that the RH was relatively low in the period of 12.7–12.1 cal ka BP (RH avg. 79%, 1σ 4.9%) and then turned to relatively high values during 12.1–11.7 cal ka BP (RH avg. 88.6%, 1σ 3.9%). A dry interval happened from the end of the YD to 11.3 cal ka BP (RH< 80%). A general wetting trend during the YD period in central China contrasts with the prevailing drying in northern China and maybe also in southern China. The occurrence of a wetting trend during the YD period in central China probably results from the interplay between the westerlies and the East Asian summer monsoon under a context with weak summer monsoon intensity.

Hydrocarbons in the water and bottom sediments of Sivash Bay (the Azov Sea) during its salinization.

Sivash Bay is a unique hypersaline lagoon located in the northern part of the Crimean Peninsula. In 2014, due to political events in connection with the closure of the North Crimean Canal, the inflow of fresh water to Sivash Bay has been significantly reduced. As a result, there has been a steady increase in salinity since 2014 to the present. The main purpose of this work was to determine the spatial distribution and qualitative composition of hydrocarbons (aliphatic hydrocarbons, n-alkanes, polycyclic aromatic hydrocarbons) in the water and bottom sediments of the hypersaline Sivash Bay under increasing water salinity. The analysis of the physico-chemical parameters of Sivash Bay in 2020 showed the continued salinization and change of physico-chemical conditions of the lagoon. At the same time, spatially, the change in salinity affected only the total content and qualitative composition of hydrocarbons in the water. The content of the studied classes of hydrocarbons in the bottom sediments did not demonstrate a reliable correlation with the concentration of salts. There was also no statistically significant dependence of Eh and pH of bottom sediments on salinity. In accordance with the composition of n-alkanes and polyaromatic hydrocarbons, as well as on the basis of PCA analysis, it is possible to make a conclusion on natural, mainly autochthonous, sources of this class of substances and low toxicity of bottom sediments of the bay. Low concentrations and composition of hydrocarbons indicate an insignificant input of pollutants of anthropogenic origin in Sivash Bay during its salinization.